U.S. patent application number 17/098817 was filed with the patent office on 2021-05-13 for systems and methods for the oxidative coupling of methane.
The applicant listed for this patent is Lummus Technology LLC. Invention is credited to Joel CIZERON, Rong FAN, David C. GRAUER, Satish LAKHAPATRI, Franciscus J.A. MARTENS, Jarod McCORMICK, Guido RADAELLI, Daniel ROSENBERG, David SHERIDAN, Gregory J. TURK, Fabio R. ZURCHER.
Application Number | 20210139392 17/098817 |
Document ID | / |
Family ID | 1000005355316 |
Filed Date | 2021-05-13 |
United States Patent
Application |
20210139392 |
Kind Code |
A1 |
CIZERON; Joel ; et
al. |
May 13, 2021 |
SYSTEMS AND METHODS FOR THE OXIDATIVE COUPLING OF METHANE
Abstract
The present disclosure provides systems and methods for
producing olefins via an oxidative coupling of methane (OCM)
process. The systems and methods may comprise the use of a staged
process comprising at least one non-adiabatic section that is in
thermal communication with a heat transfer medium and at least one
substantially adiabatic section. The systems and methods may also
comprise the use of a diluent stream which may improve methane
conversion in an OCM reactor and an ethylene/ethane ratio in a
post-bed cracking unit. The methods and systems may further
comprise injecting oxygen (O.sub.2) and a paraffin into a gas
stream containing a radical transfer agent to provide a reaction
mixture. The reaction mixture may be held in a vessel for a time
period greater than an auto-ignition delay time (AIDT), such that
the reaction mixture may ignite to liberate heat and convert to a
product mixture comprising olefins.
Inventors: |
CIZERON; Joel; (Redwood
City, CA) ; SHERIDAN; David; (Menlo Park, CA)
; TURK; Gregory J.; (Oakland, CA) ; LAKHAPATRI;
Satish; (San Francisco, CA) ; FAN; Rong;
(Castro Valley, CA) ; RADAELLI; Guido; (Pleasant
Hill, CA) ; MARTENS; Franciscus J.A.; (Calgary,
CA) ; McCORMICK; Jarod; (Palo Alto, CA) ;
GRAUER; David C.; (San Francisco, CA) ; ZURCHER;
Fabio R.; (Brisbane, CA) ; ROSENBERG; Daniel;
(San Francisco, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Lummus Technology LLC |
The Woodlands |
TX |
US |
|
|
Family ID: |
1000005355316 |
Appl. No.: |
17/098817 |
Filed: |
November 16, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16030298 |
Jul 9, 2018 |
10836689 |
|
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17098817 |
|
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|
|
62557597 |
Sep 12, 2017 |
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62530639 |
Jul 10, 2017 |
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62529942 |
Jul 7, 2017 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 2208/00911
20130101; B01J 2208/0053 20130101; B01J 8/025 20130101; B01J
2208/00212 20130101; B01J 2208/00548 20130101; B01J 2208/00017
20130101; B01J 19/242 20130101; B01J 2219/00788 20130101; B01J
12/007 20130101; B01J 2208/00539 20130101; C07C 2/84 20130101; B01J
8/06 20130101; B01J 8/067 20130101; C07C 2521/04 20130101; B01J
2219/0079 20130101; B01J 2208/025 20130101; B01J 2208/021 20130101;
C07C 2521/06 20130101; B01J 19/0093 20130101; B01J 8/0415 20130101;
C07C 2523/10 20130101; C07C 2523/02 20130101; B01J 2208/00495
20130101 |
International
Class: |
C07C 2/84 20060101
C07C002/84; B01J 8/02 20060101 B01J008/02; B01J 19/00 20060101
B01J019/00; B01J 8/06 20060101 B01J008/06; B01J 8/04 20060101
B01J008/04; B01J 12/00 20060101 B01J012/00; B01J 19/24 20060101
B01J019/24 |
Claims
1. A method for producing an olefin, the method comprising: (a)
producing a gas stream comprising methane (CH.sub.4), oxygen
(O.sub.2), and a diluent; and (b) passing the gas stream over an
oxidative coupling of methane (OCM) catalyst at a pressure of at
least 2 bar(g) to convert at least some of the CH.sub.4 into
hydrocarbon compounds having two or more carbon atoms (C.sub.2+
compounds), wherein a ratio of diluent molecules to carbon atoms in
the gas stream is at least 0.1:1.
2. The method of claim 1, wherein the diluent comprises water
(H.sub.2O).
3. The method of claim 1, wherein the diluent comprises carbon
dioxide (CO.sub.2).
4. The method of claim 1, wherein the diluent comprises H.sub.2O
and CO.sub.2.
5. The method of claim 1, wherein the ratio of diluent molecules to
carbon atoms in the gas stream is at least 0.5:1.
6. The method of claim 1, wherein the ratio of diluent molecules to
carbon atoms in the gas stream is at most 20:1.
7. The method of claim 1, wherein the ratio of diluent molecules to
carbon atoms in the gas stream is from 0.1:1 to 5:1.
8. The method of claim 1, wherein the pressure is at least 4
bar(g).
9. The method of claim 1, wherein the pressure is from 2 bar(g) to
10 bar(g).
10. A method for producing ethylene, the method comprising: (a)
injecting an oxygen stream comprising oxygen (O.sub.2), a methane
stream comprising methane (CH.sub.4), and a diluent stream
comprising water (H.sub.2O), carbon dioxide (CO.sub.2), or both
H.sub.2O and CO.sub.2, into a reactor containing an oxidative
coupling of methane (OCM) catalyst to produce an OCM effluent gas
containing a diluent, wherein at least one of: (i) at least 20 mol
% of the streams injected into the reactor is from the diluent gas
stream; (ii) a methane conversion is at least about 10%; or (iii)
an outlet temperature of the reactor is at least 800.degree. C., is
satisfied; and (b) injecting the OCM effluent gas and an ethane
stream containing ethane into a post bed cracking (PBC) unit,
wherein the PBC unit converts at least a portion of the ethane in
the OCM effluent gas and the ethane stream to ethylene, thereby
generating a PBC effluent stream having an ethylene-to-ethane ratio
greater than 3:1.
11. The method of claim 10, wherein at least 20 mol % of the gas
streams injected into the reactor is from the diluent gas stream
and the outlet temperature of the reactor is at least 800.degree.
C.
12. The method of claim 10, wherein the reactor containing the OCM
catalyst and the PBC unit are contained in a single vessel.
13. The method of claim 10, further comprising mixing the oxygen
stream and the diluent stream to produce a diluted oxygen stream,
and injecting the diluted oxygen stream into the reactor containing
the OCM catalyst.
14. The method of claim 13, wherein the diluted oxygen stream is
injected into the reactor containing the OCM catalyst downstream of
the methane stream.
15. The method of claim 10, further comprising generating the
diluent stream by directing a stream containing H.sub.2O to a heat
exchanger that is in thermal communication with the OCM effluent
gas to produce a steam stream and directing at least a portion of
the steam stream as a portion of the diluent stream into the
reactor containing the OCM catalyst.
16. The method of claim 15, wherein the heat exchanger is
integrated with the reactor.
17. The method of claim 15, wherein the reactor containing the OCM
catalyst, the heat exchanger, and the PBC unit are contained in a
single vessel.
18. A system for producing ethylene comprising: (a) an oxidative
coupling of methane (OCM) reactor comprising an OCM catalyst that
facilitates an OCM reaction, the OCM reactor configured to receive
an oxidant stream comprising oxygen (O.sub.2), a methane stream
comprising methane (CH.sub.4), and a diluent stream comprising
water (H.sub.2O), and to permit at least a portion of the CH.sub.4
and the O.sub.2 to react in the OCM reaction to yield an OCM
effluent stream; (b) a heat exchanger downstream of and in thermal
and fluid communication with the OCM reactor, wherein the heat
exchanger is configured to receive a stream containing H.sub.2O and
produce a steam stream by exchanging heat with the OCM effluent
stream and to direct at least a portion of the steam stream into
the OCM reactor as a portion of the diluent stream; and (c) a
post-bed cracking (PBC) unit downstream of and in fluid
communication with the heat exchanger, wherein the PBC unit is
configured to receive the OCM effluent stream and a stream
comprising ethane and to convert at least some ethane to ethylene,
thereby generating a PBC effluent stream comprising ethylene.
19. The system of claim 18, further comprising a mixer upstream of
and in fluid communication with the OCM reactor, wherein the mixer
is configured to receive and mix the oxidant stream and the diluent
stream to produce a diluted oxygen stream that is injected into the
OCM reactor.
20. The system of claim 18, wherein the OCM reactor, the heat
exchanger, and the PBC unit are contained in a single vessel.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Non-Provisional
patent application Ser. No. 16/030,298, filed on Jul. 9, 2018,
which claims the benefit of U.S. Provisional Patent Application No.
62/529,942, filed on Jul. 7, 2017, U.S. Provisional Patent
Application No. 62/530,639, filed on Jul. 10, 2017, and U.S.
Provisional Patent Application No. 62/557,597, filed on Sep. 12,
2017, each of which is entirely incorporated herein by reference
for all purposes.
BACKGROUND
[0002] Olefins are an important product within the petrochemical
industry. In order to produce olefins, various processes can be
used. Some of these processes may include cracking of naphtha,
cracking of ethane or propane, and oxidative coupling of methane.
The oxidative coupling of methane (OCM) process is a way to
generate olefins, including ethylene and propylene, from methane.
The OCM process may utilize an OCM catalyst that is held within an
OCM reactor. Methane and oxygen may flow through the OCM reactor to
produce higher hydrocarbon products.
SUMMARY
[0003] Recognized herein is the need for novel and more efficient
reactors, processes, and methods for producing olefins from
methane. The present disclosure describes methods and systems for
conducting an oxidative coupling of methane (OCM) process by
controlling various parameters associated with the OCM reactor. In
some aspects of the present disclosure, incorporation of the OCM
methods within an integrated process is provided.
[0004] The high temperature requirements, fast kinetics, and highly
exothermic nature of the oxidative coupling of methane reaction may
cause it to be a difficult reaction to control. In order to improve
the process, it may be desirable to control some process
variables.
[0005] The process variables may include the temperature/pressure
of the OCM reactor effluent gas, conversion of methane and
selectivity for olefin. Some or all of these parameters may be
connected, however with the proper reactor and process design, they
can be controlled and optimized. By utilizing a reactor that
comprises substantially adiabatic and non-adiabatic sections, many
benefits can be achieved. Additionally, special control over feed
injection (including such as gas velocity and contact time) can
award superior reactor and process performance.
[0006] For a packed bed that is substantially adiabatic, the
temperature profile of the process gas through the bed may be
determined primarily by the relative concentrations of the feed
gases and the inherent thermodynamics of the oxidative coupling of
methane. However, using a staged system that comprises at least one
substantially adiabatic section and at least one non-adiabatic
section may add another dimension of control. By removing heat from
the reaction at some points within the reactor, and allowing the
reaction enthalpy to heat the process gas in others, a high level
of control over the temperature profile of the reactor can be
achieved.
[0007] The section or sections of the reactor that are
substantially adiabatic may be insulated, or may be in thermal
isolation from a heat transfer medium, while the non-adiabatic
section or sections may be in thermal communication with a heat
transfer medium. The use of a heat transfer medium may enable both
an improved control over the temperature profile of the bed as well
as heat integration in the process. The hot heat transfer medium
may be used to preheat the feed streams, heat process gas in
another location in a plant, or to generate electricity in a heat
engine. The heat transfer medium may be water, or it may be a
liquid with a high heat capacity, such as a molten salt.
[0008] Control of the location of feed component injection may be
another way to manipulate the process variables. If a reactor
comprises a number of tubes, then smaller concentric tubes of
variable length can be used to add reactants in through the length
of the reactor tube. A diffuser tube, comprising a tube with
perforations that allow gas to escape downward along the tube
length, can be an effective way to control the injection of various
components. Components including methane, ethane, and oxygen can be
injected into the reactor tube using diffuser tubes.
[0009] An aspect of the present disclosure provides a method for
producing an olefin, the method comprising: (a) injecting a feed
stream comprising oxygen (O.sub.2) and methane (CH.sub.4) into a
non-adiabatic section of a reactor, which non-adiabatic section is
in thermal communication with a heat transfer medium and comprises
an oxidative coupling of methane (OCM) catalyst that facilitates an
OCM reaction, wherein a maximum temperature within the
non-adiabatic section is less than about 1,000.degree. C. and heat
generated from the OCM reaction is at least partially transferred
to the heat transfer medium to produce an intermediate gas stream
that contains at least about 1 mol % of the O.sub.2; and (b)
injecting the intermediate gas stream into a substantially
adiabatic section of the reactor, wherein at least one of (i) a
difference between a time when the intermediate gas stream exits
the non-adiabatic section and a time when the intermediate gas
enters the substantially adiabatic section is less than about 50
milliseconds (ms), (ii) an effluent gas at an outlet of the
substantially adiabatic section contains less than about 500 parts
per million (ppm) O.sub.2, and (iii) a temperature at the outlet of
the substantially adiabatic section is at least about 880.degree.
C., is satisfied.
[0010] In some embodiments, at least two of the (i)-(iii) are
satisfied. In some embodiments, all three of the (i)-(iii) are
satisfied. In some embodiments, the method further comprises: (i)
injecting an oxygen stream containing oxygen (O.sub.2) and a
methane stream containing methane (CH.sub.4) into a mixer at a
temperature of less than about 450.degree. C. and a pressure less
than about 10 bar (gauge, "g") to produce a mixed gas stream; and
(ii) increasing a temperature of the mixed gas stream to at least
about 450.degree. C. by putting the mixed gas stream into thermal
communication with the heat transfer medium to produce the feed
stream. In some embodiments, the method further comprises
preheating a stream containing methane to a temperature of at least
about 500.degree. C. to produce a preheated methane stream. In some
embodiments, the method further comprises mixing the preheated
methane stream with a stream containing O.sub.2 to produce a
mixture having a temperature that is less than about 600.degree. C.
In some embodiments, a temperature of the stream containing O.sub.2
is less than about 200.degree. C. In some embodiments, the method
further comprises flowing the mixture over an OCM catalyst to
produce the feed stream. In some embodiments, the method further
comprises flowing the mixture over an inert packing to produce the
feed stream. In some embodiments, the inert packing comprises
alumina (Al.sub.2O.sub.3), silica (SiO.sub.2), Fe.sub.2O.sub.3,
MgO, Na.sub.2O, or another metal oxide. In some embodiments, the
heat transfer medium is a molten salt. In some embodiments, the
molten salt is used to increase the temperature of the mixed gas
stream. In some embodiments, a temperature of the molten salt, when
in thermal communication with the mixed gas stream, is at least
about 500.degree. C. In some embodiments, the molten salt flows
countercurrent to the mixed gas stream in the non-adiabatic
section. In some embodiments, the heat transfer medium is liquid
water. In some embodiments, the liquid water is at a temperature of
at least about 150.degree. C. In some embodiments, the heat
transfer medium is steam. In some embodiments, the method further
comprises injecting ethane into the reactor. In some embodiments, a
stream containing the ethane is injected into the reactor
downstream of where the oxygen and methane are injected. In some
embodiments, the stream containing the ethane is injected using a
diffuser tube. In some embodiments, the ethane is injected into the
substantially adiabatic section of the reactor. In some
embodiments, the method further comprises injecting propane into
the reactor. In some embodiments, the propane is injected into the
substantially adiabatic section of the reactor. In some
embodiments, the method further comprises injecting an effluent of
the non-adiabatic section into a post bed cracking unit. In some
embodiments, the post bed cracking unit does not contain an OCM
catalyst. In some embodiments, the post bed cracking unit converts
ethane to ethylene. In some embodiments, the method further
comprises injecting an additional stream comprising ethane into the
post bed cracking unit. In some embodiments, the O.sub.2 is
injected downstream of where the methane is injected. In some
embodiments, the O.sub.2 is injected using a diffuser tube. In some
embodiments, the O.sub.2 and ethane are injected into the
non-adiabatic section of the reactor downstream of where the
methane is injected. In some embodiments, the O.sub.2 and the
ethane are injected using concentric diffuser tubes. In some
embodiments, the method further comprises transferring heat from
the heat transfer medium to a steam superheater to produce a stream
containing superheated steam. In some embodiments, the steam
superheater raises a temperature of steam. In some embodiments, a
steam enters the steam superheater at a temperature of at least
about 150.degree. C. In some embodiments, the steam exiting the
steam superheater has a temperature of at least about 400.degree.
C. In some embodiments, the method further comprises injecting the
stream containing superheated steam into a unit that produces
electricity. In some embodiments, the unit is a steam turbine. In
some embodiments, the non-adiabatic section comprises at least
about 10 tubes. In some embodiments, a pressure drop across each
tube is less than about 3 bar(g). In some embodiments, each tube
has a diameter that is greater than about 0.75 inches and less than
about 2.25 inches. In some embodiments, each tube has a length that
is greater than about 4 feet and less than about 12 feet. In some
embodiments, a gas velocity in each tube is greater than about 3
meters per second (m/s) and less than about 10 meters per second
(m/s). In some embodiments, a pressure of the gas in each tube is
greater than about 4 bar(g) and less than about 10 bar(g).
[0011] Another aspect of the present disclosure provides a method
for producing ethylene, the method comprising: (a) injecting an
oxygen stream containing oxygen (O.sub.2), a methane stream
containing methane (CH.sub.4), and a diluent stream containing
water (H.sub.2O), carbon dioxide (CO.sub.2), or combinations
thereof, into a reactor containing an oxidative coupling of methane
(OCM) catalyst to produce an OCM effluent gas containing a diluent,
wherein at least one of (i) at least about 20 mol % of the gas
injected into the reactor is from the diluent stream, (ii) a
methane conversion is at least about 10%, and (iii) an outlet
temperature of the reactor is at least about 800.degree. C., is
satisfied; and (b) injecting the OCM effluent gas and an ethane
stream containing ethane into a post bed cracking (PBC) unit,
wherein the PBC unit converts ethane comprised in the OCM effluent
gas and the ethane stream to ethylene, thereby generating a PBC
effluent stream having an ethylene-to-ethane ratio greater than
about 3:1.
[0012] In some embodiments, at least two of the (i)-(iii) are
satisfied. In some embodiments, all three of the (i)-(iii) are
satisfied. In some embodiments, the method further comprises
producing a steam by putting water in thermal communication with
the gas within the reactor. In some embodiments, the method further
comprises injecting the steam into the reactor. In some
embodiments, the steam produced is the same as the diluent stream.
In some embodiments, the oxygen stream is pre-mixed with the
diluent stream to produce a diluted O.sub.2 stream. In some
embodiments, the diluted O.sub.2 stream is injected into the
reactor downstream of where the methane stream is injected. In some
embodiments, the diluted O.sub.2 stream is injected using a
diffuser tube. In some embodiments, the method further comprises
injecting a stream containing ethane into the reactor. In some
embodiments, the stream containing ethane is injected downstream of
the methane stream. In some embodiments, the stream containing
ethane is injected using a diffuser tube.
[0013] Another aspect of the present disclosure provides a method
for producing an olefin, the method comprising: (a) injecting a
stream containing methane (CH.sub.4) and oxygen (O.sub.2) into a
non-adiabatic section of a reactor, which non-adiabatic section is
in thermal communication with a heat transfer medium that contains
an oxidative coupling of methane (OCM) catalyst to produce an
intermediate gas stream, wherein the OCM catalyst undergoes
deactivation over time, such that (i) an outlet temperature of the
non-adiabatic section decreases over time, (ii) an oxygen
concentration at an outlet of the non-adiabatic section increases
over time, and (iii) the oxygen concentration at the outlet of the
non-adiabatic section is at least about 500 parts per million
(ppm); and (b) injecting the intermediate gas stream into a
substantially adiabatic section of the reactor, wherein with the
catalyst deactivation (i) an oxygen concentration at an inlet of
the substantially adiabatic section increases over time, (ii) an
outlet temperature of the substantially adiabatic section increases
over time, and (iii) an oxygen concentration at an outlet of the
substantially adiabatic section is less than about 50 parts per
million (ppm).
[0014] In some embodiments, the OCM catalyst displays lower methane
conversion over time with the deactivation. In some embodiments, a
maximum temperature in the non-adiabatic section of the reactor
decreases over time with the deactivation. In some embodiments, the
method further comprises pre-mixing a methane stream and an oxygen
stream to product the stream. In some embodiments, the outlet
temperature of the substantially adiabatic section of the reactor
is between 700-900.degree. C. at any catalyst deactivation
percentage.
[0015] Another aspect of the present disclosure provides an
apparatus for producing ethylene, the apparatus comprising: (a) a
first section that is configured to mix a methane stream containing
methane (CH.sub.4) and an oxygen stream containing oxygen (O.sub.2)
to generate a mixed stream of CH.sub.4 and O.sub.2; (b) a second
section that is configured to heat the mixed stream to a
temperature of at least about 400.degree. C.; (c) a third section
that comprises at least about 50 tubes, wherein a given tube of the
at least about 50 tubes comprises at least two of (i) an oxidative
coupling of methane (OCM) catalyst, (ii) an outer diameter greater
than about 0.5 inches, (iii) a length of at least about 3 feet, and
(iv) at least a portion that is in thermal communication with a
heat transfer medium; and (d) a fourth section that that is
downstream of and fluidically coupled to the third section, wherein
the fourth section is substantially adiabatic.
[0016] In some embodiments, the apparatus further comprises a tube
that injects the oxygen stream downstream of a location at which
the methane stream is injected. In some embodiments, the tube is a
diffuser tube. In some embodiments, the apparatus further comprises
a fifth section for injecting ethane. In some embodiments, the
fifth section is a tube that extends beyond the first section. In
some embodiments, the fifth section is a diffuser tube. In some
embodiments, there is substantially no air gap between the third
section and the fourth section. In some embodiments, a maximum
temperature of the third section is less than about 1,000.degree.
C. In some embodiments, a pressure drop in the given tube is less
than about 3 bar(g). In some embodiments, the heat transfer medium
is molten salt. In some embodiments, the heat transfer medium is a
liquid. In some embodiments, the liquid comprises water. In some
embodiments, an oxygen concentration at an exit of the fourth
section is less than about 50 parts per million (ppm). In some
embodiments, an oxygen concentration at an exit of the third
section is at least about 500 ppm. In some embodiments, the given
tube of the at least about 50 tubes comprises at least three of the
(i)-(iv). In some embodiments, the given tube of the at least about
50 tubes comprises all of the (i)-(iv).
[0017] Another aspect of the present disclosure provides a method
for producing an olefin, the method comprising: (a) providing a
reactor having an isothermal section, which isothermal section
contains a catalyst capable of promoting an oxidative coupling of
methane (OCM) reaction and is in thermal communication with a heat
transfer medium; and (b) introducing a gas mixture into the
isothermal section of the reactor, which gas mixture comprises
oxygen (O.sub.2) and methane (CH.sub.4), whereby at least about 75
mol % of the O.sub.2 reacts with the CH.sub.4 to produce an
effluent stream comprising hydrocarbon compounds having two or more
carbon atoms (C.sub.2+ compounds) and non-C.sub.2+ impurities.
[0018] In some embodiments, the OCM reaction has a selectivity for
C.sub.2+ compounds of at least about 50% at 700.degree. C. In some
embodiments, the OCM reaction has a selectivity for C.sub.2+
compounds of at least about 60% at 750.degree. C. In some
embodiments, the OCM reaction has a selectivity for C.sub.2+
compounds of at least about 65% at 800.degree. C. In some
embodiments, the gas mixture has a temperature between about
650.degree. C. and about 750.degree. C. In some embodiments, the
effluent stream has temperature between about 800.degree. C. and
about 900.degree. C. In some embodiments, the gas mixture contains
between about 13 mol % and about 17 mol % O.sub.2. In some
embodiments, the effluent stream contains between about 0.5 mol %
and about 3 mol % O.sub.2. In some embodiments, between about 12
mol % and about 16 mol % of the CH.sub.4 is converted to C.sub.2+
compounds and non-C.sub.2+ impurities in the isothermal section. In
some embodiments, the catalyst is a perovskite or comprises a
lanthanide element. In some embodiments, the catalyst does not
shrink or sinter. In some embodiments, at least about 80 mol % of
the O.sub.2 reacts with the CH.sub.4 to produce C.sub.2+ compounds
and non-C.sub.2+ impurities. In some embodiments, the method
further comprises: directing an additional gas mixture comprising
methane (CH.sub.4) and an oxidizing agent into a light-off section
in fluid communication with and upstream of the isothermal section,
which light-off section is in thermal communication with an
additional heat transfer medium and contains an additional catalyst
capable of promoting an additional OCM reaction; and converting at
least a portion of the CH.sub.4 and the oxidizing agent from the
additional gas mixture in the additional OCM reaction to produce
additional C.sub.2+ compounds. In some embodiments, the heat
transfer medium and the additional heat transfer medium are molten
salts. In some embodiments, the additional OCM reaction has a
selectivity for C.sub.2+ compounds of at least about 30% at
550.degree. C. In some embodiments, the additional OCM reaction has
a selectivity for C.sub.2+ compounds of at least about 40% at
600.degree. C. In some embodiments, the reactor further comprises a
heating section in fluid communication with and upstream of the
light-off section, which heating section is in thermal
communication with a further additional heat transfer medium, which
further additional heat transfer medium comprises a molten salt. In
some embodiments, the additional gas mixture has a temperature
between about 450.degree. C. and about 580.degree. C. In some
embodiments, the method further comprises generating an additional
effluent stream comprising the additional C.sub.2+ compounds,
wherein the additional effluent stream has a temperature between
about 650.degree. C. and about 750.degree. C. In some embodiments,
the additional gas mixture contains between about 15 mol % and
about 20 mol % O.sub.2. In some embodiments, the method further
comprises generating an additional effluent stream comprising the
additional C.sub.2+ compounds, wherein the additional effluent
stream contains between about 13 mol % and about 17 mol % O.sub.2.
In some embodiments, between about 3 mol % and about 5 mol % of the
CH.sub.4 from the additional gas mixture is converted to C.sub.2+
compounds and non-C.sub.2+ impurities in the light-off section. In
some embodiments, the additional catalyst comprises nanowires. In
some embodiments, the additional catalyst is capable of performing
oxidative dehydrogenation (ODH). In some embodiments, at least
about 10 mol % the O.sub.2 from the additional gas mixture reacts
with the CH.sub.4 to produce C.sub.2+ compounds and non-C.sub.2+
impurities. In some embodiments, the method further comprises:
directing the effluent stream from the isothermal section into an
adiabatic section in fluid communication with and downstream of the
isothermal section, which adiabatic section is insulated and
contains an additional catalyst capable of promoting an additional
OCM reaction reacting at least a portion of the effluent stream in
the additional OCM reaction to yield a product stream, which
product stream has an oxygen concentration that is less than or
equal to about 2,000 parts per million (ppm). In some embodiments,
the additional OCM reaction has a net selectivity for C.sub.2+
compounds of between about 0% and about 20% at 850.degree. C. In
some embodiments, the effluent stream comprises unreacted CH.sub.4
and wherein less than about 10 mol % of unreacted CH.sub.4 is
reformed into CO and H.sub.2. In some embodiments, the additional
catalyst is a perovskite. In some embodiments, the additional
catalyst facilities oxidative dehydrogenation (ODH). In some
embodiments, the effluent stream comprises unreacted CH.sub.4 and
wherein between about 0 mol % and about 3 mol % of the unreacted
CH.sub.4 is converted to C.sub.2+ compounds and non-C.sub.2+
impurities in the adiabatic section. In some embodiments, the
method further comprises adding between about 0 mol % and about 5
mol % ethane (C.sub.2H.sub.6) to the effluent stream near an inlet
of the adiabatic section. In some embodiments, the effluent stream
is introduced into the adiabatic section at a temperature between
about 800.degree. C. and about 900.degree. C. In some embodiments,
a product stream exits the adiabatic section at a temperature
between about 850.degree. C. and about 950.degree. C. In some
embodiments, the reactor further comprises a post-bed cracking
(PBC) section in fluid communication with and downstream of the
adiabatic section, which PBC section converts C.sub.2H.sub.6 into
C.sub.2H.sub.4 using heat derived from the OCM reaction and/or the
additional OCM reaction. In some embodiments, the method further
comprises adding between about 1 mol % and about 5 mol % ethane
(C.sub.2H.sub.6) to a PBC process stream near an inlet of the PBC
section. In some embodiments, at least about 20 mol % of the
CH.sub.4 is converted to C.sub.2+ compounds and non-C.sub.2+
impurities in the combination of the light-off section, the
isothermal section and the adiabatic section.
[0019] Another aspect of the present disclosure provides a system
for performing oxidative coupling of methane (OCM), the system
comprising a reactor comprising: (a) a light-off section that is
adapted to accept a gas mixture comprising oxygen (O.sub.2) and
methane (CH.sub.4) and contains a first OCM catalyst that
facilities an OCM reaction which converts the O.sub.2 and the
CH.sub.4 into hydrocarbon compounds having two or more carbon atoms
(C.sub.2+ compounds) at a selectivity of at least about 30% at
550.degree. C., wherein the light-off section is in thermal
communication with a first heat transfer medium; (b) an isothermal
section in fluidic communication with and downstream of the
light-off section, which isothermal section contains a second OCM
catalyst that has a selectivity for C.sub.2+ compounds of at least
about 50% at 700.degree. C., wherein the isothermal section is in
thermal communication with a second heat transfer medium; and/or
(c) an adiabatic section in fluidic communication with and
downstream of the isothermal section, which adiabatic section
contains a third OCM catalyst that has a net selectivity for
C.sub.2+ compounds of at least about 0% at 850.degree. C.
[0020] In some embodiments, the reactor further comprises a
post-bed cracking (PBC) section in fluid communication with and
downstream of the adiabatic section, which PBC section converts
C.sub.2H.sub.6 into C.sub.2H.sub.4 using heat derived from the OCM
reaction. In some embodiments, the reactor comprises both the
light-off section and the adiabatic section. In some embodiments,
the reactor is adapted to operate at a pressure of greater than
about 2 bar(g). In some embodiments, the reactor is a tubular
reactor. In some embodiments, the first transfer medium and the
second heat transfer medium are the same. In some embodiments, the
first transfer medium and/or the second heat transfer medium are
molten salts. In some embodiments, the system further comprises a
methanation reactor that is in fluid communication with the first
heat transfer medium or the second heat transfer medium. In some
embodiments, the reactor further comprises a methanation section in
fluidic communication with and upstream of the light-off section,
which methanation section contains a methanation catalyst.
[0021] Another aspect of the present disclosure provides a method
for producing an olefin, the method comprising producing a gas
stream comprising methane (CH.sub.4), oxygen (O.sub.2), and a
diluent and passing the gas stream over an oxidative coupling of
methane (OCM) catalyst at a pressure of at least about 2 bar(g) to
convert at least some of the CH.sub.4 into hydrocarbon compounds
having two or more carbon atoms (C.sub.2+ compounds), wherein a
ratio of diluent molecules to carbon atoms in the gas stream is at
least about 0.1.
[0022] In some embodiments, the diluent comprises water (H.sub.2O).
In some embodiments, the diluent comprises carbon dioxide
(CO.sub.2). In some embodiments, the ratio is at least about 0.5.
In some embodiments, the ratio is at most about 5. In some
embodiments, the ratio is between about 0.1 and about 5. In some
embodiments, the pressure is at least about 4 bar(g).
[0023] Another aspect of the present disclosure provides a method
for producing an olefin, the method comprising: (a) injecting an
oxidizing agent and a paraffin into a gas stream containing a
radical transfer agent to provide a reaction mixture in a vessel,
which reaction mixture is at a reaction temperature and at a
reaction pressure sufficient to result in ignition of the reaction
mixture; and (b) holding the reaction mixture in the vessel for a
time period that is sufficient to permit the reaction mixture to
convert to a product mixture, whereby the paraffin is converted to
the olefin in the product mixture at an apparent selectivity of at
least about 30%.
[0024] In some embodiments, the method further comprises,
subsequent to (b), cooling the product mixture. In some
embodiments, the method further comprises repeating (a)-(b) to
produce additional olefins. In some embodiments, the time period
held in (b) is the auto-ignition delay time (AIDT). In some
embodiments, the time period held in (b) is sufficient to
accumulate a critical concentration of radical species. In some
embodiments, (i) the reaction mixture is converted to the product
mixture in a first stage, (ii) at least a portion of the product
mixture is directed to a second stage downstream of the first
stage, and (ii) an additional oxidizing agent and paraffin are
injected in the second stage. In some embodiments, (a)-(b) are
performed at least two times. In some embodiments, upon ignition of
the reaction mixture, the radical transfer agent is radicalized to
yield a radicalized transfer agent. In some embodiments, the
radicalized transfer agent radicalizes the paraffin to yield a
radicalized paraffin, and wherein the radicalized paraffin oxidizes
to form the olefin. In some embodiments, the radical transfer agent
is methane, water, hydrogen, or any combinations thereof. In some
embodiments, upon ignition of the reaction mixture, at least one of
a hydroxyl radical (HO.), a methyl radical (H.sub.3C.) and a
hydrogen radical (H.) are produced. In some embodiments, the vessel
contains a radicalization initiator. In some embodiments, the
radicalization initiator is a solid catalyst. In some embodiments,
the solid catalyst is an oxidative coupling of methane (OCM)
catalyst. In some embodiments, the paraffin is ethane and the
olefin is ethylene. In some embodiments, the paraffin is propane
and the olefin is propylene. In some embodiments, the reaction
temperature is at least about 450.degree. C. In some embodiments,
prior to cooling the product mixture, the product mixture has a
temperature of less than about 850.degree. C. In some embodiments,
the reaction pressure is about 8 bar(g). In some embodiments, the
apparent selectivity is at least about 85%. In some embodiments,
the apparent selectivity is a molar fraction of olefin produced per
parent alkane consumed, and wherein the parent alkane is an alkane
with the same number of carbons as the olefin produced. In some
embodiments, a portion of the paraffin is converted to CO,
CO.sub.2, or any combinations thereof (CO.sub.x). In some
embodiments, the paraffin is converted to the olefin at a carbon
efficiency that is at least about 50%, and wherein the carbon
efficiency is a percentage of olefin produced relative to CO.sub.x
formed. In some embodiments, the AIDT is about 10 milliseconds
(ms). In some embodiments, the oxidizing agent in the reaction
mixture is less than about 1%. In some embodiments, a concentration
of the paraffin in the reaction mixture is less than about 10 mol
%. In some embodiments, the gas stream is an OCM effluent. In some
embodiments, the gas stream is superheated steam. In some
embodiments, the oxidizing agent is O.sub.2. In some embodiments,
the oxidizing agent, the paraffin and the radical transfer agent
are different species.
[0025] Another aspect of the present disclosure provides a system
for performing oxidative coupling of methane (OCM), comprising: an
OCM reactor comprising an OCM catalyst that facilitates an OCM
reaction, the OCM reactor configured to receive methane and an
oxidizing agent and permit at least a portion of the methane and
the oxidizing agent to react in the OCM reaction to yield an
effluent stream; and an oxidative dehydrogenation (ODH) reactor
downstream of and in fluidic communication with the OCM reactor,
which ODH reactor receives at least a portion of the effluent
stream from the OCM reactor, wherein the ODH reactor comprises an
ODH catalyst that facilities an ODH reaction in which at least a
portion of paraffins from the effluent stream is converted into
olefins.
[0026] In some embodiments, the OCM reactor is a molten salt
reactor. In some embodiments, the molten salt reactor is a tubular
reactor. In some embodiments, the ODH catalyst comprises
Cr.sub.2O.sub.3 supported on SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2
or ZrO.sub.2, Cr/SO.sub.4--SiO.sub.2, K--Cr/SO.sub.4--SiO.sub.2,
K--Cr--Mn/SiO.sub.2, Cr/H-ZSM-5, Cr/Silicalite-2,
Fe--Mn/Silicalite-2, Cr--Mn/Silicalite-2, Cr--Mn--Ni/Silicalite-2,
MnO.sub.2, K-doped MnO.sub.2, Na.sub.2WO.sub.4--Mn/SiO.sub.2,
CeO.sub.2, Fe--Cr/ZrO.sub.2, or combinations thereof. In some
embodiments, the paraffins comprise ethane and/or propane. In some
embodiments, the olefins comprise ethylene and/or propylene.
[0027] Another aspect of the present disclosure provides a method
for performing oxidative coupling of methane (OCM), the method
comprising: directing methane and an oxidizing agent into an OCM
reactor, wherein the OCM reactor comprises an OCM catalyst that
facilitates an OCM reaction and is configured to permit at least a
portion of the methane and the oxidizing agent to react in the OCM
reaction to yield an effluent stream; and directing at least a
portion of the effluent stream into an oxidative dehydrogenation
(ODH) reactor downstream of and in fluidic communication with the
OCM reactor, wherein the ODH reactor comprises an ODH catalyst that
facilities an ODH reaction in which at least a portion of paraffins
from the effluent stream is converted into olefins.
[0028] In some embodiments, the oxidizing agent is oxygen. In some
embodiments, the effluent stream comprises unreacted oxidizing
agent. In some embodiments, at least a portion of the unreacted
oxidizing agent is used as an oxidant in the ODH reaction. In some
embodiments, the effluent stream comprises carbon dioxide
(CO.sub.2). In some embodiments, at least a portion of the CO.sub.2
is used as an oxidant in the ODH reaction. In some embodiments, the
method further comprises converting the at least the portion of the
CO.sub.2 to carbon monoxide (CO) in the ODH reaction. In some
embodiments, the method further comprises directing at least a
portion of the CO into a methanation reactor to generate a
methanation product stream comprising methane. In some embodiments,
the method further comprises directing at least a portion of the
methanation product stream into the OCM reactor.
[0029] Another aspect of the present disclosure provides a system
for performing a catalytic reaction comprising: a reactor
comprising a catalyst bed, the catalyst bed comprising a void
material having a void fraction of greater than or equal to about
70% and a catalytic material that facilitates the catalytic
reaction.
[0030] In some embodiments, the void fraction is greater than or
equal to about 85%. In some embodiments, the void material and the
catalytic material is pre-assembled prior to being loaded into the
reactor. In some embodiments, catalytic material is deposited as a
film onto a surface of the void material. In some embodiments, the
reactor comprises a liner in contact with an inner surface of the
reactor. In some embodiments, the liner is a flexible metal foil.
In some embodiments, the void material and the catalytic material
are deposited onto the liner.
[0031] Another aspect of the present disclosure provides a method
for producing higher hydrocarbon compounds, the method comprising:
directing a feed stream comprising ethylene into a separations unit
comprising a pressure swing adsorption (PSA) unit and/or a
temperature swing adsorption (TSA) unit to adsorb at least a
portion of the ethylene from the feed stream at a first pressure
and/or a first temperature; and adjusting the first pressure and/or
the first temperature of the separations unit to a second pressure
and/or a second temperature to (i) desorb at least a portion of the
at least the portion of the ethylene and (ii) convert at least an
additional portion of the at least the portion of the ethylene to
the higher hydrocarbon compounds in an ethylene conversion
reaction.
[0032] In some embodiments, the second pressure is lower than the
first pressure. In some embodiments, the second temperature is
higher than the first temperature. In some embodiments, the first
temperature is less than or equal to about 50.degree. C. In some
embodiments, the first pressure is greater than or equal to about 6
bar(a). In some embodiments, the second temperature is greater than
or equal to about 100.degree. C. In some embodiments, the second
pressure is less than or equal to about 5 bar(a). In some
embodiments, the feed stream is an oxidative coupling of methane
(OCM) effluent stream. In some embodiments, the method further
comprises directing methane and an oxidizing agent into an OCM
reactor to producing the OCM effluent stream. In some embodiments,
the ethylene conversion reaction comprises a dimerization reaction
and/or an oligomerization reaction. In some embodiments, the higher
hydrocarbon compounds comprise butene. In some embodiments, the
method further comprises directing a separations effluent stream
comprising the higher hydrocarbon compounds from the separations
unit into a metathesis unit to yield a product stream comprising
propylene. In some embodiments, the separations unit comprises a
material that facilitates ethylene selective adsorption and the
ethylene conversion reaction. In some embodiments, the material is
an adsorbent and/or catalyst. In some embodiments, the material
comprises porous zeolites. In some embodiments, the porous zeolites
have an average pore diameter between about 4 .ANG. and about 8
.ANG.. In some embodiments, the materials comprise zeolites doped
with transition metals. In some embodiments, the zeolites comprise
Fe-ZSM-5, ZSM-5, ZSM-23 or combinations thereof.
[0033] Another aspect of the present disclosure provides a system
for performing oxidative coupling of methane (OCM), the system
comprising: an OCM reactor comprising at least one corrugated metal
foil and a catalyst that facilitates an OCM reaction, wherein the
at least one corrugated metal foil comprising ridges and
intervening grooves between the ridges and wherein the catalyst is
disposed within the intervening grooves.
[0034] In some embodiments, the OCM reactor comprises a plurality
of corrugated metal foils. In some embodiments, each of the
plurality of corrugated metal foils comprises perforations that
create passageways among the plurality of corrugated metal foils.
In some embodiments, the at least one corrugated metal foil
comprises an active zone. In some embodiments, the OCM reaction in
conducted in the active zone. In some embodiments, the grooves are
micro-channels.
[0035] Additional aspects and advantages of the present disclosure
will become readily apparent to those skilled in this art from the
following detailed description, wherein only illustrative
embodiments of the present disclosure are shown and described. As
will be realized, the present disclosure is capable of other and
different embodiments, and its several details are capable of
modifications in various obvious respects, all without departing
from the disclosure. Accordingly, the drawings and description are
to be regarded as illustrative in nature, and not as
restrictive.
INCORPORATION BY REFERENCE
[0036] All publications, patents, and patent applications mentioned
in this specification are herein incorporated by reference to the
same extent as if each individual publication, patent, or patent
application was specifically and individually indicated to be
incorporated by reference.
BRIEF DESCRIPTION OF THE FIGURES
[0037] The novel features of the invention are set forth with
particularity in the appended claims. A better understanding of the
features and advantages of the present invention will be obtained
by reference to the following detailed description that sets forth
illustrative embodiments, in which the principles of the invention
are utilized, and the accompanying drawings or figures (also "FIG."
and "FIGs." herein), of which:
[0038] FIG. 1A shows an oxidative coupling of methane (OCM) system
that comprises an adiabatic section and a non-adiabatic
section;
[0039] FIG. 1B shows an example of an OCM system that comprises a
light-off section;
[0040] FIG. 2 shows an oxidative coupling of methane system that
comprises a mixer, an adiabatic section, and a non-adiabatic
section;
[0041] FIG. 3 shows an oxidative coupling of methane system that
comprises a methane preheat section, an adiabatic section, and a
non-adiabatic section;
[0042] FIG. 4 shows an oxidative coupling of methane system that
comprises a methane preheater and a steam superheater;
[0043] FIG. 5 shows an oxidative coupling of methane system that
comprises a mixer and a steam superheater;
[0044] FIG. 6 shows an oxidative coupling of methane system that
comprises a heat exchanger downstream of the oxidative coupling of
methane reactor;
[0045] FIG. 7 shows an oxidative coupling of methane system that
uses a heat transfer medium to preheat the feed gas;
[0046] FIG. 8 shows an oxidative coupling of methane reactor that
comprises an adiabatic section and a non-adiabatic section;
[0047] FIG. 9 shows an oxidative coupling of methane reactor that
comprises diffuser tubes, adiabatic, and non-adiabatic
sections;
[0048] FIG. 10 shows an example of a diffuser tube;
[0049] FIG. 11 shows an oxidative coupling of methane reactor that
uses molten salt as a heat transfer medium;
[0050] FIG. 12 shows an oxidative coupling of methane system using
a diluent;
[0051] FIG. 13 shows an oxidative coupling of methane system using
a steam diluent that is heated in an oxidative coupling of methane
reactor;
[0052] FIG. 14 shows an oxidative coupling of methane system that
mixes oxygen with a diluent prior to injection in an oxidative
coupling of methane reactor;
[0053] FIG. 15 shows an oxidative coupling of methane system in
which oxygen and a diluent are added downstream of methane;
[0054] FIG. 16 shows an oxidative coupling of methane system that
comprises multiple ethane injection locations;
[0055] FIG. 17 shows a result of a simulation that calculates the
temperature profile in an oxidative coupling of methane
reactor;
[0056] FIG. 18 shows a combination of alkane, radical transfer
agent, and O.sub.2 to generate olefin;
[0057] FIG. 19 shows a system for increasing olefin concentrations
in the cooled effluent gas by converting additional alkane;
[0058] FIG. 20 shows a system for increasing olefin concentrations
in the effluent gas of an oxidative coupling of methane (OCM)
process;
[0059] FIG. 21 shows a system for using a steam superheater as a
radical transfer agent source in olefin production;
[0060] FIG. 22 shows a modular system for increasing olefin
concentrations in an effluent stream;
[0061] FIG. 23 shows a staged system for increasing olefin
concentrations in an effluent stream;
[0062] FIG. 24 shows an example of a multistage system for
increasing olefin concentrations in an oxidative coupling of
methane effluent stream;
[0063] FIG. 25 shows an example concentration profile of ethane
while reacting with oxygen and methane in a vessel;
[0064] FIG. 26 shows an example concentration profile of ethylene
generated from a reaction of ethane with oxygen and methane;
[0065] FIG. 27 shows example concentration and temperature profiles
that describe behavior of a reaction in a vessel;
[0066] FIG. 28 shows examples of reactions and selectivities;
[0067] FIG. 29 shows an example of a block flow diagram of an OCM
reaction system utilizing a molten salt heat exchange medium;
[0068] FIG. 30 shows an example of operation of an OCM reactor
comprising an isothermal section, an adiabatic section, and a
post-bed cracking section;
[0069] FIG. 31 shows an example of the reduction in cross section
of a tubular OCM reactor resulting in a more even temperature
profile;
[0070] FIG. 32 shows a computer system that is programmed or
otherwise configured to implement methods of the present
disclosure, such as regulating a reaction;
[0071] FIG. 33 shows an example reactor comprising a catalyst bed
having a composite packing;
[0072] FIG. 34 shows an example reactor which comprises a foil wrap
used for assembling void materials and catalytic materials within
the reactor;
[0073] FIG. 35 shows an example reactor comprising a metal mesh
brazed on an inner wall of the reactor;
[0074] FIG. 36 illustrates an example method for producing
hydrocarbon compounds comprising propylene using catalytic pressure
swing adsorption (PSA) or temperature swing adsorption (TSA);
[0075] FIG. 37 shows an example OCM reactor comprising two catalyst
assembly stacks with perforations for feed inlet and product
outlet; and
[0076] FIG. 38 shows an example OCM reactor comprising a metal
sheet having multiple active zones.
DETAILED DESCRIPTION
[0077] While various embodiments of the invention have been shown
and described herein, it will be obvious to those skilled in the
art that such embodiments are provided by way of example only.
Numerous variations, changes, and substitutions may occur to those
skilled in the art without departing from the invention. It should
be understood that various alternatives to the embodiments of the
invention described herein may be employed.
[0078] The term, "adiabatic" or "adiabatic process," generally
refers to a process in which the pressure of a gas may be allowed
to increase without substantial heat losses to the surroundings. A
substantially adiabatic unit or element may permit little to no
heat transfer between units or elements, such as, for example, less
than 15%, 10%, 5%, 4%, 3%, 2%, or 1% heat transfer (e.g., as
measured by total heat input and heat output from the unit).
[0079] The term "non-adiabatic," as used herein, generally refers
to a unit or process element that may exchange heat with another
unit or process element. Such unit or process element may be in
thermal communication with a heat transfer unit (e.g., a heat
exchanger or heat transfer medium).
[0080] The term "heat transfer medium," as used herein, generally
refers to material (e.g., a solid or a liquid) that can be used to
store thermal energy.
[0081] The terms "C.sub.2+" and "C.sub.2+ compound," as used
herein, generally refer to a compound comprising two or more carbon
atoms, e.g., two carbon atoms (C.sub.2), three carbon atoms
(C.sub.3), etc. C.sub.2+ compounds include, without limitation,
alkanes, alkenes, alkynes and aromatics containing two or more
carbon atoms. In some cases, C.sub.2+ compounds include aldehydes,
ketones, esters and carboxylic acids. Examples of C.sub.2+
compounds include ethane, ethylene, acetylene, propane, propene,
butane, butene, etc.
[0082] The term "non-C.sub.2+ impurities," as used herein,
generally refers to material that does not include C.sub.2+
compounds. Examples of non-C.sub.2+ impurities, which may be found
in certain product streams (e.g., oxidative coupling of methane
product stream), include nitrogen (N.sub.2), oxygen (O.sub.2),
water (H.sub.2O), argon (Ar), hydrogen (H.sub.2) carbon monoxide
(CO), carbon dioxide (CO.sub.2) and methane (CH.sub.4).
[0083] The term "light-off" as used herein, generally refers to
initiation of an oxidative coupling of methane (OCM) reaction, for
example at a low temperature, such as less than about 600.degree.
C., less than about 550.degree. C., less than about 500.degree. C.,
less than about 450.degree. C., or less than about 400.degree.
C.
[0084] The term "radical transfer agent," as used herein, generally
refers to a species of molecule that can undergo a transformation
from its neutral form into a free radical under temperatures and
pressures that species is exposed to in a process.
[0085] The term "auto-ignition delay time" (AIDT), as used herein,
generally refers to the difference in time between when a fuel and
oxidizer come into contact, in the absence of any external ignition
source, and when the spontaneous combustion of the fuel and
oxidizer mixture occurs.
[0086] The term "apparent selectivity," as used herein, generally
refers to the fraction of the carbon of a selected species
contained in the reactor effluent stream when compared to the
amount of carbon contained in the reactor effluent stream excluding
methane. For example, as an oxidative coupling of methane reactor
feed stream may contain a number of hydrocarbon species beside
methane, some of the desired products (e.g., ethylene) can be
formed from multiple sources of methane, ethane and propane.
[0087] The term "net selectivity," as used herein, generally refers
to a ratio of a desired product(s) formed (in moles of Carbon) to
the sum of all products formed (desired and undesired) (in moles of
Carbon) in a given process. The process can be a single-step or
multi-step process. For example, a net selectivity for C.sub.2+
compounds in an OCM process performed in an OCM system comprising a
light off section, an isothermal section and an adiabatic section
is determined as a ratio of (C.sub.2+ compounds produced in the OCM
system)/(C.sub.2+ and non-C.sub.2+ compounds produced in the OCM
system). As the feed mixture to the reactor may contain ethane and
propane, this measurement may enable to evaluate the net generation
of coupling products from OCM when in competition with higher
alkane combustion and/or ODH.
[0088] The term "carbon efficiency," as used herein, generally
refers to the extent to which an alkane is converted to an olefin
relative to an oxidized compound (e.g. CO, CO.sub.2, generally
referred to as CO.sub.x), and may be expressed as a percentage.
[0089] The term "unit," as used herein, generally refers to a unit
operation, which is a basic operation in a process. Unit operations
may involve a physical change or chemical transformation, such as,
for example, separation, crystallization, evaporation, filtration,
polymerization, isomerization, transformation, and other reactions.
A given process may require one or a plurality of unit operations
to obtain the desired product(s) from a starting material(s), or
feedstock(s).
[0090] The term "paraffin," as used herein, generally refers to a
saturated hydrocarbon. A paraffin may be an alkane having the
formula C.sub.nH.sub.2n+2, wherein `n` is an integer greater than
or equal to 1.
[0091] In an OCM process, methane (CH.sub.4) reacts with an
oxidizing agent over a catalyst bed to generate C.sub.2+ compounds.
For example, methane can react with oxygen over a suitable catalyst
to generate ethylene, e.g.,
2CH.sub.4+O.sub.2.fwdarw.C.sub.2H.sub.4+2H.sub.2O (See, e.g.,
Zhang, Q., Journal of Natural Gas Chem., 12:81, 2003; Olah, G.
"Hydrocarbon Chemistry," Ed. 2, John Wiley & Sons (2003)). This
reaction may be exothermic (.DELTA.H=-67 kcals/mole) and may have
been shown to occur at very high temperatures (e.g.,
>450.degree. C. or >700.degree. C.). Non-selective reactions
that can occur include (a) CH.sub.4+2O.sub.2 CO.sub.2+2H.sub.2O and
(b) CH.sub.4+1/2O.sub.2.fwdarw.CO+2H.sub.2. These non-selective
reactions may also be exothermic, with reaction heats of -891
kJ/mol and -36 kJ/mol respectively. The conversion of methane to
COx products may be undesirable due to both heat management and
carbon efficiency concerns.
[0092] Experimental evidence suggests that free radical chemistry
may be involved. (Lunsford, J. Chem. Soc., Chem. Comm., 1991; H.
Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the
reaction, methane (CH.sub.4) is activated on the catalyst surface,
forming methyl radicals which then couples in the gas phase to form
ethane (C.sub.2H.sub.6), followed by dehydrogenation to ethylene
(C.sub.2H.sub.4). The OCM reaction pathway can have a
heterogeneous/homogeneous mechanism, which involves free radical
chemistry. Experimental evidence has shown that an oxygen active
site on the catalyst activates the methane, removes a single
hydrogen atom and creates a methyl radical. Methyl radicals may
react in the gas phase to produce ethane, which is either oxidative
or non-oxidatively dehydrogenated to ethylene. The main reactions
in this pathway can be as follows: (a)
CH.sub.4+O.sup.-.fwdarw.CH.sub.3*+OH.sup.-; (b)
2CH.sub.3*.fwdarw.C.sub.2H.sub.6; (c)
C.sub.2H.sub.6+O.sup.-.fwdarw.C.sub.2H.sub.4+H.sub.2O. In some
cases, to improve the reaction yield, ethane can be introduced
downstream of the OCM catalyst bed and thermally dehydrogenated via
the following reaction:
C.sub.2H.sub.6.fwdarw.C.sub.2H.sub.4+H.sub.2. This reaction can be
endothermic (.DELTA.H=-144 kJ/mol), which can utilize the
exothermic reaction heat produced during methane conversion.
Combining these two reactions in one vessel can increase thermal
efficiency while simplifying the process.
[0093] Several catalysts have shown activity for OCM, including
various forms of iron oxide, V.sub.2O.sub.5, MoO.sub.3,
Co.sub.3O.sub.4, Pt--Rh, Li/ZrO.sub.2, Ag--Au, Au/Co.sub.3O.sub.4,
Co/Mn, CeO.sub.2, MgO, La.sub.2O.sub.3, Mn.sub.3O.sub.4,
Na.sub.2WO.sub.4, MnO, ZnO, and combinations thereof, on various
supports. A number of doping elements have also proven to be useful
in combination with the above catalysts.
[0094] Since the OCM reaction was first reported over thirty years
ago, it has been the target of intense scientific and commercial
interest, but the fundamental limitations of the conventional
approach to C--H bond activation appear to limit the yield of this
attractive reaction under practical operating conditions.
Specifically, numerous publications from industrial and academic
labs have consistently demonstrated characteristic performance of
high selectivity at low conversion of methane, or low selectivity
at high conversion (J. A. Labinger, Cat. Lett., 1:371, 1988).
Limited by this conversion/selectivity threshold, no OCM catalyst
has been able to exceed 20-25% combined C.sub.2 yield (i.e., ethane
and ethylene), and more importantly, all such reported yields
operate at extremely high temperatures (>800.degree. C.). Novel
catalysts and processes have been described for use in performing
OCM in the production of ethylene from methane at substantially
more practicable temperatures, pressures and catalyst activities.
These are described in, for example, U.S. Patent Publication Nos.
2012/0041246, 2013/0023709, 2013/165728, 2014/0012053 and
2014/0018589, each of which is entirely incorporated herein by
reference for all purposes.
[0095] An OCM reactor can include a catalyst that facilitates an
OCM process. The catalyst may include a compound including at least
one of an alkali metal, an alkaline earth metal, a transition
metal, and a rare-earth metal. The catalyst may be in the form of a
honeycomb, packed bed, or fluidized bed. In some embodiments, at
least a portion of the OCM catalyst in at least a portion of the
OCM reactor can include one or more OCM catalysts and/or
nanostructure-based OCM catalyst compositions, forms and
formulations described in, for example, U.S. Patent Publication
Nos. 2012/0041246, 2013/0023709, 2013/0158322, 2013/0165728 and
2014/0274671, each of which is entirely incorporated herein by
reference. Using one or more nanostructure-based OCM catalysts
within the OCM reactor, the carbon efficiency of the OCM process
can be at least 50%, at least 60%, at least 70%, at least 80%, or
at least 90%.
Adiabatic and Non-Adiabatic Staged Reactors
[0096] An adiabatic process is one that may occur without transfer
of heat or matter between a thermodynamic system and its
surroundings. In an adiabatic process, energy may be transferred to
its surroundings only as work. Some chemical and physical processes
may occur so rapidly that they may be conveniently described by the
term "adiabatic approximation," meaning that there may not be
enough time for the transfer of energy as heat to take place to or
from the system. By way of example, the adiabatic flame temperature
is an idealization that uses the "adiabatic approximation" so as to
provide an upper limit calculation of temperatures produced by
combustion of a fuel. The adiabatic flame temperature is the
temperature that may be achieved by a flame if the process of
combustion took place in the absence of heat loss to the
surroundings.
[0097] For a closed system, one may write the first law of
thermodynamics as: .DELTA.U=Q+W, where .DELTA.U denotes the change
of the system's internal energy, Q the quantity of energy added to
it as heat, and W the work done on it by its surroundings. If the
system has rigid walls such that work may not be transferred in or
out (W=0), and the walls of the system are not adiabatic and energy
is added in the form of heat (Q>0), and there is no phase
change, the temperature of the system may rise. If the system has
rigid walls such that pressure-volume work cannot be done, and the
system walls are adiabatic (Q=0), but energy is added as isochoric
work in the form of friction or the stirring of a viscous fluid
within the system (W>0), and there is no phase change, the
temperature of the system may rise. If the system walls are
adiabatic (Q=0), but not rigid (W.noteq.0), and, in a fictive
idealized process, energy is added to the system in the form of
frictionless, non-viscous pressure-volume work, and there is no
phase change, the temperature of the system may rise. Such a
process sometimes is called an isentropic process and is said to be
"reversible". Fictively, if the process is reversed, the energy
added as work can be recovered entirely as work done by the system.
If the system contains a compressible gas and is reduced in volume,
the uncertainty of the position of the gas may be reduced, and
seemingly may reduce the entropy of the system, but the temperature
of the system may rise as the process is isentropic (.DELTA.S=0).
Should the work be added in such a way that friction or viscous
forces are operating within the system, then the process may not be
isentropic, and if there is no phase change, then the temperature
of the system may rise, the process is said to be "irreversible,"
and the work added to the system may not be entirely recoverable in
the form of work.
[0098] Adiabatic processes may be irreversible (entropy is
produced). Energy may be transferred as work into an adiabatically
isolated system. In some cases, there may be no entropy produced
within the system (no friction, viscous dissipation, etc.), and the
work may only be pressure-volume work (denoted by P dV). This may
occur only approximately, because it may demand a substantially
slow process and no sources of dissipation. In some cases, the work
is isochoric work (dV=0), for which energy may be added as work
solely through friction or viscous dissipation within the system. A
stirrer that transfers energy to a viscous fluid of an
adiabatically isolated system with rigid walls, without phase
change, may cause a rise in temperature of the fluid, but that work
may not be recoverable. Isochoric work may be irreversible. An
aspect of the present disclosure provides a method for controlling
a temperature and influencing product composition within an
oxidative coupling of methane (OCM) reactor by using a staged
reactor design. The staged reactor may comprise combinations of
adiabatic and non-adiabatic sections. An adiabatic section may be
distinguished by insulation, or the lack of significant external
convective heat transfer.
[0099] A non-adiabatic section of a reactor may be in thermal
communication with a heat transfer medium. Energy may flow from the
process gas to the heat transfer medium if the heat transfer medium
is lower in temperature than the process gas. Energy may from the
heat transfer medium to the process gas if the heat transfer medium
is higher in temperature than the process gas. The non-adiabatic
section can be distinguished by a convective heat transfer fluid
external to the bed. Alternatively, the non-adiabatic section can
be distinguished by having a low Grashof number (Gr). The Grashof
number (Gr) is a dimensionless number in fluid dynamics and heat
transfer which approximates the ratio of the buoyancy to viscous
force acting on a fluid. Free convection is caused by a change in
density of a fluid due to a temperature change or gradient. The
density may decrease due to an increase in temperature and causes
the fluid to rise. This motion may be caused by the buoyancy force.
The major force that resists the motion may be the viscous force.
The Grashof number is a way to quantify the opposing forces. The
Grashof number at the outer wall of the non-adiabatic section is
typically <1, dependent on the characteristic length.
[0100] The non-adiabatic section may also be distinguished by the
Nusselt Number. Nusselt number (Nu) is the ratio of convective to
conductive heat transfer across (normal to) the boundary. In this
context, convection may include both advection and diffusion. Nu
may be a dimensionless number. The conductive component may be
measured under the same conditions as the heat convection but with
a (hypothetically) stagnant (or motionless) fluid. A similar
non-dimensional parameter may be Biot number, with the difference
that the thermal conductivity is of the solid body and not the
fluid. This number may give an idea that how heat transfer rate in
convection is related to the resulting of heat transfer rates in
conduction, e.g., a system comprising a hot fluid getting heated
which is in contact with a metal wall. A Nusselt number close to
one, namely convection and conduction of similar magnitude, may be
characteristic of "slug flow" or laminar flow. A larger Nusselt
number may correspond to more active convection, with turbulent
flow typically in the 100-1000 range. The convection and conduction
heat flows may be parallel to each other and to the surface normal
of the boundary surface, and may be all perpendicular to the mean
fluid flow in the simple case.
[0101] The Nusselt Number at an outer wall of the non-adiabatic
section may be less than about 1000, 100, 10, 1, or less, depending
on the characteristic length.
[0102] Characteristic length is a term that may be used to
represent a typical dimension in a fluid flow medium when studying
it in fluid mechanics. It can be anything. For example, for
internal flows of air (which is a fluid) in a room, then any of the
length L, width W, or height H can be chosen as a characteristic
length depending on the direction of the flow. Similarly, for
external or internal flows over or inside a circular cylinder, the
diameter D, or maybe the length L can be chosen as the length scale
depending on the flow direction.
[0103] If the oxidative coupling of methane reaction is occurring
within a non-adiabatic section of a reactor that is in thermal
communication with a heat transfer medium (such as a heat transfer
fluid), and the heat transfer medium has a lower temperature than
the process gas, the process gas may reach a temperature lower than
a temperature of a process gas generated by an OCM reaction
occurred in a substantially adiabatic section of a reactor.
[0104] Additionally, if the process gas is inside a non-adiabatic
section of a reactor that is in thermal communication with a heat
transfer medium and the process gas is too low in temperature for
the oxidative coupling of methane to occur, the heat transfer
medium can heat the process gas if the heat transfer medium is
higher in temperature than the process gas.
[0105] A non-adiabatic section of a reactor that is in thermal
communication with a heat transfer medium can therefore be used to
heat or cool the process gas. Incorporating a non-adiabatic section
of a reactor that is in thermal communication with a heat transfer
medium can serve to control a temperature of the process gas within
the reactor.
[0106] An adiabatic section of a reactor can be insulated. Within
an adiabatic section of an OCM reactor, a temperature of the
process gas may monotonically increase along a length of the
adiabatic section. This may be caused by the exothermic reaction of
oxygen with methane and other C.sub.2+ hydrocarbons. As the process
gas flows through the adiabatic section, oxygen is depleted.
[0107] FIG. 1A shows an oxidative coupling of methane system 100
that includes an adiabatic section and a non-adiabatic section. A
source containing methane 101 and a source containing oxygen 102
are injected into a section of a reactor that is non-adiabatic and
in thermal communication with a heat transfer medium 103, and then
subsequently injected into a section of a reactor that is
substantially adiabatic 104.
[0108] In some cases, the reactor has an isothermal section and a
light-off section before the isothermal section. As shown in FIG.
1B, the OCM feed (e.g., comprising methane and oxygen) can be mixed
and enter the light-off section 105. The light-off section can have
a first OCM catalyst that initiates an OCM reaction at a low
temperature (e.g., less than about 600.degree. C., less than about
550.degree. C., less than about 500.degree. C., less than about
450.degree. C., or less than about 400.degree. C.). The light-off
section can be in thermal communication with a heat transfer medium
106, such as a molten salt. In some cases, the isothermal section
107 and the light-off section use the same molten salt. In some
instances, there is a heating section 108 of the reactor before the
light-off section, which can be in thermal communication with a
heat transfer medium 109. In some embodiments, the heat transfer
medium in thermal communication with the heating section is
different than the medium in communication with the light-off
section (i.e., because having a molten salt mix between a heating
section and a cooling section may not ideal for either heating or
cooling). With continued reference to FIG. 1B, the OCM feed 110 can
be converted to OCM products 111 including C.sub.2+ compounds and
non-C.sub.2+ impurities. The OCM reactor can include an adiabatic
section 112 as described herein, i.e., which may be insulated as
opposed to being in contact with a heat transfer medium.
[0109] The source containing methane or the source containing
oxygen can also include ethane. The source containing methane or
the source containing oxygen can also include propane.
[0110] The source containing oxygen and/or the source containing
methane can be injected in different locations of the reactor. The
source containing oxygen and/or the source containing methane can
be injecting using a diffuser tube.
[0111] The source containing oxygen can be the same as the source
containing methane. This can be the case if a stream containing
methane and substantially no oxygen is mixed with a stream
containing oxygen and substantially no methane in a section of the
reactor that is upstream of the non-adiabatic section that is in
thermal communication with a heat transfer medium.
[0112] Over time, the oxidative coupling of methane catalyst can
become deactivated. This deactivation can be characterized by a
reduction in the maximum temperature in the non-adiabatic section
of the reactor that is in thermal communication with a heat
transfer medium. With deactivation, there can be a corresponding
reduction in the conversion of oxygen in the non-adiabatic section.
As the oxidative coupling of methane catalyst in the non-adiabatic
section becomes deactivated, the concentration of O.sub.2 at the
outlet of the non-adiabatic section that is in thermal
communication with a heat transfer medium increases. The gas at the
exit of the non-adiabatic section that is in thermal communication
with at heat transfer medium is an intermediate gas stream.
[0113] The intermediate gas stream may contain at least about 100
parts per million (ppm) oxygen, at least about 150 parts per
million (ppm) oxygen, at least about 200 parts per million (ppm)
oxygen, at least about 250 parts per million (ppm) oxygen, at least
about 300 parts per million (ppm) oxygen, at least about 350 parts
per million (ppm) oxygen, at least about 400 parts per million
(ppm) oxygen, at least about 450 parts per million (ppm) oxygen, at
least about 500 parts per million (ppm) oxygen, at least about 550
parts per million (ppm) oxygen, at least about 600 parts per
million (ppm) oxygen, at least about 1000 parts per million (ppm)
oxygen, or more.
[0114] As the oxidative coupling of methane catalyst deactivates,
the concentration of oxygen at the exit of the non-adiabatic
section of the reactor may increase. This corresponds to an
increased concentration of oxygen in the substantially adiabatic
section of the reactor. The increased oxygen concentration in the
substantially adiabatic section of the reactor corresponds to an
increased temperature at the outlet of the substantially adiabatic
section of the reactor.
[0115] As the oxidative coupling of methane catalyst deactivates,
one or more of the following may occur: (i) a concentration of
oxygen at an outlet of the non-adiabatic section in thermal
communication with a heat transfer medium may increase, (ii) a
temperature at the outlet of the non-adiabatic section of the
reactor that is in thermal communication with a heat transfer
medium may decrease, (iii) the concentration of oxygen at an inlet
of the substantially adiabatic section may increase, and (iv) a
temperature at an outlet of the substantially adiabatic section may
increase.
[0116] The percentage of catalyst deactivation in the non-adiabatic
section that is in thermal communication with a heat transfer
medium may correspond to the oxygen conversion (x.sub.O2) at some
time to compared with the conversion at some later time t, such
that catalyst deactivation=[1-x.sub.O2(t)/x.sub.O2(t.sub.o)]*100.
For example, on day 1 the conversion of oxygen in the non-adiabatic
section in thermal communication with a heat transfer medium is
0.99, and on day 100 the conversion of oxygen in the non-adiabatic
section that is in thermal communication with a heat transfer
medium is 0.95. The percentage of catalyst deactivation is then
[1-(0.95)/(0.99)]*100=4.04%.
[0117] The temperature at the outlet of the substantially adiabatic
section may increase over time with deactivation. Under any
deactivation percentage, the temperature at the outlet of the
substantially adiabatic section may be between 500-1000.degree. C.,
between 550-1000.degree. C., between 600-1000.degree. C., between
700-1000.degree. C., between 700-950.degree. C., between
700-900.degree. C., between 750-900.degree. C., or between
750-850.degree. C.
[0118] FIG. 2 shows an oxidative coupling of methane system 200
that uses a mixer, an adiabatic section, and a non-adiabatic
section. A source containing methane 201, and a source containing
an oxidizing agent (e.g., oxygen) 202 are injected into a mixer 203
to produce a mixed gas stream. The temperature of the mixed gas
stream is increased in a heater 204 to bring it to a temperature at
which the oxidative coupling of methane reaction can occur to
produce a heated mixed gas stream. The heated mixed gas stream can
then be injected into a section of a reactor that is non-adiabatic
and in thermal communication with a heat transfer medium 205 to
produce an intermediate gas stream. The intermediate gas stream can
then be injected into a substantially adiabatic section of the
reactor 206.
[0119] The concentration of the oxidizing agent at the inlet of the
non-adiabatic section of the reactor that is in thermal
communication with a heat transfer medium may be greater than or
equal to about 0.1%, 0.5%, 1%, 1.5%, 2%, 5%, 10%, 20% (mol %), or
more.
[0120] The concentration of oxygen at the inlet of the
substantially adiabatic section may be decreased to a percentage of
its inlet concentration, and can be decreased to at least about
0.1%, at least about 0.5%, at least about 1%, at least about 2%, at
least about 5%, at least about 10%, or at least about 20% of its
inlet concentration.
[0121] The time that it takes for the gas to travel between the
non-adiabatic section that is in thermal communication with a heat
transfer medium and the section that is substantially adiabatic
section may be less than about 100 milliseconds (ms), less than
about 80 milliseconds (ms), less than about 50 milliseconds (ms),
less than about 20 milliseconds (ms), less than about 10
milliseconds (ms), less than about 5 milliseconds (ms), less than
about 2 milliseconds (ms) or less than about 1 millisecond
(ms).
The concentration of oxygen (O.sub.2) that exits the adiabatic
section may be less than or equal to about about 1 mol %, 0.5 mol
%, 0.2 mol %, 1000 parts per million (ppm), 500 ppm, 400 ppm, 300
ppm, 200 ppm, 100 ppm, 90 ppm, 80 ppm, 70 ppm, 60 ppm, 50 ppm, 20
ppm, 10 ppm, 5 ppm or less.
[0122] The temperature at the outlet of the adiabatic section may
be greater than or equal to about 600.degree. C., 700.degree. C.,
800.degree. C., 850.degree. C., 880.degree. C., 900.degree. C.,
920.degree. C., 950.degree. C. or more.
[0123] The temperature of the process gas within the non-adiabatic
section of the reactor that is in thermal communication with a heat
transfer medium may reach a maximum within the non-adiabatic
section. The maximum temperature within the non-adiabatic section
that is in thermal communication with a heat transfer medium may be
less than or equal to about 1150.degree. C., 1100.degree. C.,
1050.degree. C., 1000.degree. C., 950.degree. C., 900.degree. C.,
850.degree. C., 800.degree. C., or less.
[0124] The temperature of the source containing oxygen and the
source containing methane before entering into the mixer may be
less than or equal to about 600.degree. C., 550.degree. C.,
500.degree. C., 450.degree. C., 400.degree. C., 350.degree. C., or
less..
[0125] The temperature of the source containing oxygen and the
source containing methane before entering into the mixer may be
less than or equal to about 20 bar(gauge, "g"), less than or equal
to about 15 bar(g) less than or equal to about 10 bar(g), less than
or equal to about 8 bar(g), less than or equal to about 6 bar(g),
less than or equal to about 4 bar(g) or less than or equal to about
2 bar(g).
[0126] FIG. 3 shows an oxidative coupling of methane system 300
that uses methane preheat, adiabatic, and non-adiabatic sections. A
source containing methane 301 is injected into a methane preheater
303 to produce a preheated methane stream. The preheated methane
stream and a source containing oxygen 302 are mixed to produce a
mixture, and injected into a non-adiabatic section of a reactor
that is in contact with a heat transfer medium 304 to produce an
intermediate gas stream. The intermediate gas stream is injected
into a substantially adiabatic section of a reactor 305.
[0127] The source containing methane may be preheated to a
temperature of greater than or equal to about 300.degree. C.,
350.degree. C., 400.degree. C., 450.degree. C., at 500.degree. C.,
550.degree. C., or 600.degree. C.
[0128] Once the preheated methane stream is mixed with the source
containing oxygen to produce the mixture, the temperature of the
mixture may be less than or equal to about 800.degree. C., less
than or equal to about 700.degree. C., less than or equal to about
600.degree. C., less than or equal to about 550.degree. C., less
than or equal to about 500.degree. C., or less than or equal to
about 450.degree. C.
[0129] Before the source containing oxygen is mixed with the
preheated methane stream, the source containing oxygen may have a
temperature of less than or equal to about 300.degree. C., less
than or equal to about 250.degree. C., less than or equal to about
200.degree. C., less than or equal to about 150.degree. C., or less
than or equal to about 100.degree. C.
[0130] When the mixture is injected into the non-adiabatic section
of the reactor, it can flow over an inert packing or an oxidative
coupling of methane catalyst. The inert packing can be alumina
(Al.sub.2O.sub.3), silica (SiO.sub.2), Fe.sub.2O.sub.3, MgO,
Na.sub.2O, another metal oxide, or combinations thereof.
[0131] In another aspect, described herein is a method for
producing an olefin. The method can comprise providing a reactor
having an isothermal section. The isothermal section can contain a
catalyst capable of promoting an oxidative coupling of methane
(OCM) reaction and can be in thermal communication with a heat
transfer medium. In some cases, the isothermal section comprises
the heat transfer medium. The method can include introducing a gas
mixture into the isothermal section of the reactor. The gas mixture
comprises oxygen (O.sub.2) and methane (CH.sub.4), whereby at least
about 75 mol % of the O.sub.2 reacts with the CH.sub.4 to produce
C.sub.2+ compounds and non-C.sub.2+ impurities.
[0132] In some cases, the catalyst promotes an OCM reaction having
a selectivity for C.sub.2+ compounds of at least about 50% at
700.degree. C. In some instances, the catalyst promotes an OCM
reaction having a selectivity for C.sub.2+ compounds of at least
about 60% at 750.degree. C. In some embodiments, the catalyst
promotes an OCM reaction having a selectivity for C.sub.2+
compounds of at least about 65% at 800.degree. C. In some cases,
the gas mixture is introduced into the isothermal section at a
temperature between about 650.degree. C. and about 750.degree. C.
In some cases, the gas mixture exits the isothermal section at a
temperature between about 800.degree. C. and about 900.degree.
C.
[0133] The gas mixture can contain any suitable amount of O.sub.2
when it enters the isothermal section. In some cases, the gas
mixture contains between about 13% and about 17% (mol %) O.sub.2
when it enters the isothermal section. In some cases, the gas
mixture contains greater than or equal to about 5%, 8%, 10%, 12%,
14%, 16%, 18%, 20%, 25% (mol %) O.sub.2, or more, when it enters
the isothermal section. In some cases, the gas mixture contains
less than or equal to about 25%, 20%, 18%, 16%, 14%, 12%, 10% 8%
(mol %) O.sub.2, or less when it enters the isothermal section.
[0134] The gas mixture can contain any suitable amount of O.sub.2
when it exits the isothermal section. In some cases, the gas
mixture contains between about 0.5% and about 3% (mol %) O.sub.2
when it exits the isothermal section. In some cases, the gas
mixture contains greater than or equal to about 0.1%, 0.3%, 0.5%,
1%, 2%, 3%, 5%, 7%, 10% (mol %) O.sub.2, or more when it exits the
isothermal section. In some cases, the gas mixture contains less
than or equal to about 10%, 7%, 5%, 3%, 2%, 1%, 0.5%, 0.3%, 0.1%
(mol %) O.sub.2, or less when it exits the isothermal section.
[0135] Any suitable amount of the CH.sub.4 is converted to C.sub.2+
compounds and non-C.sub.2+ impurities in the isothermal section. In
some cases, between about 12% and about 16% (mol %) of the CH.sub.4
is converted to C.sub.2+ compounds and non-C.sub.2+ impurities in
the isothermal section. In some embodiments, greater than to equal
to about 3%, 5%, 7%, 10%, 12%, 14%, 16%, 18%, 20% (mol %) of the
CH.sub.4, or more is converted to C.sub.2+ compounds and
non-C.sub.2+ impurities in the isothermal section. In some
embodiments, less than or equal to about 20%, 18%, 16%, 14%, 12%,
10%, 9%, 7%, 5%, 3% (mol %) of the CH.sub.4, or less is converted
to C.sub.2+ compounds and non-C.sub.2+ impurities in the isothermal
section.
[0136] The catalyst in the isothermal section can be a perovskite
or comprises a lanthanide element. In some cases, the catalyst does
not shrink or sinter when operated at OCM performance
conditions.
[0137] A relatively large amount of the O.sub.2 can be reacted in
the isothermal section. In some cases, greater than or equal to
about 70%, 75%, 80%, 85%, 90%, 95% (mol %) of the O.sub.2, or more
reacts with the CH.sub.4 to produce C.sub.2+ compounds and
non-C.sub.2+ impurities. In some cases, less than or equal to about
95%, 90%, 85%, 80%, 75%, 70% (mol %) of the O.sub.2, or less reacts
with the CH.sub.4 to produce C.sub.2+ compounds and non-C.sub.2+
impurities.
[0138] The reactor can further comprise a light-off section in
fluid communication with and upstream from the isothermal section.
The light-off section can be in thermal communication with an
additional heat transfer medium and contains a catalyst capable of
promoting an OCM reaction. The light-off section may comprise the
additional heat transfer medium. The catalyst in the light-off
section can be different than the OCM catalyst in the isothermal
section.
[0139] The method can further comprise introducing a gas mixture
into the light-off section of the reactor. The gas mixture can
comprises oxygen (O.sub.2) and methane (CH.sub.4), whereby at least
at least some of the O.sub.2 reacts with the CH.sub.4 to produce
C.sub.2+ compounds before the gas mixture enters the isothermal
section.
[0140] The heat transfer medium and the additional heat transfer
medium can be molten salts, optionally the same molten salt. Any
suitable molten salt can be used. In some cases, the molten salt
has a melting point less than about 700.degree. C. and a boiling
point greater than about 700.degree. C. In some cases, the melting
point is less than about 400.degree. C., less than about
450.degree. C., less than about 500.degree. C., less than about
550.degree. C., less than about 600.degree. C., less than about
650.degree. C., less than about 700.degree. C., or less than about
750.degree. C. In some cases, the boiling point is greater than
about 600.degree. C., greater than about 650.degree. C., greater
than about 700.degree. C., greater than about 750.degree. C.,
greater than about 800.degree. C., greater than about 850.degree.
C., greater than about 900.degree. C., or greater than about
950.degree. C. The molten salt does not decompose at the operating
temperature of OCM.
[0141] The molten salt can be any suitable salt. Suitable anions
can include chlorides, fluorides, fluoroborates, perchlorates,
carbonates, or oxides. Suitable cations can include any element
from groups 1 to 14 of the periodic table. The molten salt can
include a mixture of salts, such as a eutectic mixture. Particular
eutectic mixtures include MgCl.sub.2/KCl (e.g., at 33/67 mol %);
NaCl/KCl/ZnCl.sub.2 (e.g., at 8-10%/10-20%/60-80 mol %); and
LiF/NaF/BeF.sub.2 (e.g., at 31/31/38 mol %).
[0142] The catalyst in the light-off section can promote an OCM
reaction having a selectivity for C.sub.2+ compounds of at least
about 30% at 550.degree. C. In some embodiments, the catalyst in
the light-off section can promote an OCM reaction having a
selectivity for C.sub.2+ compounds of at least about 40% at
600.degree. C.
[0143] In some cases, the reactor further comprises a heating
section in fluid communication with and upstream of the light-off
section, which heating section is in thermal communication with a
further additional heat transfer medium, which is optionally a
molten salt. The heating section may comprise the further
additional heat transfer medium. Suitable molten salts are
described above. In some cases, the molten salt in contact with the
heating section does not mix with the molten salt in contact with
the light-off or isothermal sections of the OCM reactor.
[0144] The gas mixture can be introduced into the light-off section
at any suitable temperature. In some embodiments, the temperature
is between about 450.degree. C. and about 580.degree. C. In some
cases, the temperature at the inlet to the light-off section is
less than about 650.degree. C., less than about 620.degree. C.,
less than about 600.degree. C., less than about 580.degree. C.,
less than about 560.degree. C., less than about 540.degree. C.,
less than about 520.degree. C., less than about 500.degree. C.,
less than about 480.degree. C., less than about 460.degree. C.,
less than about 440.degree. C., less than about 420.degree. C., or
less than about 400.degree. C.
[0145] The gas mixture can exit the light-off section at any
suitable temperature. In some embodiments, the gas mixture exits
the light-off section at a temperature between about 650.degree. C.
and about 750.degree. C. In some cases, the exit temperature is
about 550.degree. C., about 600.degree. C., about 650.degree. C.,
about 700.degree. C., about 750.degree. C., about 800.degree. C.,
or about 850.degree. C.
[0146] Any suitable amount of CH.sub.4 can be converted to C.sub.2+
compounds and non-C.sub.2+ impurities in the light-off section. In
some cases, between about 3% and about 5% (mol %) of the CH.sub.4
in the feed is converted to C.sub.2+ compounds and non-C.sub.2+
impurities in the light-off section. In some embodiments, greater
than or equal to about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% (mol %) of
the CH.sub.4, or more is converted to C.sub.2+ compounds and
non-C.sub.2+ impurities in the light-off section.
[0147] The gas mixture can contain any suitable amount of O.sub.2
when it enters the light-off section. In some cases, the gas
mixture contains between about 15% and about 20% (mol %) O.sub.2
when it enters the light-off section. In some embodiments, the gas
mixture contains greater than or equal to about 5%, 10%, 15%, 20%,
25%, 30%, 35% (mol %) O.sub.2, or more when it enters the light-off
section. In some embodiments, the gas mixture contains less than or
equal to about 35%, 30%, 25%, 20%, 15%, 10% (mol %) O.sub.2, or
less when it enters the light-off section.
[0148] The gas mixture can contain any suitable amount of O.sub.2
when it exits the light-off section. In some cases, the gas mixture
contains between about 13% and about 17% (mol %) O.sub.2 when it
exits the light-off section. In some embodiments, the gas mixture
contains greater than or equal to about 5%, 10%, 15%, 20%, 25%,
30%, 35% (mol %) O.sub.2, or more when it exits the light-off
section. In some embodiments, the gas mixture contains less than or
about 35%, 30%, 25%, 20%, 15%, 10%, (mol %) O.sub.2, or less when
it exits the light-off section.
[0149] The catalyst in the light-off section can be any material
which catalyzes an OCM reaction at the conditions in the OCM
reactor. In some cases, the catalyst comprises nanowires. The
catalyst in the light-off section can be capable of performing
oxidative dehydrogenation (ODH). Suitable catalysts can be found in
U.S. Pat. Nos. 9,718,054 and 8,962,517, each of which are
incorporated herein by reference in their entirety.
[0150] Any suitable amount of the O.sub.2 entering the light-off
section can be converted to C.sub.2+ compounds and non-C.sub.2+
impurities. In some embodiments, greater than or equal to about 5%,
10%, 15%, 20%, 25%, 30% (mol %) of the O.sub.2, or more entering
the light-off section reacts with the CH.sub.4 to produce C.sub.2+
compounds and non-C.sub.2+ impurities. In some embodiments, less
than or equal to about 30%, 25%, 20%, 15%, 10% (mol %) of the
O.sub.2, or less entering the light-off section reacts with the
CH.sub.4 to produce C.sub.2+ compounds and non-C.sub.2+
impurities.
[0151] In some embodiments, the reactor further comprises an
adiabatic section in fluid communication with and downstream from
the isothermal section. The adiabatic section can be insulated and
contain a catalyst capable of promoting an OCM reaction. The
catalyst in the adiabatic section can be different than or the same
as the catalyst in the light-off and isothermal sections of the
reactor. In some cases, the catalyst is a perovskite. In some
embodiments, the catalyst also performs oxidative dehydrogenation
(ODH).
[0152] In some cases, the method further comprises introducing the
gas mixture exiting the isothermal section into the adiabatic
section, whereby the concentration of O.sub.2 exiting the adiabatic
section is less than about 2000 parts per million (ppm), less than
about 1000 ppm, less than about 500 ppm, less than about 100 ppm,
less than about 50 ppm, less than about 10 ppm, or less than about
5 ppm.
[0153] The adiabatic section can contain a catalyst capable of
promoting an OCM reaction at a net selectivity for C.sub.2+
compounds of between about 0% and about 20% at 850.degree. C. In
some cases the net selectivity is at least about 0%, at least about
5%, at least about 10%, at least about 15%, at least about 20%, at
least about 25%, at least about 30%, or at least about 40%.
[0154] In some cases, relatively little reforming reaction takes
place in the adiabatic section of the OCM reactor. In some
embodiments, less than or equal to 30%, 25%, 20%, 15%, 10%, 5%, 3%,
1% (mol %) of the CH.sub.4, or less that enters the adiabatic
section is reformed into CO and H.sub.2.
[0155] In some cases, the adiabatic section scrubs the remaining
O.sub.2 from the OCM product stream and relatively little methane
is converted in the adiabatic section compared to the amount
converted in the light-off and isothermal sections. In some
instances, between about 0% and about 3% (mol %) of the CH.sub.4 is
converted to C.sub.2+ compounds and non-C.sub.2+ impurities in the
adiabatic section. In some cases, less than or equal to about 15%,
10%, 5%, 3%, 2%, 1% (mol %) of the CH.sub.4 in the feed, or less is
converted to C.sub.2+ compounds and non-C.sub.2+ impurities in the
adiabatic section.
[0156] Ethane can be added to the adiabatic section. The method can
further comprise adding between about 0% and about 5% (mol %)
ethane (C.sub.2H.sub.6) to the gas mixture near the inlet of the
adiabatic section.
[0157] The gas mixture can enter the adiabatic section at any
suitable temperature. In some cases, the gas mixture is introduced
into the adiabatic section at a temperature between about
800.degree. C. and about 900.degree. C. In some cases, the inlet
temperature is at least about 650.degree. C., at least about
700.degree. C., at least about 750.degree. C., at least about
800.degree. C., at least about 850.degree. C., at least about
900.degree. C., or at least about 950.degree. C. In some cases, the
inlet temperature is at most about 650.degree. C., at most about
700.degree. C., at most about 750.degree. C., at most about
800.degree. C., at most about 850.degree. C., at most about
900.degree. C., or at most about 950.degree. C.
[0158] The gas mixture can exit the adiabatic section at any
suitable temperature. In some cases, the gas mixture exits the
adiabatic section at a temperature between about 850.degree. C. and
about 950.degree. C. In some cases, the exit temperature is at
least about 650.degree. C., at least about 700.degree. C., at least
about 750.degree. C., at least about 800.degree. C., at least about
850.degree. C., at least about 900.degree. C., or at least about
950.degree. C. In some cases, the exit temperature is at most about
650.degree. C., at most about 700.degree. C., at most about
750.degree. C., at most about 800.degree. C., at most about
850.degree. C., at most about 900.degree. C., or at most about
950.degree. C.
[0159] The reactor can further comprise a post-bed cracking (PBC)
section in fluid communication with and downstream of the adiabatic
section, which PBC section converts C.sub.2H.sub.6 into
C.sub.2H.sub.4 using heat derived from OCM. The method can further
comprise adding between about 1% and about 5% (mol %) ethane
(C.sub.2H.sub.6) to the gas mixture near the inlet of the PBC
section.
[0160] The reactor described herein, including an isothermal
section and optionally a heating section, light-off section,
adiabatic section and PBC section converts a relatively high amount
of methane into C.sub.2+ compounds. In some cases, greater than or
equal to about 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% (mol %) of
the CH.sub.4 in the feed, or more is converted to C.sub.2+
compounds and non-C.sub.2+ impurities in the OCM reactor.
[0161] In another aspect, described herein is a system for
performing oxidative coupling of methane (OCM). The system can
comprise a reactor having an isothermal section and either a
light-off section or an adiabatic section. The reactor can have
both the light-off section and the adiabatic section.
[0162] The light-off section can be adapted to accept a gas mixture
comprising oxygen (O.sub.2) and methane (CH.sub.4) and contains a
first OCM catalyst that can convert the O.sub.2 and CH.sub.4 into
C.sub.2+ compounds at a selectivity of at least about 30% at
550.degree. C., wherein the light-off section is in thermal
communication with a first heat transfer medium. The light-off
section may comprise the first heat transfer medium.
[0163] The isothermal section can be in fluidic communication with
and downstream of the light-off section and contain a second OCM
catalyst that has a selectivity for C.sub.2+ compounds of at least
about 50% at 700.degree. C., wherein the isothermal section is in
thermal communication with a second heat transfer medium. The
isothermal section may comprise the second heat transfer
medium.
[0164] The adiabatic section can be in fluidic communication with
and downstream of the isothermal section and contain a third OCM
catalyst that has a net selectivity for C.sub.2+ compounds of at
least about 0% at 850.degree. C.
[0165] In some cases, the reactor further comprises a post-bed
cracking (PBC) section in fluid communication with and downstream
of the adiabatic section, which PBC section converts C.sub.2H.sub.6
into C.sub.2H.sub.4 using heat derived from OCM.
[0166] The reactor can be adapted to operate at a pressure of
greater than or equal to about 2 bar(g), greater than about 4
bar(g), or greater than about 8 bar(g).
[0167] The reactor can be a tubular reactor. The first and second
heat transfer medium can be the same material, such as a molten
salt.
[0168] Methanation is an exothermic reaction. In some cases, the
conversion in a methanation reactor is limited by the ability to
handle the temperature rise of the reaction, e.g., by removing
heat. If one were to practice the systems and methods described
herein and use a molten salt OCM reactor, that molten salt system
could also be used to cool a methanation reactor. The methanation
could be performed in a separate reactor or in a separate section
of the same OCM reactor (e.g., upstream of the light-off section).
In some cases, the system further comprises a methanation reactor
that is in fluid communication with the first heat transfer medium
or the second heat transfer medium. The methanation section can be
in fluidic communication with and upstream of the light-off section
which contains a methanation catalyst. Further embodiments
describing the use of methanation in OCM systems and suitable
methanation catalysts can be found in U.S. Pat. No. 9,701,597,
which is incorporated herein by reference in its entirety.
[0169] In some cases, the source containing methane and the source
containing oxygen can be mixed before being heated, and
subsequently be heated over an inert packing in the non-adiabadic
section of the reactor.
[0170] FIG. 4 shows an oxidative coupling of methane system that
includes a methane preheater and a steam superheater 400. A source
containing methane 401 is injected into a methane preheater 403 to
produce a preheated methane stream. A source containing oxygen 402
and the preheated methane stream are injected into a non-adiabatic
section of a reactor 404. The non-adiabatic section is in thermal
communication with a heat transfer agent that is in circulation
with a steam superheater 406. The heat transfer agent that is in
circulation with a steam superheater can be a molten salt. The
steam superheater can be integrated with the non-adiabatic section
of the reactor in a single vessel. Effluent from the non-adiabatic
section is injected into an adiabatic section of a reactor 405.
[0171] FIG. 5 shows an oxidative coupling of methane system that
includes a mixer and a steam superheater 500. A source containing
methane 501 and a source containing oxygen 502 are injected into a
mixer 503 to produce a mixture. The mixture is injected into a
preheater 504 to produce a preheated mixture. The preheated mixture
is injected into a non-adiabatic section of a creator that is in
thermal communication with a heat transfer medium. The heat
transfer medium is in circulation with a steam superheater 507. The
effluent of the non-adiabatic section is injected into a
substantially adiabatic section 506.
[0172] FIG. 6 shows an oxidative coupling of methane system that
includes a heat exchanger downstream of the oxidative coupling of
methane reactor 600. A source containing ethane 606 and a source
containing methane 605 are injected into a feed preheater 604. A
source containing a fuel 603 is also injected into the feed
preheater 604 to produce a preheated hydrocarbon stream. The
preheated hydrocarbon stream and a source containing oxygen 601 are
injected into a reactor that includes at least one non-adiabatic
section and at least one substantially adiabatic section 602 to
produce an OCM reactor effluent. The OCM reactor effluent is
subsequently injected into a heat exchanger 607.
[0173] FIG. 7 shows an oxidative coupling of methane system that
uses a heat transfer medium to preheat the feed gas 700. A source
containing oxygen 701, a source containing methane 702, and a
source containing ethane 703 are injected into a reactor that
includes a mixer, at least one non-adiabatic section and at least
one substantially adiabatic section 704 to produce an OCM reactor
effluent. The OCM reactor effluent is subsequently injected into a
heat exchanger 707.
[0174] FIG. 8 shows an oxidative coupling of methane reactor that
includes an adiabatic and non-adiabatic sections 800. The reactor
may comprise tubes that contain OCM catalyst 803. One end of the
tube is surrounded by insulation 801, constituting a substantially
adiabatic section of the reactor. The middle section of the tubes
is surrounded by a heat transfer medium 802 constituting a
non-adiabatic section that is in thermal communication with a heat
transfer medium. The opposing end of the tube is surrounded by
insulation, constituting a second substantially adiabatic section
804.
[0175] The reactor can contain greater than or equal to about 2, 5,
10, 20, 30, 40, 50, 60, 70, 80, 90, 100 tubes or more.
[0176] The pressure drop across the tubes may be less than or equal
to 3 bar(g), 2.5 bar(g), 2 bar(g), 1.5 bar(g), 1 bar(g), 0.5 bar(g)
or less.
[0177] The diameter of each tube may be greater than or equal to
about 0.25 inches, 0.5 inches, 0.75 inches, 1 inch, 1.25 inches or
more.
[0178] The length of each tube may be greater than about 4 feet and
less than about 12 feet, greater than about 5 feet and less than
about 11 feet, greater than about 6 feet and less than about 10
feet, or greater than about 7 feet and less than about 9 feet.
[0179] The gas velocity in each tube may be greater than about 3
meters per second (m/s) and less than about 10 meters per second
(m/s), greater than about 4 meters per second (m/s) and less than
about 9 meters per second (m/s), or. greater than about 5 meters
per second (m/s) and less than about 8 meters per second (m/s).
[0180] The pressure of gas within each tube may be greater than
about 4 bar(g) and less than about 10 bar(g), greater than about 5
bar(g) and less than about 9 bar(g), or greater than about 6 bar(g)
and less than about 8 bar(g).
[0181] In the non-adiabatic section of the reactor that is in
thermal communication with a heat transfer medium, there may be a
temperature gradient within each tube between the center of the
tube and the wall of the tube. The temperature gradient may be at
least about 1.degree. C./inch, at least about 10.degree. C./inch,
at least about 20.degree. C./inch, at least about 30.degree.
C./inch, at least about 40.degree. C./inch, at least about
50.degree. C./inch, at least about 60.degree. C./inch, at least
about 70.degree. C./inch, at least about 80.degree. C./inch, at
least about 90.degree. C./inch, at least about 100.degree. C./inch,
at least about 120.degree. C./inch, at least about 150.degree.
C./inch, at least about 175.degree. C./inch, at least about
200.degree. C./inch, or at least about 250.degree. C./inch.
[0182] FIG. 9 shows an oxidative coupling of methane reactor that
includes diffuser tubes, adiabatic, and non-adiabatic sections 900.
A feed gas is injected into the reactor using a diffuser tube 901.
The reactor comprises tubes that contain catalyst 904 and inert
packing material 902. The inert packing material at the entrance of
the tube 902 is in a non-adiabatic section of the reactor that is
in thermal communication with a heat transfer medium 903. One gas
is fed into the reactor on the interior of the diffuser tube and
one gas is fed on the exterior of the diffuser tube. The tubes at
the exit of the reactor are surrounded by insulation, constituting
a substantially adiabatic section of the reactor 905.
[0183] A portion of the substantially adiabatic section may or may
not contain OCM catalyst. Ethane can optionally be added to the
substantially adiabatic section of the reactor, and may undergo
post bed cracking to generate ethylene.
[0184] FIG. 10 shows a diffuser tube within a reactor tube 1000.
The diffuser tube may comprise a number of manifolds for the
addition of gases 1001-1003. These manifolds are attached to
concentric perforated tubes 1004-1005 that injects gas feeds into
the reactor tube 1006.
[0185] FIG. 11 shows an oxidative coupling of methane reactor that
uses molten salt as a heat transfer medium. This may include a
vessel that is partially filled with molten salt 1101 and
surrounded by insulation 1102. The top section of the reactor is
filled with air, and corresponds to a substantially adiabatic
section. The portion that is filled with molten salt is a
non-adiabatic section. The process gas 1105 is fed into the
U-shaped tube reactor that contains inert packing 1103. This
section of the reactor serves to mix and preheat the feed gas. The
gas makes a turn and enters a section that contains an OCM catalyst
1104. This section is non-adiabatic. The gas then moves to a
section of the reactor that does not contain molten salt, and is
substantially adiabatic.
[0186] In some cases, the reactor, salt bath, and other process
equipment are made of materials that are compatible with molten
salts. Examples include high nickel content steels (e.g., >20
mol % Ni), austentic steels, carbon steels, or nickel cladded
steels. In some embodiments, the process equipment is protected by
cathodic protection. A sacrificial reductant can be used. This can
reduce corrosion of the reactor body. For example, magnesium,
zirconium, or beryllium can be in the salt as particles or used as
billets on the reactor bath interior. Any metal can be used with a
standard reduction potential more negative than Cr.sub.3+/Cr redox
couple (i.e., less than about 0.77 vs. Standard Hydrogen
Electrode). In some embodiments, the bath atmosphere can be
controlled. For example an inert gas can be used as a blanket. In
some cases, O.sub.2 and H.sub.2O are at less than about 10 ppm.
[0187] FIG. 29 shows an example of a block flow diagram. The
natural gas inlet 2901 can contain 0-30 mol % ethane, 0-30 mol %
propane, 0-30 mol % butane, 0-20 wt % light naptha, and 8-20 mol %
O.sub.2. The start-up reactor 2902 can be a fired heater, for
example, with an outlet temperature of less than about 800.degree.
C. The start-up reactor can be an adiabatic OCM reactor and can be
bypassed after initial salt heating. The main reactor 2903 can be a
reactor having an isothermal section as described herein. In some
cases, it has a post-bed cracking section. The salt reservoir 2904
can be used for heat exchange, and can be used to produce high
pressure (HP) steam. Heat exchangers 2905 can be used to recover
heat and cool the stream. A separation module 2906 can be used to
recover products or a recycle stream.
[0188] In some cases, the reactor is tubular. In some instances,
the reactor does not have a constant cross sectional area. With
reference to FIG. 31, a narrowing cross section can be used to
achieve a more uniform temperature profile across the reactor. For
example, when the reactor is of uniform width 3100, in this case a
1 inch diameter by 30 inch length tube, the temperature has a sharp
profile 3102. However, when tube inserts restrict the periphery of
the tube 3104 to narrow it, the temperature profile is more flat
3106. Here, the tube starts at 2 inches and reduces to 0.5 inches,
having an average diameter of 1 inch (matching 3100). The reactor
diameter can also be narrowed by inserting rods in the center of
the reactor 3108 to achieve a similar flat temperature profile
3110.
OCM Reactor Configurations
[0189] In some cases, it may be desirable to have an OCM system
with at least about 30% capital expenditure (Capex) reduction
compared to convention methods for OCM reactions. This can be
achieved by doubling the ethylene yield of an OCM process. One way
to achieve the target (i.e., doubling the ethylene yield) is to
double the methane conversion while maintaining the same
selectivity for ethylene. Since the OCM reaction may be limited by
a concentration of oxidizing agents (e.g., oxygen), the methane
conversion can be elevated by increasing a concentration of the
oxidizing agents. In cases where an OCM feed stream comprises an
increased concentration of oxidizing agents, a substantially
adiabatic reactor may not be suitable for performing an OCM process
due to a significant increase in heat generation during the OCM
process. A tubular reactor system may be used for removing the heat
generated by the OCM process such that the OCM process can be
conducted using a feed having an increased concentration (relevant
to a concentration used in conventional OCM processes) of oxidizing
agents, which OCM processes may yield a higher methane conversion
while maintaining a similar outlet temperature and/or ethylene
selectivity. In some cases, the tubular reactor system is a molten
salt tubular reactor system.
[0190] An OCM product gas may comprise ethane and ethylene. As
discussed above and elsewhere herein, a Post Bed Cracking unit
(PBC) can be utilized to convert the ethane from the OCM product
gas to additional ethylene. However, in some situations, it may not
be ideal to use a PBC unit in a molten salt tubular reactor system.
For example, in some cases, an outlet temperature of the reactor
system does not fall within a desired range (e.g., greater than or
equal to about 800.degree. C., 850.degree. C., 900.degree. C.,
950.degree. C. or more) and since the molten salt tubular reactor
is very efficient in removing heat, once the oxidizing agent is
depleted, the temperature may drop rapidly. In view of this, some
aspects of the present disclosure provide alternative designs of
OCM systems.
[0191] An OCM system may comprise a molten salt reactor and a
substantially adiabatic reactor in fluidic and/or thermal
communication with the molten salt reactor. The molten salt reactor
may be configured to receive an OCM feed stream comprising an
oxidizing agent (e.g., oxygen) and methane. The molten salt reactor
may comprise a catalyst that may facilitate an OCM reaction. The
molten salt reactor may permit at least a portion of the oxidizing
agent and the methane to react in an OCM reaction with the aid of
the catalyst. The OCM reaction may generate a product stream
comprising higher hydrocarbons (e.g., C.sub.2+ compounds),
unreacted methane, unreacted oxidizing agent and/or impurities. The
product stream may be directed into the substantially adiabatic
reactor. The substantially adiabatic reactor may comprise a
catalyst that may facilitate OCM reactions. The substantially
adiabatic reactor may react at least a portion of the unreacted
methane and oxidizing agent in an OCM reaction with the aid of the
catalyst within the reactor. The OCM reaction occurred in the
substantially adiabatic reactor may generate heat. The heat may
increase an outlet temperature of the reactor to a predetermined
value or range (e.g., greater than or equal to about 800.degree.
C., 850.degree. C., 900.degree. C., 950.degree. C. or more). In
some cases, an OCM system may comprise a plurality of OCM reactors.
At least some of the OCM reactors may comprise multiple sections
(e.g., a molten salt section and a substantially adiabatic
section).
[0192] In some cases, an OCM system comprises a molten salt reactor
and an oxidative dehydrogenation (ODH) reactor in fluidic and/or
thermal communication with the molten salt reactor. The molten salt
reactor may be configured to receive an OCM feed stream comprising
an oxidizing agent (e.g., oxygen) and methane. The molten salt
reactor may comprise a catalyst that may facilitate an OCM
reaction. The molten salt reactor may permit at least a portion of
the oxidizing agent and the methane to react in an OCM reaction
with the aid of the catalyst.
[0193] The ODH reactor may comprise a catalyst. The catalyst may
facilitate an ODH reaction. The ODH reactor may be configured to
receive an effluent stream from the molten salt reactor. The
effluent stream may comprise methane, higher hydrocarbon compounds
(e.g., C.sub.2+ compounds), unreacted oxidizing agents and/or
non-C.sub.2+ impurities (e.g., hydrogen, nitrogen, carbon monoxide
and carbon dioxide). The ODH reactor may convert ethane into
ethylene with the aid of a catalyst. In some cases, the ODH reactor
utilizes carbon dioxide or oxygen to convert paraffins to olefins
(e.g., ethane to ethylene, or propane to propylene). In cases where
carbon dioxide is used to convert paraffins to olefins in an ODH
reaction, the ODH reaction may yield a product stream which
comprises carbon monoxide. At least a portion of the carbon
monoxide generated in the ODH reaction may be directed into a
methanation unit for a methanation reaction. Some or all of methane
generated in the methanation reaction may be recycled to the molten
salt reactor.
[0194] In some cases, an OCM system may comprise a plurality of OCM
reactors. At least some of the OCM reactors may comprise multiple
sections (e.g., a molten salt section and an ODH section). In some
cases, an OCM system comprises a single reactor comprising a first
catalyst that facilitates OCM reactions and a second catalyst that
facilitates ODH reactions. The second catalyst may be downstream of
the first catalyst. In some cases, an OCM system comprises an OCM
reactor that facilitates both an OCM reaction and an ODH reaction.
In some cases, an OCM system may comprise a catalyst which is a
blend of an OCM catalyst and an ODH catalyst. In some cases, an OCM
system comprises a gradient reactor that starts with 100% OCM
catalysts and ends with 100% ODH catalysts.
[0195] An ODH reaction may be conducted at a temperature that is
greater than or equal to about 500.degree. C., 550.degree. C.,
600.degree. C., 650.degree. C., 700.degree. C., 750.degree. C.,
800.degree. C., 850.degree. C., 900.degree. C. or more. In some
cases, an ODH reaction is conducted at a temperature that is less
than or equal to about 1,000.degree. C., 950.degree. C.,
900.degree. C., 850.degree. C., 800.degree. C., 750.degree. C.,
700.degree. C., 650.degree. C., 600.degree. C., or less. In some
cases, an ODH reaction is conducted at a temperature that is
between any two values described herein, for example, between about
500.degree. C. and 900.degree. C., or between about 600.degree. C.
and 800.degree. C.
[0196] Various catalysts can be used in an ODH reaction (e.g., a
CO.sub.2 ODH reaction or a O.sub.2 ODH reaction). Non-limiting
examples of ODH catalysts include, Cr.sub.2O.sub.3 supported on
SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2 or ZrO.sub.2,
Cr/SO.sub.4--SiO.sub.2, K--Cr/SO.sub.4--SiO.sub.2,
K--Cr--Mn/SiO.sub.2, Cr/H-ZSM-5, Cr/Silicalite-2,
Fe--Mn/Silicalite-2, Cr--Mn/Silicalite-2, Cr--Mn--Ni/Silicalite-2,
MnO.sub.2, K-doped MnO.sub.2, Na.sub.2WO.sub.4--Mn/SiO.sub.2,
CeO.sub.2, Fe--Cr/ZrO.sub.2, or combinations thereof.
[0197] In some aspects of the present disclosure, a system for
performing oxidative coupling of methane (OCM) is provided. The
system may comprise an OCM reactor. The OCM reactor may be a
micro-channel OCM reactor. The OCM reactor may comprise at least
one corrugated metal foil. The metal foil may comprise ridges and
intervening grooves between the ridges. In some cases, the
intervening grooves are between each two adjacent ridges. The
grooves may be micro-channels. The micro-channels may have an
average width greater than or equal to about 50 micrometers
(.mu.m), 75 .mu.m, 100 .mu.m, 150 .mu.m, 200 .mu.m, 250 .mu.m, 300
.mu.m, 350 .mu.m, 400 .mu.m, 450 .mu.m, 500 .mu.m, or more. In some
cases, the micro-channels have an average width less than or equal
to about 1,000 .mu.m, 900 .mu.m, 800 .mu.m, 700 .mu.m, 600 .mu.m,
500 .mu.m, 400 .mu.m, 300 .mu.m, 200 .mu.m, 100 .mu.m, or less. In
some cases, the micro-channels have an average width falling
between any of the two values described herein, for example,
between about 200 .mu.m and about 500 .mu.m.
[0198] The OCM reactor may also comprise a catalyst that may
facilitate an OCM reaction. The catalyst may be disposed within the
grooves of the metal foil. In some cases, the OCM reactor comprises
a plurality of the corrugated metal plates or foils (e.g., greater
than or equal to about 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30,
35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120,
130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350, 400, 450,
500 or more). Some or all of the metal foils may be assembled in
stacks. At least a portion of the metal foils (e.g., greater than
or equal to about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%,
95%, or more) may comprise perforations. The perforations may
create passageways between the metal foils. The perforations may be
made in selected areas of the metal foil by cutting or pressing on
die. The metal foils may comprise active areas (or zones). The
catalyst may be disposed in the active areas only. The OCM reaction
may be conducted in the active areas.
[0199] In some cases, the system comprises a flow through
component. The flow through component may be integrated with an OCM
reactor. The flow through component may be a part of an OCM
reactor. The flow through component may enable a low velocity
operation with large surface area for process gas to enter the
catalyst bed of the OCM reactor. In some cases, the velocity is
less than or equal to about 3 m/s, 2 m/s, 1 m/s, 0.9 m/s, 0.8 m/s,
0.7 m/s, 0.6 m/s, 0.5 m/s, 0.4 m/s, 0.3 m/, 0.2 m/s, 0.1 m/s, 0.09
m/s, 0.08 m/s, 0.07 m/s, 0.06 m/s. 0.05 m/s, 0.04 m/s, 0.03 m/s,
0.02 m/s, 0.01 m/s, or less. In some cases, the velocity is between
any of the two values described herein, for example, between about
0.05 m/s and about 0.3 m/s.
[0200] In some cases, the system comprises a manifold design in
fluidic communication with the OCM reactor. The manifold may be
used for gas distribution. Layer(s) of thermal isolation material
may be used in inlet gas distribution manifold or on a side of
catalyst pack bed assembly so as to provide a feed gas with a
homogeneous temperature across the catalyst pack bed assembly.
[0201] FIGS. 37 and 38 show example of micro-channel OCM reactors.
FIG. 37 shows a side view of a set of two catalyst assembly stacks
comprising offset perforations for feed inlet and product outlet.
Small dots comprised in each sheet represent packed catalyst
particles. In FIG. 38, an OCM reactor may comprise a metal plate
comprising multiple active zones (e.g., 32 squares in the figure).
Remaining areas in the plate may be used for feed conditioning or
distribution. The feed flow path in such areas (i.e., the remaining
areas) may be designed with race tracks so as to provide sufficient
heat exchange to obtain substantially the same temperature in each
active zone. The different zones may be created in the same plate
(or sheet) through stamping different corrugation patterns and
perforations. Some or all of the zones may be used to conduct the
same or different reactions. In some cases, feed and product gas
are put in thermal contact to minimize the need to pre-heating the
feed prior to the reaction.
Dilution of Feed for Increased Methane Conversion
[0202] Another aspect of the present disclosure is to provide a
method for improving methane conversion in an oxidative coupling of
methane process using a diluent. A diluent, such as water
(H.sub.2O), carbon dioxide (CO.sub.2), or combinations thereof, can
absorb energy during an exothermic oxidative coupling of methane
reaction, and can provide energy during an endothermic cracking
operation. Further, a diluent can be used to reduce the
concentration of oxygen (O.sub.2) in a feed stream, which can
improve the durability of an apparatus that is used to inject a
source containing oxygen (O.sub.2). The oxygen and the diluent can
be pre-mixed before adding to a reactor, and a pre-mixed oxygen and
diluent stream can be added to a reactor downstream of where a
stream containing methane is injected.
[0203] In another aspect of the present disclosure, provided herein
is a method for producing an olefin. The method can comprise
producing a gas stream comprising methane (CH.sub.4), oxygen
(O.sub.2), and a diluent and passing the gas stream over an
oxidative coupling of methane (OCM) catalyst at a pressure of at
least about 2 bar(g) to convert at least some of the CH.sub.4 into
C.sub.2+ compounds, wherein a ratio of diluent molecules to carbon
atoms in the gas stream is at least about 0.1.
[0204] The diluent can comprise water (H.sub.2O) and/or carbon
dioxide (CO.sub.2).
[0205] The ratio of diluent molecules to carbon atoms in the gas
stream can be any suitable value. In some cases, the ratio of
diluent molecules to carbon atoms in the gas stream is at least
about 0.01, at least about 0.05, at least about 0.1, at least about
0.5, at least about 1, at least about 5, at least about 10, or at
least about 20. In some cases, the ratio of diluent molecules to
carbon atoms in the gas stream is at most about 0.01, at most about
0.05, at most about 0.1, at most about 0.5, at most about 1, at
most about 5, at most about 10, or at most about 20. The ratio of
diluent molecules to carbon atoms in the gas stream can be between
about 0.1 and about 5.
[0206] The pressure can be greater than or equal to about 4 bar(g),
5 bar(g), 6 bar(g), 7 bar(g), 8 bar(g), 9 bar(g), 10 bar(g), or
more in some cases.
[0207] FIG. 12 shows an oxidative coupling of methane process using
a diluent stream 1200. A stream containing oxygen 1201, a stream
containing methane 1202, and a stream containing a diluent 1203 are
injected into a reactor containing an oxidative coupling of methane
catalyst 1204. The effluent of the reactor is then injected into a
post bed cracking unit 1205 that does not contain an oxidative
coupling of methane catalyst.
[0208] The stream containing oxygen can be the same as the stream
containing methane, or the stream containing oxygen can be the same
as the stream containing the diluent.
[0209] The diluent can be water (H.sub.2O), carbon dioxide
(CO.sub.2), or combinations thereof.
[0210] The fraction of gas that is injected into the reactor that
is a diluent may be greater than or equal to about 5%, 10%, 20%,
25%, 30%, 35%, 40%, 45%, 50% (mol %), or more.
[0211] The temperature of effluent gas at the exit of the reactor
containing an oxidative coupling of methane effluent may be at
least about 600.degree. C., at least about 650.degree. C., at least
about 700.degree. C., at least about 750.degree. C., at least about
800.degree. C., at least about 850.degree. C., at least about
900.degree. C., or at least about 950.degree. C.
[0212] The conversion of methane in the reactor containing an
oxidative coupling of methane catalyst may be at least about 5%, at
least about 7%, at least about 8%, at least about 9%, at least
about 10%, at least about 11%, at least about 12%, at least about
13%, at least about 14%, or at least about 15%.
[0213] Within the post-bed cracking unit, ethane can be
dehydrogenated and converted into ethylene. A source containing
ethane can be added to the post-bed packing unit downstream of the
reactor containing an oxidative coupling of methane catalyst.
[0214] The post-bed cracking unit and the reactor containing an
oxidative coupling of methane catalyst can be contained within the
same vessel.
[0215] The ratio of ethylene to ethane at the outlet of the
post-bed cracking unit may be at least about 1:1, at least about
1.5:1, at least about 2:1, at least about 2.5:1, at least about
3:1, at least about 3.5:1, at least about 4:1, at least about
4.5:1, or at least about 5:1.
[0216] A stream containing ethane can optionally be added to the
reactor containing an oxidative coupling of methane catalyst. A
stream containing ethane can optionally be added to the post-bed
cracking unit.
[0217] FIG. 13 shows an oxidative coupling of methane system using
a steam diluent that is heated in an oxidative coupling of methane
reactor 1300. A source containing oxygen (O.sub.2) 1301 and a
source containing methane 1302 are injected into a reactor
containing an oxidative coupling of methane catalyst 1304 to
produce a hot OCM gas. The hot OCM gas is put into thermal contact
with a stream containing water 1303 within a heat exchanger 1305 to
produce a steam stream. The steam stream is then injected into the
oxidative coupling of methane reactor 1304. The steam stream can be
used as a diluent.
[0218] The heat exchanger can be integrated with the oxidative
coupling of methane reactor as an integrated non-adiabatic
reactor.
[0219] The effluent of the oxidative coupling of methane reactor
can then be injected into a post-bed reactor. The post bed reactor
can be in the same vessel as the oxidative coupling of methane
reactor. The post bed reactor can be in the same vessel as the heat
exchanger.
[0220] FIG. 14 shows an oxidative coupling of methane system that
mixes oxygen with a diluent prior to injection in an oxidative
coupling of methane reactor 1400. A stream containing oxygen 1401
and a stream containing a diluent 1402 are pre-mixed in a mixer
1404 to produce a diluted oxygen stream. The diluted oxygen stream
and a stream containing methane 1403 are injected into an oxidative
coupling of methane reactor 1405.
[0221] FIG. 15 shows an oxidative coupling of methane system in
which oxygen and a diluent are added downstream of methane 1500. A
stream containing oxygen 1501 and a stream containing a diluent
1502 are pre-mixed in a mixer to produce a pre-mixed oxygen stream.
A stream containing methane is injected into an oxidative coupling
of methane reactor 1506. The pre-mixed oxygen stream is injected
downstream of the stream containing methane using an injector 1505
that extends into the oxidative coupling of methane reactor 1506.
The injector can be a diffuser tube.
Ethane Injection
[0222] Utilization of ethane to produce olefins in combination with
OCM can be advantageous as it can lead to an increased production
rates and concentrations of the desired product for a fixed size
reactor. The capital intensity of the integrated process can be
reduced by as much as 30% with addition of ethane in front of the
OCM catalytic bed and/or in the reactor back end (referred to as
post-bed cracking section).
[0223] Described herein is an improvement in utilization of ethane.
The methods described herein for introducing ethane in the process
can result in an incremental capex intensity reduction of at least
about 10%. The method described herein can also be integrated with
high yield OCM fix bed reactors using molten salt as described
herein. In some cases, ethane conversion in this type of reactor is
more constraint due to reduced CH.sub.4 plant traffic. The methods
described herein involve moving the point at which ethane is mixed
in the process from before the entrance to the OCM catalytic bed
(or pre-OCM reactor) to now injecting ethane directly within the
OCM catalyst bed. In some cases, the method includes propane
injection.
[0224] The amount of ethane added can also be increased. With
front-end injection, the amount of ethane is typically between
about 3% to about 5% ethane. With the in-bed injection described
herein, about 3% to 15% ethane can be used. Percentages are of
injected ethane compared to the total process stream molar
flow.
[0225] In some cases, the most desirable place to inject ethane
into the OCM catalyst bed is at an axial location where the OCM
catalyst bed is at temperature above 700.degree. C. and bellow
900.degree. C., preferably above 750.degree. C. and below
850.degree. C. In some cases, some unreacted O.sub.2 remains in the
OCM process stream to enable some oxidative conversion of ethane to
ethylene. In some cases, it is undesirable to have ethane in
contact with the OCM catalyst at a temperature of less than about
650.degree. C.
[0226] This ethane to ethylene conversion can be the result of a
combination of direct oxidative dehydrogenation of ethane, methyl
radical attack of ethane or thermal cracking.
[0227] One of the main features of this process is that it is not
endothermic, therefore the amount of ethane added is not limited by
the heat capacity of the effluent into which ethane is added. In
some cases, PBC ethane processing capacity is limited by heat
capacity.
[0228] Another important feature is that injected ethane is not in
contact with OCM catalyst operated at modest temperature in the
range of 450.degree. C. to 700.degree. C. where ODH selectivity is
poor. In some cases, part of the mixed O.sub.2+methane+ethane
stream can be bypassed to minimize ethane loss to combustion.
[0229] In some embodiments, oxygen can be added to the ethane
containing stream with or without another gas (e.g., steam,
N.sub.2, methane, CO.sub.2) injected into the bed. In some cases,
this enables greater control of the O.sub.2 partial pressure at the
point of ethane injection and decouple control of the O.sub.2
concentration profile through the OCM catalyst bed for the main
process stream. In some cases, the in bed added stream contains
propane. In some cases, higher hydrocarbons are mixed into the
stream.
[0230] In some instances, the multiple injection points are used
add the added higher alkane stream is rapidly switched between
these locations resulting in temperature oscillation of the solids
in the packed bed. These injection points may be in the same plane
relative to the flow direction or staggered, resulting in injection
with different level of O.sub.2 and different bed temperature to be
combined.
[0231] FIG. 16 shows an oxidative coupling of methane system that
includes multiple ethane injection points 1600. Methane and oxygen
can be injected into tubes at the top of the reactor 1601 which are
a section of the reactor that is non-adiabatic and in contact with
a heat transfer medium. A heat transfer medium (e.g. molten salt)
is injected near the top of the reactor 1602 and flows down the
shell side of the reactor 1603, absorbing heat from the oxidative
coupling of methane reaction taking place in the tubes and finally
flowing out of the reactor at an elevated temperature 1608. In
between the non-adiabatic tubes and the substantially adiabatic
section that includes an oxidative coupling of methane catalyst
1607, ethane can be injected 1604. An additional injection of
ethane can be made in between the non-adiabatic section that
contains an oxidative coupling of methane catalyst and a
non-adiabatic section that does not contain an oxidative coupling
of methane catalyst 1605. The non-adiabatic section that does not
contain an oxidative coupling of methane catalyst can serve as a
post-bed cracking unit 1606. The non-adiabatic sections are
surrounded by an insulating material 1609.
[0232] The temperature of the heat transfer medium at the inlet of
the reactor can be less than about 650.degree. C., less than about
600.degree. C., less than about 550.degree. C., less than about
500.degree. C., less than about 450.degree. C., less than about
400.degree. C., less than about 350.degree. C., or less than about
300.degree. C.
[0233] The temperature in between the non-adiabatic section that is
in thermal communication with a heat transfer medium and the
substantially adiabatic section can be at least about 600.degree.
C., at least about 650.degree. C., at least about 700.degree. C.,
at least about 750.degree. C., at least about 800.degree. C., at
least about 850.degree. C., at least about 900.degree. C., or at
least about 950.degree. C.
[0234] The temperature at the outlet of the substantially adiabatic
section that contains an oxidative coupling of methane catalyst may
be at least about 700.degree. C., at least about 750.degree. C., at
least about 800.degree. C., at least about 850.degree. C., at least
about 900.degree. C., at least about 950.degree. C., or at least
about 1000.degree. C.
[0235] The temperature of the gas at the entrance of the
non-adiabatic section that is in thermal communication with a heat
transfer medium may be at least about 400.degree. C., at least
about 450.degree. C., at least about 480.degree. C., or at least
about 500.degree. C.
[0236] The gas at the entrance of the non-adiabatic section that is
in thermal communication with a heat transfer medium may optionally
include ethane. The concentration of ethane at the entrance of the
non-adiabatic section that is in thermal communication with a heat
transfer medium may be greater than or equal to about 0.1%, 0.2%,
0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% (mol %), or
more.
[0237] The concentration of ethane after ethane injection into the
substantially adiabatic section that contains an oxidative coupling
of methane catalyst may be greater than or equal to about 1%, 2%,
3%, 4%, 5% (mol %), or more.
[0238] The concentration of ethane after ethane injection into the
substantially adiabatic section that does not contain an oxidative
coupling of methane catalyst may be greater than or equal to about
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% (mol %), or more.
[0239] The temperature of the heat transfer medium at the outlet of
the reactor may be at least about 600.degree. C., at least about
650.degree. C., at least about 700.degree. C., at least about
750.degree. C., at least about 800.degree. C., at least about
850.degree. C., at least about 900.degree. C., at least about
950.degree. C., or at least about 1000.degree. C.
Alkane Conversion Process and Systems
[0240] The thermal cracking of alkanes, including ethane and
propane, has been practiced in order to produce olefins, which is a
basic feedstock of the petrochemical industry. Olefins, including
ethylene and propylene, are important feedstocks in the chemicals
industry. In an olefin production process, steam cracking or
pyrolysis of ethane or naphtha at high temperatures may be
conducted to yield a mixture of products with modest conversions of
alkane.
[0241] Recognized herein is the need for efficient and commercially
viable olefin production systems and methods for converting alkanes
into olefins.
[0242] The present disclosure provides systems and methods for
generating olefins. In some embodiments, a process for generating
olefins comprises converting alkanes into a mixture comprising
olefins using an oxidizing agent (e.g., oxygen (O.sub.2)) and a
radical transfer agent, and waiting for a time period which is
greater than the auto-ignition delay time (AIDT). In some cases,
the mixture is cooled. This approach may be used to increase the
olefin yield through repeating the process of addition of the
oxidizing agent and, in some cases, heat removal. The amount of
oxygen containing species produced, including CO and CO.sub.2
("CO.sub.x"), can be minimized through the addition of a minimal
amount of the oxidizing agent (e.g., O.sub.2) relative to the
amount of alkane being converted.
[0243] An aspect of the present disclosure provides methods for
forming an olefin from a mixture of alkane, oxygen (O.sub.2), and
radical transfer agent within a reactor. The transformation of
alkane to olefin within the reactor can proceed through the
formation free alkyl radical species (e.g. an ethyl radical,
H.sub.3C.), that can later proceed to an olefin molecule. The free
alkyl radical species can be generated from the combination of an
alkane species with oxygen (O.sub.2) and a radical transfer agent.
The radical transfer agent can intermediate the transformation of
an alkane to an olefin. The radical transfer agent can be derived
from any molecule that can be radicalized, e.g. H.sub.2, water
(H.sub.2O), and methane (CH.sub.4), or any combination thereof. The
radical transfer agent species can then form transient free
radicals during the reaction, including hydroxyl radical (HO.),
methyl radical (H.sub.3C.), hydrogen radical (H.), or any
combination thereof. The selectivity for any individual alkane
species (e.g., C.sub.2H.sub.6) to be radicalized over another
individual alkane species (e.g., CH.sub.4) can be about
proportional to the relative concentrations of the two individual
alkane species.
[0244] FIG. 18 shows a process for generating olefins 1800, as may
be employed for use with methods (or processes) and systems of the
present disclosure. The process 1800 includes a source of alkane
1801, a source of radical transfer agent 1802, a source of oxygen
(O.sub.2) 1803, at least one reactor 1804, and in some cases a
cooling system 1805. Inputs and outputs into respective units are
indicated by arrows. The source of alkane can be a natural gas
source that includes C.sub.2+ compounds and in some cases non
C.sub.2+ impurities. The source of alkane can include the effluent
from an oxidative coupling of methane process. The source of alkane
can be a stream emanating from one or more separation units which
separate alkane from any non-alkane components. The source of
radical transfer agent can include a natural gas feed stream
comprising CH.sub.4 and in some cases C.sub.2+ compounds and non
C.sub.2+ impurities. The source of radical transfer agent can
include the effluent from an oxidative coupling of methane process.
The source of radical transfer agent can include a source of water
(H.sub.2O). The source of radical transfer agent can include a
source of hydrogen (H.sub.2). The source of radical transfer agent
can be the same as the source of alkane, which can also be the
source of oxygen (O.sub.2).
[0245] During use, alkane from the source of alkane 1801, and
radical transfer agent from the source of radical transfer agent
1802, and oxygen (O.sub.2) from the source of oxygen (O.sub.2) 1804
can be directed into the reactor unit 1804, which reacts the alkane
with O.sub.2. This reaction mixture can be held for a time that is
greater than the auto-ignition delay time (AIDT), and then exit the
reactor 1804. The composition of the gas exiting the reactor can
then contain a greater fraction of olefin than the gas entering the
reactor. The gas exiting the reactor can then be cooled in a
cooling unit 1805.
[0246] The at least one reactor can be operated under about
adiabatic conditions, wherein heat removal from the reactor is
minimized.
[0247] The at least one reactor can be operated under about
isothermal conditions, wherein heat is removed from the bed by some
heat transfer medium.
[0248] The temperature of the stream or streams entering the
reactor can be less than about 600.degree. C., less than about
550.degree. C., less than about 500.degree. C., less than about
450.degree. C., less than about 400.degree. C., less than about
350.degree. C., or less than about 300.degree. C. The temperature
of the gas exiting the reactor can be greater than about
600.degree. C., greater than about 650.degree. C., greater than
about 700.degree. C., greater than about 750.degree. C., greater
than about 800.degree. C., greater than about 850.degree. C.,
greater than about 900.degree. C., greater than about 950.degree.
C., greater than about 1000.degree. C., greater than about
1050.degree. C., or greater than about 1100.degree. C. The reaction
can generate additional components, including CO and CO.sub.2.
[0249] The pressure in the reactor can be at least about 0 bar (g),
at least about 1 bar(g), at least about 2 bar(g), at least about 3
bar(g), at least about 4 bar(g), at least about 5 bar(g), at least
about 6 bar(g), at least about 7 bar(g), at least about 8 bar(g),
at least about 9 bar(g), at least about 10 bar(g), at least about
11 bar(g), at least about 12 bar(g), at least about 13 bar(g), at
least about 14 bar(g), at least about 15 bar(g), at least about 16
bar(g), at least about 17 bar(g), at least about 18 bar(g), at
least about 19 bar(g), at least about 20 bar(g), at least about 25
bar(g), at least about 30 bar(g), at least about 35 bar(g), or at
least about 40 bar(g).
[0250] The apparent selectivity in the reactor can be at least
about 1%, at least about 5%, at least about 10%, at least about
15%, at least about 20%, at least about 25%, at least about 30%, at
least about 35%, at least about 40%, at least about 45%, at least
about 50%, at least about 55%, at least about 60%, at least about
65%, at least about 70%, at least about 75%, at least about 80%, at
least about 85%, at least about 90%, at least about 95%, at least
about 100%, at least about 110%, or at least about 120%.
[0251] The carbon efficiency in the reactor can be at least about
5%, at least about 10%, at least about 15%, at least about 20%, at
least about 25%, at least about 30%, at least about 35%, at least
about 40%, at least about 45%, at least about 50%, at least about
55%, at least about 60%, at least about 65%, at least about 70%, at
least about 75%, at least about 80%, at least about 85%, at least
about 90%, at least about 95%, or at least about 100%.
[0252] Once the radical transfer agent, oxygen (O.sub.2), and
alkane are mixed within the reactor, the species can be held for a
time that is greater than the auto-ignition delay time (AIDT). The
AIDT can be at least about 1 millisecond (ms), at least about 2
milliseconds (ms), at least about 3 milliseconds (ms), at least
about 5 milliseconds (ms), at least about 10 milliseconds (ms), at
least about 15 milliseconds (ms), at least about 20 milliseconds
(ms), at least about 30 milliseconds (ms), at least about 40
milliseconds (ms), at least about 50 milliseconds (ms), at least
about 75 milliseconds (ms), at least about 100 milliseconds (ms),
or at least about 200 milliseconds (ms).
[0253] FIG. 19 shows a process 1900, which includes a stream that
is the effluent of a process to generate olefin 1901 (e.g., an OCM
process), a source of alkane 1902, a source of O.sub.2 1903, a
source of radical transfer agent 1904, and at least one reactor
1905.
[0254] The stream that is the effluent of a process to generate
olefin can be from an oxidative coupling of methane (OCM) process.
The stream that is the effluent of a process to generate olefin can
be from an ethane cracking process. The stream that is the effluent
of a process to generate olefin can be from a naphtha cracking
process. An oxidative coupling of methane (OCM) process can include
the conversion of methane (CH.sub.4) into C.sub.2+ products.
Examples of the oxidative coupling of methane (OCM) process can be
found in U.S. Patent Publication No. 2012/0041246, U.S. Pat. Nos.
9,751,079, and 9,352,295, each of which is incorporated herein by
reference in its entirety. The oxidative coupling of methane (OCM)
process can include an oxidative coupling of methane (OCM)
catalyst. Examples of OCM catalysts can be found in U.S. Patent
Publication No. 2012/0041246, U.S. Pat. No. 8,921,256, 9,956,544 or
9,751,079, each of which is incorporated herein by reference in its
entirety.
[0255] The stream that is the effluent of a process to generate
olefin 1901 can contain a radical transfer agent. In some cases,
the percentage of the stream that is radical transfer agent is
greater than or equal to about 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%,
60%, 70%, 80%, 90%, 95% (mol %), or more. In some cases, the stream
that is the effluent of a process to generate olefin 1901 can
contain alkane. In some cases, the percentage of the stream that is
alkane is greater than or equal to about 1%, 2%, 5%, 10%, 20%, 30%,
40%, 50%, 60%, 70%, 80%, 90%, 95% (mol %), or more.
[0256] In some cases, the stream that is the effluent of a process
to generate olefin 1901 can contain O.sub.2. In some cases, the
percentage of the stream that is O.sub.2 is less than or equal to
about 50%, 40%, 30%, 20%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%,
0.5%, 0.1% (mol %) or less. The amount of oxygen in stream can be a
small amount relative to the amount of the alkane and/or the
radical transfer agent. In some cases, the ratio of oxygen to
alkane and/or radical transfer agent is less than or equal to about
0.5, 0.3, 0.1, 0.05, 0.01, 0.001 or less.
[0257] In some cases, the stream that is the effluent of a process
to generate olefin 1901 also serves as the source of alkane 1902.
In some instances, the stream that is the effluent of a process to
generate olefin 1901 also serves as the source of O.sub.2 1903. In
some embodiments, the stream that is the effluent of a process to
generate olefin 1901 also serves as the source of radical transfer
agent 1904.
[0258] FIG. 20 shows a system for increasing the concentration of
olefin in an oxidative coupling of methane effluent 2000, which
includes a source of oxidative coupling of methane effluent 2001, a
cooling unit 2002, a source of alkane 2003, a source of O.sub.2
2004, a source of radical transfer agent 2005. The system may
include a cooling unit 2006.
[0259] The source of oxidative coupling of methane effluent 2001
can contain a radical transfer agent. In some cases, the percentage
of the stream that is radical transfer agent is greater than or
equal to about 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,
90%, 95% (mol %), or more. The source of oxidative coupling of
methane effluent 2001 can contain alkane. In some cases, the
percentage of the stream that is alkane is greater than or equal to
about 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%
(mol %), or more. The source of oxidative coupling of methane
effluent 2001 can contain O.sub.2. In some cases, the percentage of
the stream that is O.sub.2 is less than or equal to about 50%, 40%,
30%, 20%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1% (mol
%), or less. The amount of oxygen in stream can be a small amount
relative to the amount of the alkane and/or the radical transfer
agent. In some cases, the ratio of oxygen to alkane and/or radical
transfer agent is less than or equal to about 0.5, 0.3, 0.1, 0.05,
0.01, 0.001 or less.
[0260] In some cases, the source of oxidative coupling of methane
effluent 2001 also serves as the source of alkane 2002. In some
cases, the source of oxidative coupling of methane effluent 2001
also serves as the source of O.sub.2 2002. In some cases, the
source of oxidative coupling of methane effluent 2001 also serves
as the source of radical transfer agent 2002.
[0261] In some cases, the product of the cooling operation 2007 is
the same as the source of oxidative coupling of methane effluent
2001.
[0262] FIG. 21 shows a system for using a steam superheater as a
radical transfer agent source in olefin production 2100, which
includes a steam superheater 2101, a source of alkane 2102, a
source of O.sub.2 2103, a source of radical transfer agent 2104,
and at least one reactor 2105. In some cases, the system includes a
cooling unit 2106.
[0263] The steam super heater source 2101 can also be the source of
radical transfer agent 2104. The source of alkane 2102 can be the
effluent of an oxidative coupling of methane process. The effluent
of the cooling unit 2106 can also be the source of alkane 2102. The
effluent of the cooling unit 2106 can also be the radical transfer
agent 2104.
[0264] FIG. 22 shows a modular system for increasing the olefin
concentration in an effluent stream 2200, which includes a source
of oxidative coupling of methane effluent 2201, and a modular
system for increasing olefin concentration 2202, a cooling unit
2208, a source of alkane 2209, a source of O.sub.2 2210, a source
of radical transfer agent 2211, at least one reactor 2212. In some
cases, the cooling unit 2208 is precluded. The modular system for
increasing olefin concentration 2202 can be comprised of an cooling
unit 2203, a source of alkane 2204, a source of O.sub.2 2205, a
source of radical transfer agent 2206, at least one reactor
2207.
[0265] The modular system for increasing olefin concentration 2202
can be repeated at least 1, at least 2, at least 3, at least 4, at
least 5, at least 6, at least 7, at least 8, at least 9, at least
10, at least 11, at least 12, at least 13, at least 14, at least
15, at least 20, at least 30 times or more.
[0266] FIG. 23 shows a system for increasing the olefin
concentration in an effluent stream 2300, which includes a source
of oxidative coupling of methane effluent 2301, a cooling unit
2302, a source of alkane 2303, a source of O.sub.2 2304, a source
of radical transfer agent 2305, at least one reactor 2306, a
cooling unit 2307, a source of alkane 2308, a source of O.sub.2
2309, a source of radical transfer agent 2310, at least one reactor
2311, a cooling unit 2312, a source of alkane 2313, a source of
O.sub.2 2314, a source of radical transfer agent 2315, at least one
reactor 2316, a cooling unit 2317, a source of alkane 2318, a
source of O.sub.2 2319, a source of radical transfer agent 2320,
and at least one reactor 2321. In some cases, the system includes a
cooling unit 2322.
[0267] The system 2300 is an illustrative example of system 2200
which in a case that includes three modular systems for increasing
olefin concentration in the effluent stream 2202.
[0268] The systems and methods provided herein can be performed in
some cases without a radicalization initiator. In some embodiments,
the reactor (e.g., 1804 in FIG. 18) contains a radicalization
initiator (i.e., any material which promotes radicalization of the
radical transfer agent and/or production of olefins). Catalysts can
serve as radical initiation inhibitors. OCM catalysts can serve as
radicalization initiators. Examples of OCM catalysts can be found
in U.S. Patent Publication No. 2012/0041246, U.S. Pat. No.
8,921,256, 9,956,544 or U.S. Pat. No. 9,751,079, each of which is
incorporated herein by reference in its entirety.
[0269] Some aspects of the present disclosure provide systems and
methods for performing a catalytic reaction (e.g., an OCM reaction,
an ODH reaction). Such systems and methods may provide a greater
control of flow of gas and/or liquid carrying reagents and/or
reaction products across the reactor, which may enable an operation
of process at high flow velocities or with lower pressure drop as
compared to a conventional reactor. Materials with different flow
resistance properties may be used in a reactor for conducting a
catalytic reaction. The materials may comprise solid materials. The
materials may comprising a void material which has a high void
fraction (e.g., a void fraction greater than or equal to about 55%,
60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more). The void material
may allow easy flow of gas along a length of a reactor. The
materials may also comprise a catalytic material which may
facilitate one or more catalytic reactions. The void material and
the catalytic materials may be combined or mixed to form a
hybrid/composite material. The hybrid material may comprise a
certain percentage of the catalytic materials. In some cases, the
hybrid material comprises greater than about 1%, 5%, 10%, 15%, 20%,
25%, 30%, 35%, 40% (mol %) catalytic materials, or more. In some
cases, the hybrid materials comprises less than or equal to about
70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25% (mol %) catalytic
materials, or less. In some cases, the hybrid material comprises
catalytic materials at a concentration that falls between any two
values described herein, e.g., between about 2% and about 40% (mol
%). The hybrid packing may be self-assembled into the reactor
vessel or reactor tubes in case of a multi-tubular reactor. The
hybrid materials may be pre-assembled prior to loading. In some
cases, the hybrid packing is a combination of pre-assembled and
self-assembled packing.
[0270] The catalytic materials may be contained in separate
particles per-formed and mixed as a solid into the hybrid
structure. In some cases, the catalytic materials are deposited as
a film onto a surface of the void materials. Coating of the void
material may be performed by washing-coating using a slurry, powder
coating or other techniques such as chemical vapor deposition (CVD)
or physical vapor deposition (PVD). In some cases, the high void
fraction material is assembled around each individual catalytic
particle. In some cases, the void materials are deposited as films.
The catalytic materials (e.g., catalytic particles) may be
deposited onto the films. In some cases, both materials (i.e., the
void materials and the catalytic materials) are formed as films and
multi-layer composite materials maybe formed using the films. In
some cases, the void materials are formed in secondary particles
and loaded into the reactor at the same time as the catalytic
materials are loaded. Depending on e.g., a ratio of sizes of the
secondary particles to catalytic materials, or relevant
volume/amount of each material loaded, the catalytic materials may
well be dispersed in the hybrid bed (FIG. 33) or segregating from
the void materials to form a network of the catalytic materials
each being in direct contact with one another.
[0271] Various materials can be used as void materials.
Non-limiting examples of the void materials may comprise pieces of
ceramic foam, self-assembled stacks of highly anisotropic
refractory particles (e.g., rods, thin rings or ring fragments,
filaments, acicular crystals) with greater than or equal to about
one millimeter (mm) length in a given direction, metal filament
bundles and mesh, metal foams, wire bundles or foam, coater metal
filament, mesh, foam, silicon carbide fibers, boron nitride fibers,
carbon fibers (in reducing environments), acicular mullite, alumina
reticulated foam, cordierite foams and extrudates pieces,
electro-spun formed ceramic wires, stainless steel alloy wires,
zirconia wires, titanium wires, nickel wires, inconel alloy wires,
or combinations thereof. High void fraction foam and mesh can also
be prepared by mixing fibers of different compositions. For
example, Zirconia wires could be mixed with Stainless steel wires
to form a mesh.
[0272] In some cases, the void materials are metal materials (such
as metal mesh, wire bundles, metal foams or metal fibers). In some
examples, the void materials are metal foams. The foam may be
relatively isotropic at large scale. The foam material may have a
pore per inch (PPI) that is greater than or equal to about 1, 5,
10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, or more. In some
cases, the foam material has a PPI that is less than or equal to
about 200, 180, 160, 150, 140, 130, 120, 110, 100, 80, 60, 40, 20,
10, or less. In some cases, the foam material has a PPI falling
with a range of any two values described herein, e.g., between
about 10 and about 100.
[0273] In cases where a reactor is a tubular reactor comprising
metal walls, thermal contact between the reactor and the void
materials may be improved by brazing and/or sintering the void
materials into the tube.
[0274] Alternatively or additionally, the void materials may be
sintered and/or brazed onto a thin sheet (such as a liner in
contact with an inner wall or surface of a reactor). The thin sheet
may be a metal foil. The sheet may be flexible. The flexible sheet
may conform to a shape of the reactor. The liner may be removed
with the void materials and/or catalytic materials. The liner may
be replaced. The liner may be disposable. The liner may be reused.
The liner may be removed at a regular interval to dispose catalytic
materials. FIG. 34 shows an example reactor which uses a foil wrap
to assemble void materials and catalytic materials within the
reactor tube.
[0275] In some examples, as illustrated in FIG. 35, the void
materials are sintered/brazed near the inner surface of a reactor,
leaving an open space inside the reactor for loading and/or
unloading the catalytic materials (e.g., catalytic particles) and
remaining void materials (i.e., void materials not
sintered/brazed). Such systems/methods may facilitate heat transfer
(e.g., heat removal) across the reactor and/or ease the
loading/unloading of the catalytic materials by providing a buffer
volume for catalytic particle growth or shrinking. In some cases,
the void materials that are sintered/brazed onto the inner tube
wall or surface are metal fibers or foam. Use of the metal fibers
and foam may afford the system a greater tolerance to thermal
cycling or gas composition cycling. The metal fibers or foam may be
attached to the inner surface or wall which may take an annular
space of between about 10% and 20% of the tube volume in case of a
tubular reactor. Catalytic materials and/or additional void
materials may be added into the middle of the tube.
[0276] In some cases, the catalytic reaction is an OCM reaction. In
some situations, as the OCM reaction is operated over a large range
of temperature, a significant portion of the reactor operating
envelop is above auto-ignition limit for pressure and/or
temperature of a feed stream. Thus, delaying the homogeneous
build-up of combustion precursors which may lead to a rapid
temperature rise and oxidizing agent consumption in the gas phase
may be desirable. Solid surfaces (of e.g., the void materials) may
interfere with this precursor build up and significantly delay
auto-ignition events. In some examples, there is greater than about
4 times (4.times.) increase in auto-ignition delay time measured in
1'' diameter test vessel when the test vessel is packed with a
ceramic packing as opposed to left empty. In another example, using
finely divided anisotropic solid filler adds a significant amount
of solid surface to the reactor volume when compared to more
standard ceramic packing. This higher surface area can be used to
enable pre-heating the feed mixture to increased temperatures. Use
of the finer divided material may also provide for a reduction in
size of the gas interparticle void between solid surfaces. The
reduction in gas void size may also decrease the propensity of the
reactive gas mixture to ignite.
[0277] Similarly, as the OCM reaction progress, suppression of the
gas phase reaction away from the catalyst particles surface may be
important. It may be achieved by maximizing the speed of the
catalytic reaction so as to remove the limiting reagent quickly
from the feed mixture which deprives the homogeneous reaction
pathway of reagent. This method may require the use of a reactor
that allows short contact times. Using finely divided material to
occupy the gaps between catalyst particle can relax the need for
rapid removal of all of the limiting reagent (e.g., oxidizing
agents in OCM) from the reaction mixture by converting highly
active combustion reaction intermediates, which may facilitate the
design of reactors that integrates heat removal and chemical
conversion in more manageable volumes.
[0278] In some OCM reactor implementations, a substantially
adiabatic reactor is closed coupled with an isotubular reactor and
an amount of oxidizing agents (such as oxygen) slipping through the
isotubular reactor may need to be controlled for proper operation
of the system. Lowering the risk of process fluctuation associated
with homogeneous reactions may be beneficial. When using void
materials (such as metal fiber) as the filler, it may maintain a
certain minimal level of oxidizing agents in the product mixture,
thereby minimizing or eliminating run away coke built up on the
metal surfaces.
Catalytic Pressure Swing Adsorption/Temperature Swing
Adsorption
[0279] In some aspects, the present disclosure provides methods and
systems for producing higher hydrocarbon compounds (e.g.,
hydrocarbon compounds with three or more carbon atoms). The methods
may comprise directing a feed stream into a separations unit. The
feed stream may comprise hydrocarbon compounds having two or more
carbon atoms (C.sub.2+ compounds) (e.g., ethane or ethylene). The
separations unit may comprise a pressure swing adsorption (PSA)
unit and/or a temperature swing adsorption (TSA) unit. The
separations unit may be configured to separate (via e.g.,
adsorption) one or more compounds from remaining compounds of the
feed stream. For example, the separations unit may be configured to
selectively adsorb one or more certain type of compounds (e.g.,
C.sub.2+ compounds). The adsorption may be performed at a first
condition including e.g., temperature, pressure and/or gas hourly
space velocity (GHSV).
[0280] Next, the first condition may be adjusted to a second
condition (including e.g., temperature, pressure and/or GHSV) to
desorb some or all of the compounds selectively adsorbed.
Alternatively or additionally, some of the adsorbed compounds may
be subject to a conversion reaction to product higher hydrocarbon
compounds. In some cases, the feed stream comprises ethylene and
the separations unit is configured to selectively adsorb at least a
portion of the ethylene. In some cases, some or all of the ethylene
that is selectively adsorbed is desorbed as the separations unit is
operated at the second condition. In some cases, the ethylene
conversion reaction comprises a dimerization reaction and/or an
oligomerization reaction. In some cases, the higher hydrocarbon
compounds comprise butane (e.g., 1-butene or 2-butene).
[0281] In some cases, the first condition comprises a first
temperature, a first pressure and/or a first GHSV, and the second
condition comprises a second temperature, a second pressure and/or
a second GHSV. The first temperature may be different than (higher
or lower than) the second temperature. The first pressure may be
different than (higher or lower than) the second pressure. The
first GHSV may be different than (higher or lower than) the second
GHSV.
[0282] In some cases, the adsorption is operated at a lower
temperature and/or higher pressure and the desorption occurs at a
higher temperature and/or lower pressure. For example, the first
temperature may be greater than or equal to about -20.degree. C.,
-15.degree. C., -10.degree. C., -5.degree. C., 0.degree. C.,
5.degree. C., 10.degree. C., 15.degree. C., 20.degree. C.,
25.degree. C., 30.degree. C., 35.degree. C., 40.degree. C.,
45.degree. C., 50.degree. C., 55.degree. C., 60.degree. C. or more.
In some cases, the first temperature is less than or equal to about
70.degree. C., 60.degree. C., 50.degree. C., 40.degree. C.,
30.degree. C., 20.degree. C., 10.degree. C., 0.degree. C., or less.
In some cases, the first temperature is between any two values
described herein, for example, between about -10.degree. C. and
about 50.degree. C.
[0283] The first pressure may be greater than or equal to about 0
bar(a), 5 bar(a), 10 bar(a), 15 bar(a), 20 bar(a), 25 bar(a), 30
bar(a), 35 bar(a), 40 bar(a), 45 bar(a), 50 bar(a) or more. The
first pressure can be less than or equal to about 60 bar(a), 50
bar(a), 40 bar(a), 30 bar(a), 20 bar(a), 10 bar(a), 5 bar(a) or
less. In some cases, the first pressure is between any two values
described herein, for example, between about 6 bar(a) and about 10
bar(a).
[0284] The first GHSV may be greater than or equal to about 100
hr.sup.-1, 500 hr.sup.-1, 1000 hr.sup.-1, 2000 hr.sup.-1, 3000
hr.sup.-1, 4000 hr.sup.-1, 5000 hr.sup.-1, 6000 hr.sup.-1, 7000
hr.sup.-1, 8000 hr.sup.-1, 9000 hr.sup.-1, 10000 hr.sup.-1, 12000
hr.sup.-1, 14000 hr.sup.-1, 16000 hr.sup.-1, 18000 hr.sup.-1, 20000
hr.sup.-1, 22000 hr.sup.-1, 24000 hr.sup.-1 or more. In some cases,
the first GHSV may be less than or equal to about 25000 hr.sup.-1,
23000 hr.sup.-1, 21000 hr.sup.-1, 19000 hr.sup.-1, 17000 hr.sup.-1,
15000 hr.sup.-1, 13000 hr.sup.-1, 11000 hr.sup.-1, 9000 hr.sup.-1,
7000 hr.sup.-1, 5000 hr.sup.-1, 3000 hr.sup.-1, 1000 hr.sup.-1, 800
hr.sup.-1, 600 hr.sup.-1, 400 hr.sup.-1, 200 hr.sup.-1, 100
hr.sup.-1, 50 hr.sup.-1 or less. In some cases, the first GHSV is
between any two values described herein, for example, between about
1000 hr.sup.-1 and about 3000 hr.sup.-1.
[0285] The second temperature may be greater than or equal to about
0.degree. C., 5.degree. C., 10.degree. C., 20.degree. C.,
40.degree. C., 60.degree. C., 80.degree. C., 100.degree. C.,
120.degree. C., 140.degree. C., 160.degree. C., 180.degree. C.,
200.degree. C., 220.degree. C., 240.degree. C., 260.degree. C.,
280.degree. C., 300.degree. C., 320.degree. C., 340.degree. C.,
360.degree. C., 380.degree. C., 400.degree. C. or more. In some
cases, the second temperature is less than or equal to about
500.degree. C., 450.degree. C., 400.degree. C., 350.degree. C.,
300.degree. C., 250.degree. C., 200.degree. C., 150.degree. C.,
100.degree. C., 80.degree. C., 60.degree. C., 40.degree. C.,
20.degree. C., 10.degree. C., 5.degree. C. or less. In some cases,
the second temperature is between any two values described herein,
for example, between about 20.degree. C. and about 350.degree.
C.
[0286] The second pressure may be greater than or equal to about 0
bar(a), 5 bar(a), 10 bar(a), 15 bar(a), 20 bar(a), 25 bar(a), 30
bar(a), 35 bar(a), 40 bar(a), 45 bar(a), 50 bar(a) or more. The
second pressure can be less than or equal to about 60 bar(a), 50
bar(a), 40 bar(a), 30 bar(a), 20 bar(a), 10 bar(a), 5 bar(a) or
less. In some cases, the second pressure is between any two values
described herein, for example, between about 0 bar(a) and about 5
bar(a).
[0287] The second GHSV may be greater than or equal to about 100
hr.sup.-1, 500 hr.sup.-1, 1000 hr.sup.-1, 2000 hr.sup.-1, 3000
hr.sup.-1, 4000 hr.sup.-1, 5000 hr.sup.-1, 6000 hr.sup.-1, 7000
hr.sup.-1, 8000 hr.sup.-1, 9000 hr.sup.-1, 10000 hr.sup.-1, 12000
hr.sup.-1, 14000 hr.sup.-1, 16000 hr.sup.-1, 18000 hr.sup.-1, 20000
hr.sup.-1, 22000 hr.sup.-1, 24000 hr.sup.-1 or more. In some cases,
the second GHSV may be less than or equal to about 25000 hr.sup.-1,
23000 hr.sup.-1, 21000 hr.sup.-1, 19000 hr.sup.-1, 17000 hr.sup.-1,
15000 hr.sup.-1, 13000 hr.sup.-1, 11000 hr.sup.-1, 9000 hr.sup.-1,
7000 hr.sup.-1, 5000 hr.sup.-1, 3000 hr.sup.-1, 1000 hr.sup.-1, 800
hr.sup.-1, 600 hr.sup.-1, 400 hr.sup.-1, 200 hr.sup.-1, 100
hr.sup.-1, 50 hr.sup.-1 or less. In some cases, the second GHSV is
between any two values described herein, for example, between about
1000 hr.sup.-1 and about 3000 hr.sup.-1.
[0288] In some cases, the feed stream comprises ethylene and the
separations unit is configured to selectively adsorb at least a
portion of the ethylene. During the desorption, a higher desorption
temperature (i.e, the second temperature) may decrease ethylene
content while increase a content of hydrocarbon compounds with
higher carbon atoms than ethylene (e.g., C.sub.3, C.sub.4, C.sub.5
compounds) due to more conversion of ethylene in an ethylene
conversion reaction. In some cases, increasing GHSV during
desorption increases ethylene content and decreases a content of
hydrocarbon compounds with higher carbon atoms than ethylene (e.g.,
C.sub.3, C.sub.4, C.sub.5 compounds) due to less conversion of
ethylene in an ethylene conversion reaction. In some cases, the
ethylene conversion reaction comprises a dimerization reaction
and/or an oligomerization reaction.
[0289] The feed stream may be an OCM effluent stream. The methods
may further comprise directing a stream comprising methane and an
oxidizing agent into an OCM reactor to producing the OCM effluent
stream. The OCM effluent may be directed in the separations unit
(e.g., a PSA/TSA unit) to selectively adsorb ethylene. During the
desorption, at least a portion of the adsorbed ethylene may be
desorbed and an additional portion of the adsorbed ethylene may be
converted to the higher hydrocarbon compounds in an ethylene
conversion reaction. The separation unit may yield a separations
effluent stream comprising the higher hydrocarbon compounds. The
separations effluent stream may be directed into a further reaction
unit (e.g., a metathesis unit) to yield a product stream comprising
product compounds (e.g., propylene).
[0290] The separations unit may comprise a material that
facilitates ethylene selective adsorption and the ethylene
conversion reaction. The material may be an adsorbent and/or a
catalyst comprising catalytic materials. The material may comprise
porous zeolites. The porous zeolites may comprise medium pore
zeolites. The porous zeolites may have an average pore size greater
than or equal to about 1 .ANG., 2 .ANG., 3 .ANG., 4 .ANG., 5 .ANG.,
6 .ANG., 7 .ANG., 8 .ANG., 9 .ANG., 10 .ANG., 12 .ANG., 14 .ANG. 16
.ANG., or more. In some cases, the porous zeolites has an average
pore size less than or equal to about 20 .ANG., 18 .ANG., 16 .ANG.,
14 .ANG., 12 .ANG., 10 .ANG., 8 .ANG., 6 A, 4 .ANG., 2 .ANG., 1
.ANG., or less. In some cases, the porous zeolites have an average
pore size falling between any of the two values described herein,
for example, between about 4 .ANG. and about 8 .ANG.. In some
cases, the material comprises zeolites doped with transition
metals, for example, transition metal doped Fe-ZSM-5, ZSM-5, ZSM-23
or combinations thereof with various Si/Al ratio (SAR). The
material can be a single bed composition or a mixture/layering of
materials within a single vessel or between different vessels of
the separations unit.
[0291] FIG. 36 illustrates an example method for producing
hydrocarbon compounds comprising propylene. As shown in FIG. 36, an
OCM product stream 3601 comprising ethylene may be generated. The
OCM product stream may be directed into a separations unit
comprising a PSA/TSA unit in which at least a portion of the
ethylene may be selectively adsorbed 3602. Unadsorbed compounds may
be directed out of the separations unit 3603. The unadsorbed
compounds may comprise CH.sub.4, CO.sub.2, CO and/or H.sub.2. Some
or all of the compounds may be directed back to an OCM reactor
and/or some additional reaction units. Upon a change of conditions
of the separations unit (e.g., an increase in temperature and/or a
decrease in pressure), some or all of the ethylene adsorbed may be
desorbed 3605. A gas stream (e.g., a hot desorption ethane) at a
moderate temperature (e.g., about 100.degree. C., 150.degree. C.,
200.degree. C., 250.degree. C., or 300.degree. C.) 3604 may be
directed to the separations unit before or during the desorption of
ethylene. In some cases, some of the ethylene is converted to
higher hydrocarbons such as butene (including butene isomers) in an
ethylene conversion reaction (such as dimerization or
oligomerization) during the desorption 3606. An effluent stream may
be generated during the desorption. The effluent stream may
comprise butene and ethylene. The effluent stream may be directed
in to a methathesis unit 3607 which may yield a product stream
comprising hydrocarbon compounds such as propylene, ethane and
ethylene.
Computer Systems
[0292] The present disclosure provides computer control systems
that are programmed or otherwise configured to implement methods
provided herein, such as OCM reactions or processes of the present
disclosure. FIG. 32 shows a computer system 3201 that includes a
central processing unit (CPU, also "processor" and "computer
processor" herein) 3205, which can be a single core or multi core
processor, or a plurality of processors for parallel processing.
The computer system 3201 also includes memory or memory location
3210 (e.g., random-access memory, read-only memory, flash memory),
electronic storage unit 3215 (e.g., hard disk), communication
interface 3220 (e.g., network adapter) for communicating with one
or more other systems, and peripheral devices 3225, such as cache,
other memory, data storage and/or electronic display adapters. The
memory 3210, storage unit 3215, interface 3220 and peripheral
devices 3225 are in communication with the CPU 3205 through a
communication bus (solid lines), such as a motherboard. The storage
unit 3215 can be a data storage unit (or data repository) for
storing data. The computer system 3201 can be operatively coupled
to a computer network ("network") 3230 with the aid of the
communication interface 3220. The network 3230 can be the Internet,
an internet and/or extranet, or an intranet and/or extranet that is
in communication with the Internet. The network 3230 in some cases
is a telecommunication and/or data network. The network 3230 can
include one or more computer servers, which can enable distributed
computing, such as cloud computing. The network 3230, in some cases
with the aid of the computer system 3201, can implement a
peer-to-peer network, which may enable devices coupled to the
computer system 3201 to behave as a client or a server.
[0293] The CPU 3205 can execute a sequence of machine-readable
instructions, which can be embodied in a program or software. The
instructions may be stored in a memory location, such as the memory
3210. The instructions can be directed to the CPU 3205, which can
subsequently program or otherwise configure the CPU 3205 to
implement methods of the present disclosure. Examples of operations
performed by the CPU 3205 can include fetch, decode, execute, and
writeback.
[0294] The CPU 3205 can be part of a circuit, such as an integrated
circuit. One or more other components of the system 3201 can be
included in the circuit. In some cases, the circuit is an
application specific integrated circuit (ASIC).
[0295] The storage unit 3215 can store files, such as drivers,
libraries and saved programs. The storage unit 3215 can store user
data, e.g., user preferences and user programs. The computer system
3201 in some cases can include one or more additional data storage
units that are external to the computer system 3201, such as
located on a remote server that is in communication with the
computer system 3201 through an intranet or the Internet. The
computer system 3201 can communicate with one or more remote
computer systems through the network 3230.
[0296] Methods as described herein can be implemented by way of
machine (e.g., computer processor) executable code stored on an
electronic storage location of the computer system 3201, such as,
for example, on the memory 3210 or electronic storage unit 3215.
The machine executable or machine readable code can be provided in
the form of software. During use, the code can be executed by the
processor 3205. In some cases, the code can be retrieved from the
storage unit 3215 and stored on the memory 3210 for ready access by
the processor 3205. In some situations, the electronic storage unit
3215 can be precluded, and machine-executable instructions are
stored on memory 3210.
[0297] The code can be pre-compiled and configured for use with a
machine having a processer adapted to execute the code, or can be
compiled during runtime. The code can be supplied in a programming
language that can be selected to enable the code to execute in a
pre-compiled or as-compiled fashion.
[0298] The computer system 3201 can be programmed or otherwise
configured to regulate one or more parameters, such as various
parameters associated with OCM reactions/processes or OCM
systems.
[0299] Aspects of the systems and methods provided herein, such as
the computer system 3201, can be embodied in programming. Various
aspects of the technology may be thought of as "products" or
"articles of manufacture" typically in the form of machine (or
processor) executable code and/or associated data that is carried
on or embodied in a type of machine readable medium.
Machine-executable code can be stored on an electronic storage
unit, such as memory (e.g., read-only memory, random-access memory,
flash memory) or a hard disk. "Storage" type media can include any
or all of the tangible memory of the computers, processors or the
like, or associated modules thereof, such as various semiconductor
memories, tape drives, disk drives and the like, which may provide
non-transitory storage at any time for the software programming.
All or portions of the software may at times be communicated
through the Internet or various other telecommunication networks.
Such communications, for example, may enable loading of the
software from one computer or processor into another, for example,
from a management server or host computer into the computer
platform of an application server. Thus, another type of media that
may bear the software elements includes optical, electrical and
electromagnetic waves, such as used across physical interfaces
between local devices, through wired and optical landline networks
and over various air-links. The physical elements that carry such
waves, such as wired or wireless links, optical links or the like,
also may be considered as media bearing the software. As used
herein, unless restricted to non-transitory, tangible "storage"
media, terms such as computer or machine "readable medium" refer to
any medium that participates in providing instructions to a
processor for execution.
[0300] Hence, a machine readable medium, such as
computer-executable code, may take many forms, including but not
limited to, a tangible storage medium, a carrier wave medium or
physical transmission medium. Non-volatile storage media include,
for example, optical or magnetic disks, such as any of the storage
devices in any computer(s) or the like, such as may be used to
implement the databases, etc. shown in the drawings. Volatile
storage media include dynamic memory, such as main memory of such a
computer platform. Tangible transmission media include coaxial
cables; copper wire and fiber optics, including the wires that
comprise a bus within a computer system. Carrier-wave transmission
media may take the form of electric or electromagnetic signals, or
acoustic or light waves such as those generated during radio
frequency (RF) and infrared (IR) data communications. Common forms
of computer-readable media therefore include for example: a floppy
disk, a flexible disk, hard disk, magnetic tape, any other magnetic
medium, a CD-ROM, DVD or DVD-ROM, any other optical medium, punch
cards paper tape, any other physical storage medium with patterns
of holes, a RAM, a ROM, a PROM and EPROM, a FLASH-EPROM, any other
memory chip or cartridge, a carrier wave transporting data or
instructions, cables or links transporting such a carrier wave, or
any other medium from which a computer may read programming code
and/or data. Many of these forms of computer readable media may be
involved in carrying one or more sequences of one or more
instructions to a processor for execution.
[0301] The computer system 3201 can include or be in communication
with an electronic display 3235 that comprises a user interface
(UI) 3240 for providing, for example, signals from a chip with
time. Examples of UI's include, without limitation, a graphical
user interface (GUI) and web-based user interface.
[0302] Methods and systems of the present disclosure can be
implemented by way of one or more algorithms. An algorithm can be
implemented by way of software upon execution by the central
processing unit 3205.
EXAMPLES
Example 1: Non-Adiabatic and Substantially Adiabatic OCM
Reactor
[0303] An oxidative coupling of methane reactor was constructed
that included a U-shaped one inch inner diameter pipe immersed in a
molten salt tank, which was insulated. About 40 cm of the reactor
was loaded with oxidative coupling of methane catalyst. The section
of the pipe upstream of the oxidative coupling of methane catalyst
contained inert packing composed of alumina (Al.sub.2O.sub.3). The
molten salt bath temperature was about 550.degree. C. A mixture of
oxygen and methane was injected into the section of the reactor
that held inert packing at a pressure of about 4 bar(g). The
section that held inert packing served as a feed gas preheater. The
section of the tube that is downstream of the section that contains
oxidative coupling of methane catalyst was not in contact with the
molten salt, and was considered substantially adiabatic. The
methane to oxygen ratio at the inlet of the reactor was 6:1, and
the methane conversion was 19%. The peak temperature in the reactor
was 925.degree. C.
Example 2: Catalyst Deactivation Effect on Non-Adiabatic and
Substantially Adiabatic OCM Reactor
[0304] FIG. 17 shows the result of a simulation that calculates the
temperature profile in an oxidative coupling of methane reactor. A
simulation of the oxidative coupling of methane reaction was
conducted in a tubular reactor that contained three sections: a
substantially adiabatic section that did not contain oxidative
coupling of methane catalyst 1703, a non-adiabatic section that was
in thermal communication with a heat transfer medium and contained
oxidative coupling of methane catalyst 1704, and finally a
substantially adiabatic section that did not contain oxidative
coupling of methane catalyst 1705. In the simulation a mixture of
oxygen and methane were fed into the first section at a temperature
of about 500.degree. C. At the exit of the first substantially
adiabatic section, the temperature of the gas was about 640.degree.
C. The gas then traveled into a non-adiabatic section within 5
milliseconds (ms) of exiting the first substantially adiabatic
section. The temperature peaked about half way through the
non-adiabatic section, and its peak temperature as well as the
temperature at the exit of the non-adiabatic section depended on
the catalyst deactivation percentage. The fresh catalyst (about 0%
deactivation), the peak temperature was about 940.degree. C. and
had an exit temperature of about 860.degree. C. 1701. Over time,
the catalyst became more deactivated. After 10,000 hours of
operation, the peak temperature in the non-adiabatic section was
about 770.degree. C. and had an exit temperature of about
760.degree. C. 1702. The gas was then injected into the second
substantially adiabatic section within 5 milliseconds (ms) of
exiting the non-adiabatic section. In the second substantially
adiabatic section, the gas temperature monotonically increased. In
the case of the fresh catalyst, the final exit temperature was
about 870.degree. C. In the case of the catalyst after 10,000 hours
of operation, the final exit temperature was about 925.degree.
C.
Example 3: Improvement in Methane Conversion Using Steam
Dilution
[0305] Methane and oxygen were injected into a reactor containing
an oxidative coupling of methane catalyst, and the effect of using
steam as a diluent on methane conversion was measured. With no
steam addition, the methane conversion was about 12.5%. Increasing
the water dilution to 15%, 30%, and 40%, the methane yield
increased to 13.2%, 14%, and 14.5%, respectively.
Example 4--Radical Transfer Agents
[0306] Additional ethane, O.sub.2, and steam are added to convert
to additional ethylene, as shown in FIG. 24 (e.g., in order to
increase the concentration of ethylene in the product gas from an
OCM reactor). The OCM effluent, including of x % ethylene, y %
ethane, and z % methane, is cooled using a heat exchanger. The
process can increase the concentration of ethylene in this stream
above x %. To do this, additional ethane, O.sub.2, and steam are
added, which correspond to the alkane, O.sub.2, and radical
transfer agent described herein. The unconverted methane from the
OCM reactor can also serve as the radical transfer agent, and there
may be additional alkanes in the stream including propane that can
convert into additional olefin including ethylene and propylene.
The amount of O.sub.2 and ethane that are added is such that the
resulting mixture entering the reactor is 6 mol % O.sub.2 and 5.5
mol % ethane in this example. This mixture is then fed into an
empty reaction vessel at 500.degree. C. When in the reactor, the
oxygen begins to catalyze the production of methyl (H.sub.3C.) and
hydroxyl (HO.) radicals from the radical transfer agents methane
and water, respectively.
[0307] FIG. 25 shows a simulation of ethane concentration inside
the reactor. Initially, the ethane concentration does not change
significantly, and then converts to ethylene.
[0308] FIG. 26 shows a simulation of ethylene concentration inside
the reactor. The ethylene generation profile roughly matches the
ethane depletion profile, because ethane is being converted to
ethane inside the reactor.
[0309] FIG. 27 shows a simulation of the reaction temperature, as
well as the concentrations of methane, ethane, ethylene, propylene,
carbon monoxide (CO), hydrogen (H.sub.2), and carbon dioxide
(CO.sub.2) over time within the reactor. A case is simulated where
the entering mixture contains 6 mol % O.sub.2. The temperature as
well as the concentrations remain roughly constant until about 250
milliseconds (ms), which is the auto-ignition delay time (AIDT) in
this case. This is the time at which the concentration of radicals
have become sufficient to sustain a chain reaction that converts
the reaction mixture to a product mixture. The temperature rapidly
climbs from about 500.degree. C. to about 800.degree. C., the
ethane rapidly depletes and ethylene forms. Some ethane is
converted to CO and H.sub.2, however there is only minimal
formation of CO.sub.2.
[0310] FIG. 28 shows the results of a simulation of this reaction
under varying inlet conditions. From this, it is seen that the
apparent selectivity for ethylene is greater than 100%, due to
conversion of propane as well as ethane to ethylene. The carbon
efficiency, estimated from the percentage of ethylene that is
formed relative to CO and CO.sub.2, is between 60% and 80%.
[0311] The end result of the reaction in the reactor is that there
is additional ethylene concentration in its effluent. This high
temperature effluent, now at about 800.degree. C., is cooled back
to 500.degree. C. using a heat exchanger. Additional O.sub.2,
steam, and ethane are added to the stream, and this new reaction
mixture flows into another vessel. The resulting product gas is
once again enriched in ethylene. This process is repeated twice
more, in order to further increase the concentration of ethylene in
the product gas. Finally, the product mixture is cooled to room
temperature, to result in product that has an ethylene
concentration of (x+a) %, where a is a number greater than
zero.
Example 5--Air-Fed OCM Integrated with Methanol Production
[0312] In some cases, an OCM reaction can be integrated with the
production of methanol (MeOH). Such integrations are described in
U.S. patent application Ser. No. 15/690,090, which is incorporated
herein by reference in its entirety. As described herein, the OCM
reaction can be fed with air, i.e., instead of O.sub.2. In some
cases, the OCM reaction can use partially enriched oxygen. In the
case where the de-methanizer overhead stream becomes the reformer
feed stream (i.e., a once-through case without methanation), the
methanol plan can be designed to handle the N.sub.2 content in the
steam methane reformer (SMR) feed stream. This design takes
advantage of an economic trade-off between the capital expenditure
increase in the methanol plant compared with the cost of an air
separation unit being avoided.
Example 6--Dry Gas Case without PBC
[0313] The inlet gas stream to the reactor is: O.sub.2 12 mol %;
C.sub.2H.sub.6<1 mol %; H.sub.2,H.sub.2O,CO.sub.2<1 mol %;
and the balance CH.sub.4. The reactor conditions are:
T.sub.salt=700.degree. C.; T.sub.inlet=500.degree. C.; and
T.sub.outlet=700.degree. C. with a pressure of 8 barg. The reactor
has a length of 36 inches, and inner diameter of 0.5''. The gas
hourly space velocity is 30000 hr.sup.-1. The reactor outlet
conditions are shown in Table 1.
TABLE-US-00001 TABLE 1 Reactor outlet for Example 6 CO 2.10%
Selectivity: CO2 4.85% 73% Ethane 3.83% Ethylene 4.62% Propane
0.11% CH.sub.4 Conversion: Propylene 0.52% 20% Methane 59.0%
O.sub.2 0.0% H.sub.2 8.0% C2+ Yield: H.sub.2O 12.27% 14.6
Example 7--Case of Natural Gas with Ethane Injection without
PBC
[0314] The inlet gas stream to the reactor is: O.sub.2 12 mol %;
C.sub.2H.sub.6 10 mol %; H.sub.2,H.sub.2O,CO.sub.2<1 mol %; and
the balance CH.sub.4. The reactor conditions are:
T.sub.salt=700.degree. C.; T.sub.inlet=500.degree. C.; and
T.sub.outlet=700.degree. C. with a pressure of 8 barg. The reactor
has a length of 36 inches, and inner diameter of 0.5''. The gas
hourly space velocity is 30000 hr.sup.-1. The reactor outlet
conditions are shown in Table 2.
TABLE-US-00002 TABLE 2 Reactor outlet for Example 7 CO 2.34%
Selectivity: CO2 5.11% 77% (Net) Ethane 3.53% Ethylene 10.43%
Propane 0.40% CH.sub.4 Conversion: Propylene 0.40% 20% Methane
54.3% O.sub.2 0.0% H.sub.2 12.01% C2+ Yield: H.sub.2O 11.47%
14.6
Example 8--Case of Natural Gas with Ethane Injection without
PBC
[0315] The inlet gas stream to the reactor is: O.sub.2 12 mol %;
C.sub.2H.sub.6 10 mol %; H.sub.2,H.sub.2O,CO.sub.2<1 mol %; and
the balance CH.sub.4. The reactor conditions are:
T.sub.salt=700.degree. C.; T.sub.inlet=500.degree. C.; and
T.sub.outlet=700.degree. C. with a pressure of 8 barg. The reactor
has a length of 36 inches, and inner diameter of 0.5''. The gas
hourly space velocity is 30000 hr.sup.-1. The catalyst is
NaMnWO.sub.4--SiO.sub.2. The reactor outlet conditions are shown
below in Table 3.
TABLE-US-00003 TABLE 3 Reactor outlet for Example 8 CO 3.11%
Selectivity: CO2 0.83% 86% (Net) Ethane 2.91% Ethylene 12.26%
Propane 0.27% CH.sub.4 Conversion: Propylene 0.50% 20% Methane
62.8% O.sub.2 0.0% H.sub.2 4.63% C2+ Yield: H.sub.2O 12.70%
14.6
Example 9--Operation of an OCM Reactor
[0316] With reference to FIG. 30, an OCM reactor was operated that
had an isothermal section, an adiabatic section, and a post-bed
cracking section. The isothermal section had an inert section
without catalyst and a section with an OCM catalyst. As shown, the
gas temperature was monitored versus position along the reactor.
The reactor performed a successful OCM reaction.
[0317] It will be appreciated that systems and methods described
herein are provided as examples and that various alternatives may
be employed. It will be further appreciated that components of
systems described herein are interchangeable.
[0318] It should be understood from the foregoing that, while
particular implementations have been illustrated and described,
various modifications can be made thereto and are contemplated
herein. It is also not intended that the invention be limited by
the specific examples provided within the specification. While the
invention has been described with reference to the aforementioned
specification, the descriptions and illustrations of the preferable
embodiments herein are not meant to be construed in a limiting
sense. Furthermore, it shall be understood that all aspects of the
invention are not limited to the specific depictions,
configurations or relative proportions set forth herein which
depend upon a variety of conditions and variables. Various
modifications in form and detail of the embodiments of the
invention will be apparent to a person skilled in the art. It is
therefore contemplated that the invention shall also cover any such
modifications, variations and equivalents. It is intended that the
following claims define the scope of the invention and that methods
and structures within the scope of these claims and their
equivalents be covered thereby.
* * * * *