U.S. patent application number 15/085379 was filed with the patent office on 2016-09-15 for process for preparation of hydrocracking catalyst for use in hydrocracking of hydrocarbon streams.
The applicant listed for this patent is Sabic Global Technologies, B.V.. Invention is credited to Mohammad JAVEED, Ravichander NARAYANASWAMY, Krishna Kumar RAMAMURTHY, Alexander STANISLAUS.
Application Number | 20160264884 15/085379 |
Document ID | / |
Family ID | 56879242 |
Filed Date | 2016-09-15 |
United States Patent
Application |
20160264884 |
Kind Code |
A1 |
NARAYANASWAMY; Ravichander ;
et al. |
September 15, 2016 |
Process for Preparation of Hydrocracking Catalyst for Use in
Hydrocracking of Hydrocarbon Streams
Abstract
A process for activating and maintaining a catalyst for use in
hydrocracking a hydrocarbon stream includes continuously contacting
a hydrocarbon stream with a hydroprocessing catalyst in the
presence of hydrogen. Sulphides and chloride compounds in the
hydrocarbon stream are used such that the hydroprocessing catalyst
has the ability to hydrogenate, dechlorinate, and hydrocrack
components of the hydrocarbon stream.
Inventors: |
NARAYANASWAMY; Ravichander;
(Bengaluru, IN) ; RAMAMURTHY; Krishna Kumar;
(Bengaluru, IN) ; STANISLAUS; Alexander;
(Bangalore, IN) ; JAVEED; Mohammad; (Bengaluru,
IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sabic Global Technologies, B.V. |
BERGEN OP ZOOM |
|
NL |
|
|
Family ID: |
56879242 |
Appl. No.: |
15/085379 |
Filed: |
March 30, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/IB2016/051135 |
Mar 1, 2016 |
|
|
|
15085379 |
|
|
|
|
62201664 |
Aug 6, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 1/10 20130101; C10G
49/06 20130101; C10G 49/04 20130101; C10G 2300/703 20130101; C10G
2300/4037 20130101; C10G 45/08 20130101; C10G 2300/202 20130101;
C10G 45/10 20130101; B01J 37/20 20130101; C10G 47/14 20130101; C10G
65/00 20130101 |
International
Class: |
C10G 65/00 20060101
C10G065/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 10, 2015 |
IN |
1166CHE2015 |
Claims
1. A process for activating and maintaining a catalyst for use in
hydrotreating a hydrocarbon stream to simultaneously reduce heavier
boiling components, chlorides, and olefins, comprising:
continuously contacting the hydrocarbon stream with a
hydroprocessing catalyst in the presence of hydrogen, wherein the
hydrocarbon stream comprises one or more chloride compounds and one
or more sulphides.
2. The process of claim 1, wherein the one or more sulphides
comprise dimethyl disulphide, mercaptans, carbon disulphide,
hydrogen sulphide, or combinations thereof.
3. The process of claim 1, wherein the one or more sulfides of the
hydrocarbon stream are present in an amount such that a sulphur
content of the hydrocarbon stream is about 0.5 wt % to about 5 wt %
based on a total weight of the hydrocarbon stream.
4. The process of claim 1, further comprising: before the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst in the presence of hydrogen, contacting a
catalyst activating stream with the hydroprocessing catalyst,
wherein the catalyst activating stream comprises one or more
sulphides.
5. The process of claim 4, wherein the one or more sulfides of the
catalyst activating stream are present in an amount such that a
sulphur content of the catalyst activating stream is about 0.5 wt %
to about 5 wt % based on a total weight of the catalyst activating
stream.
6. The process of claim 4, wherein after the step of contacting and
during the step of continuously contacting, the hydroprocessing
catalyst has hydrogenation sites and hydrocracking sites.
7. The process of claim 4, wherein the step of contacting a
catalyst activating stream with the hydroprocessing catalyst is
performed for a period of 30 hours or less, wherein the step of
continuously contacting a hydrocarbon stream with a hydroprocessing
catalyst initiates after the period elapses.
8. The process of claim 4, wherein the step of contacting a
catalyst activating stream with the hydroprocessing catalyst is
performed ex-situ of a hydroprocessing reactor.
9. The process of claim 1, wherein the step of continuously
contacting a hydrocarbon stream with a hydroprocessing catalyst is
performed ex-situ of the hydroprocessing reactor.
10. The process of claim 4, wherein the step of contacting a
catalyst activating stream with the hydroprocessing catalyst is
performed in-situ of a hydroprocessing reactor.
11. The process of claim 1, wherein the step of continuously
contacting a hydrocarbon stream with a hydroprocessing catalyst is
performed in-situ of the hydroprocessing reactor.
12. The process of claim 1, wherein the step of continuously
contacting the hydrocarbon stream with the hydroprocessing catalyst
is performed at a temperature of 100.degree. C. to 450.degree.
C.
13. The process of claim 1, wherein the step of continuously
contacting the hydrocarbon stream with the hydroprocessing catalyst
is performed at a weight hourly space velocity of 0.1 to 10
hr.sup.-1, at a hydrogen to hydrocarbon ratio of 10 to 3,000 NL/L,
and at a pressure of 1 to 200 barg.
14. The process of claim 1, wherein the hydrocarbon stream
comprises the one or more chloride compounds in a concentration of
greater than 200 ppmw based on a total weight of the hydrocarbon
stream.
15. The process of claim 1, wherein the hydrocarbon stream further
comprises one or more olefins, and wherein the one or more olefins
are present in the hydrocarbon stream in a concentration of 20 wt %
or more based on the total weight of the hydrocarbon stream.
16. The process of claim 15, wherein the hydrocarbon stream further
comprises heavy hydrocarbon molecules, wherein the at least a
portion of the one or more olefins comprises at least a portion of
the heavy hydrocarbon molecules.
17. The process of claim 1, wherein the hydrocarbon stream further
comprises paraffins.
18. The process of claim 1, wherein the hydrocarbon stream further
comprises heavy hydrocarbon molecules, and wherein a concentration
of the heavy hydrocarbon molecules in the hydrocarbon stream is 10
wt % to 90 wt % based on the total weight of the hydrocarbon
stream.
19. The process of claim 1, wherein the hydroprocessing catalyst
comprises cobalt and molybdenum on an alumina support, nickel and
molybdenum on an alumina support, tungsten and molybdenum on an
alumina support, or nickel and molybdenum sulphides.
20. The process of claim 1, wherein the hydroprocessing catalyst
comprises platinum and palladium on an alumina support.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of and claims
priority to International Application No. PCT/IB2016/051135 filed
Mar. 1, 2016, entitled "Process for Preparation of Hydrocracking
Catalyst for Use in Hydrocracking of Hydrocarbon Streams," which
claims priority to U.S. Provisional Application No. 62/201,664
filed on Aug. 6, 2015, entitled "Process for Preparation of
Hydrocracking Catalyst for Use in Hydrocracking of Hydrocarbon
Streams," and Indian Provisional Application No. 1166/CHE/2015
filed Mar. 10, 2015 entitled "Process for Preparation of
Hydrocracking Catalyst for Use in Hydrocracking of Hydrocarbon
Streams and Pyrolysis Oil," which applications are incorporated by
reference herein in their entirety.
TECHNICAL FIELD
[0002] The present disclosure relates to the preparation of
hydrocracking catalysts for the treatment of hydrocarbon streams
resulting from pyrolysis of waste plastics for use in downstream
processes.
BACKGROUND
[0003] Waste plastics contain polyvinylchloride (PVC). Through a
pyrolysis process, waste plastics can be converted to gas and
liquid products. These liquid products contain paraffins,
i-paraffins (iso-paraffins), olefins, naphthenes, and aromatic
components along with organic chlorides in concentrations of
hundreds of ppm. However, the liquid products of a pyrolysis
process (pyrolysis oils) are off-spec for use as a feedstock for
steam crackers because steam cracker feed specifications require
chloride levels less than 3 ppm, olefin content less than 1 wt %,
and boiling end point requirements of 370.degree. C.
SUMMARY
[0004] Disclosed herein is a process for activating and maintaining
a catalyst for use in hydrotreating a hydrocarbon stream to
simultaneously reduce heavier boiling components, chlorides, and
olefins, comprising continuously contacting the hydrocarbon stream
with a hydroprocessing catalyst in the presence of hydrogen,
wherein the hydrocarbon stream comprises one or more chloride
compounds and one or more sulphides.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 illustrates a hydroprocessing system which utilizes
the hydrocracking catalyst prepared as described herein for
hydrocracking, hydrogenating, and dechlorinating components of a
hydrocarbon stream to levels suitable for introduction to a steam
cracker.
[0006] FIG. 2 is a graph of a staged catalyst sulphiding protocol,
showing temperature versus time.
DETAILED DESCRIPTION
[0007] Other than in the operating examples or where otherwise
indicated, all numbers or expressions referring to quantities of
ingredients, reaction conditions, and the like, used in the
specification and claims are to be understood as modified in all
instances by the term "about." Various numerical ranges are
disclosed herein. Because these ranges are continuous, they include
every value between the minimum and maximum values. The endpoints
of all ranges reciting the same characteristic or component are
independently combinable and inclusive of the recited endpoint.
Unless expressly indicated otherwise, the various numerical ranges
specified in this application are approximations. The endpoints of
all ranges directed to the same component or property are inclusive
of the endpoint and independently combinable. The term "X or more"
means that the named component is present in an amount of the value
X, and values which are more than X.
[0008] The terms "a," "an," and "the" do not denote a limitation of
quantity, but rather denote the presence of at least one of the
referenced item. As used herein the singular forms "a," "an," and
"the" include plural referents.
[0009] As used herein, "combinations thereof" is inclusive of one
or more of the recited elements, optionally together with a like
element not recited, e.g., inclusive of a combination of one or
more of the named components, optionally with one or more other
components not specifically named that have essentially the same
function. As used herein, the term "combination" is inclusive of
blends, mixtures, alloys, reaction products, and the like.
[0010] Reference throughout the specification to "an embodiment,"
"embodiments," "another embodiment," "other embodiments,"
"alternative embodiments," "additional embodiments," "some
embodiments," and so forth (e.g., the use of "additionally" and/or
"alternatively" in the context of describing one or more
embodiments), means that a particular element (e.g., feature,
structure, property, and/or characteristic) described in connection
with the embodiment is included in at least an embodiment described
herein, and may or may not be present in other embodiments. In
addition, it is to be understood that the described element(s) can
be combined in any suitable manner in the various embodiments.
[0011] Disclosed herein are embodiments of a process for preparing
a hydrocracking catalyst for use in hydrocracking hydrocarbon
streams. The embodiments involve activating and maintaining a
catalyst for use in hydrocracking a hydrocarbon stream. Generally,
the process includes continuously contacting a hydrocarbon stream
with a hydroprocessing catalyst in the presence of hydrogen, where
the hydrocarbon stream comprises one or more chloride compounds and
one or more sulphides. In certain embodiments, before the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst in the presence of hydrogen, the process
may include contacting a catalyst activating stream with the
hydroprocessing catalyst, wherein the catalyst activating stream
comprises one or more sulphides.
[0012] Embodiments of the process for preparing a hydrocracking
catalyst are described in context with reference to FIG. 1. FIG. 1
illustrates a hydroprocessing which utilizes the hydrocracking
catalyst prepared as described herein for hydrocracking components
of a hydrocarbon stream 1 to levels suitable for introduction to a
steam cracker 30. In additional embodiments, the hydroprocessing
catalyst is used for dechlorinating chloride compounds and
hydrogenating olefins contained in a hydrocarbon stream 1 to levels
suitable for introduction to the steam cracker 30.
[0013] The hydroprocessing system 100 includes a hydroprocessing
reactor 10, a separator 20, and a steam cracker 30. The hydrocarbon
stream 1 feeds to the hydroprocessing reactor 10, and the reaction
product effluent flows from the hydroprocessing reactor 10 in the
hydrocarbon product stream 2 to the separator 20. In separator 20,
a treated product (e.g., in gas or liquid form) is recovered from
the hydrocarbon product stream 2 and flows from the separator 20
via treated hydrocarbon stream 4, with one or more
sulphur-containing gases and/or chlorine-containing gases flowing
from the separator 20 in stream 3. Embodiments of the disclosure
contemplate a second hydroprocessing reactor and a second separator
may be placed in between separator 20 and treated hydrocarbon
stream 4. The treated product flowing from the separator 20, in
such embodiments, may contain residual sulphur, and the second
hydroprocessing reactor/second separator combination may treat the
treated product flowing from the separator 20 to completely remove
the sulphur such that a second treated product flowing in the
treated hydrocarbon stream 4 from the second separator contains
less than 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6,
5, 4, 3, 2, 1, 0.5, 0.1 ppmw S based on total weight of the treated
hydrocarbon stream 4.
[0014] The treated product in the treated hydrocarbon stream 4 may
flow directly (e.g., without any separations or fractionations of
the treated hydrocarbon stream 4) or via blended hydrocarbon stream
4' (e.g., without any separations or fractionations of the treated
hydrocarbon stream 4 and blended hydrocarbon stream 4') to a steam
cracker 30, from which high value products flow in stream 6.
[0015] The hydrocarbon stream 1 generally includes one or more
hydrocarbons, at least a portion of which are heavy hydrocarbon
molecules. In embodiments, the hydrocarbon stream 1 may
additionally include one or more sulphides, one or more chloride
compounds, hydrogen, or combinations thereof. The hydrocarbon
stream 1 is generally in a liquid phase. A hydrogen (H.sub.2)
stream can be added to hydrocarbon stream 1 before entering the
hydroprocessing reactor 10. Optionally, a H.sub.2 stream is
additionally added in between various catalyst beds in a multi-bed
arrangement in the hydroprocessing reactor 10 to enrich the reactor
environment with H.sub.2.
[0016] The hydrocarbon stream 1 may be a stream from an upstream
process, such as a pyrolysis process, which contains one or more
chloride compounds, and optionally, also one or more sulphides, for
example, from the pyrolysis of waste plastics. In an embodiment
wherein the stream from the upstream process does not contain the
one or more sulphides, the hydrocarbon stream 1 may be doped with
the one or more sulphides, via a doping stream 7.
[0017] Examples of the one or more hydrocarbons which may be
included in the hydrocarbon stream 1 include paraffins (n-paraffin,
i-paraffin, or both), olefins, naphthenes, aromatic hydrocarbons,
or combinations thereof. When the one or more hydrocarbons includes
all the listed hydrocarbons, the group of hydrocarbons may be
collectively referred to as a PONA feed (paraffin, olefin,
naphthene, aromatics) or PIONA feed (n-paraffin, i-paraffin,
olefin, naphthene, aromatics). A particular embodiment of the
hydrocarbon stream 1 is a plastic pyrolysis oil, discussed in more
detail below.
[0018] Any paraffin may be included in the hydrocarbon stream 1.
Examples of paraffins which may be included in the hydrocarbon
stream 1 include, but are not limited to, C.sub.1 to C.sub.22
n-paraffins and i-paraffins. In an embodiment, the concentration of
paraffins in the hydrocarbon stream 1 may be less than 10 wt %
based on the total weight of the hydrocarbon stream 1.
Alternatively, the concentration of paraffins in the hydrocarbon
stream 1 may be 10 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt
%, or more based on the total weight of the hydrocarbon stream 1.
While embodiments include paraffins of carbon numbers up to 22, the
disclosure is not limited to carbon number 22 as an upper end-point
of the suitable range of paraffins, and the paraffins can include
higher carbon numbers, e.g., 23, 24, 25, 26, 27, 28, 29, 30, 31,
32, 33, 34, 35, 36, 37, 38, 39, 40, and higher. In embodiments, at
least a portion of the paraffins in the hydrocarbon stream 1
comprises at least a portion of the heavy hydrocarbon
molecules.
[0019] Any olefin may be included in the hydrocarbon stream 1.
Examples of olefins which may be included in hydrocarbon stream 1
include, but are not limited to, C.sub.2 to C.sub.10 olefins and
combinations thereof. In an embodiment, the concentration of
olefins in the hydrocarbon stream 1 may be less than 10 wt % based
on the total weight of the hydrocarbon stream 1. Alternatively, the
concentration of olefins in the hydrocarbon stream 1 may be 10 wt
%, 20 wt %, 30 wt %, 40 wt % or more based on the total weight of
the hydrocarbon stream 1. In embodiments, at least a portion of the
one or more olefins in the hydrocarbon stream 1 comprise at least a
portion of the heavy hydrocarbon molecules. While embodiments
include olefins of carbon numbers up to 10, the disclosure is not
limited to carbon number 10 as an upper end-point of the suitable
range of olefins, and the olefins can include higher carbon
numbers, e.g., 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29, 30, and higher.
[0020] In an embodiment, the hydrocarbon stream 1 comprises no
olefins.
[0021] Any naphthene may be included in the hydrocarbon stream 1.
Examples of naphthenes include, but are not limited to,
cyclopentane, cyclohexane, cycloheptane, and cyclooctane. In an
embodiment, the concentration of naphthenes in the hydrocarbon
stream 1 may be less than 10 wt % based on the total weight of the
hydrocarbon stream 1. Alternatively, the concentration of
naphthenes in the hydrocarbon stream 1 may be 10 wt %, 20 wt %, 30
wt %, 40 wt % or more based on the total weight of the hydrocarbon
stream 1. While embodiments include naphthenes of carbon numbers up
to 8, the disclosure is not limited to carbon number 8 as an upper
end-point of the suitable range of naphthenes, and the naphthenes
can include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15,
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and
higher. In embodiments, at least a portion of the naphthenes in the
hydrocarbon stream 1 comprise at least a portion of the heavy
hydrocarbon molecules.
[0022] Any aromatic hydrocarbon may be included in the hydrocarbon
stream 1. Aromatic hydrocarbons suitable for use in the hydrocarbon
stream 1 include, but are not limited to, benzene, toluene,
xylenes, ethyl benzene, or combinations thereof. In an embodiment,
the concentration of aromatic hydrocarbons in the hydrocarbon
stream 1 may be less than 10 wt % based on the total weight of the
hydrocarbon stream 1. Alternatively, the concentration of aromatic
hydrocarbons in the hydrocarbon stream 1 may be 10 wt %, 20 wt %,
30 wt %, 40 wt % or more based on the total weight of the
hydrocarbon stream 1. In embodiments, at least a portion of the
aromatics in the hydrocarbon stream 1 comprise at least a portion
of the heavy hydrocarbon molecules. While embodiments include
aromatic hydrocarbons of carbon numbers up to 8, the disclosure is
not limited to carbon number 8 as an upper end-point of the
suitable range of aromatic hydrocarbons, and the aromatic
hydrocarbons can include higher carbon numbers, e.g., 9, 10, 11,
12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,
29, 30, and higher. In an embodiment, the aromatic hydrocarbons
carbon number is as high as 22.
[0023] In an embodiment, the hydrocarbon stream 1 comprises no
aromatic hydrocarbons.
[0024] As discussed herein, embodiments of the processes disclosed
herein contemplate hydrocracking of molecules, and in particular,
heavy hydrocarbon molecules of the hydrocarbon stream 1. In an
embodiment, the concentration of heavy hydrocarbon molecules in the
hydrocarbon stream 1 may be less than 10 wt % based on the total
weight of the hydrocarbon stream 1. Alternatively, the
concentration of the heavy hydrocarbon molecules in the hydrocarbon
stream 1 may be 10 wt % to 90 wt % based on the total weight of the
hydrocarbon stream 1. As described above, the heavy hydrocarbon
molecules may include paraffins, i-paraffins, olefins, naphthenes,
aromatic hydrocarbons, or combinations thereof. In embodiments, the
heavy hydrocarbon molecules may include C.sub.16 and larger
hydrocarbons. Greater than 5, 10, 15, 20, 25, 30 wt % or more of
the heavy hydrocarbon molecules in the hydrocarbon stream 1 is
hydrocracked when the hydrocarbon stream 1 is contacted with the
hydroprocessing catalyst in the hydroprocessing reactor 10.
[0025] Chloride compounds which may be included in the hydrocarbon
stream 1 include, but are not limited to, aliphatic
chlorine-containing hydrocarbons, aromatic chlorine-containing
hydrocarbons, and other chlorine-containing hydrocarbons. Examples
of chlorine-containing hydrocarbons include, but are not limited
to, 1-chlorohexane, 2-chloropentane, 3-chloro-3-methyl pentane,
(2-chloroethyl) benzene, chlorobenzene, or combinations thereof.
The concentration of chloride compounds in the hydrocarbon stream 1
may be 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm,
30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500
ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 1,100 ppm,
1,200 ppm, 1,300 ppm, 1,400 ppm, 1,500 ppm, 1,600 ppm, 1,700 ppm,
1,800 ppm, 1,900 ppm, 2,000 ppm or more based on the total weight
of the hydrocarbon stream 1.
[0026] Sulphides which may be included in the hydrocarbon stream 1
include sulphur-containing compounds. For example, a sulphiding
agent such as dimethyl disulphide (C.sub.2H.sub.6S.sub.2), dimethyl
sulphide (C.sub.2H.sub.6S), mercaptans (R--SH), carbon disulphide
(CS.sub.2), hydrogen sulphide (H.sub.2S), or combinations thereof
may be used as the sulphide in the hydrocarbon stream 1.
[0027] In an embodiment, one or more sulphides (e.g., dimethyl
disulphide (C.sub.2H.sub.6S.sub.2), dimethyl sulphide
(C.sub.2H.sub.6S), mercaptans (R--SH), carbon disulphide
(CS.sub.2), hydrogen sulphide (H.sub.2S), or combinations thereof)
are added to the hydrocarbon stream 1 (e.g., the hydrocarbon stream
1 is "doped" with one or more sulphides), for example, via a doping
stream 7, before the hydrocarbon stream 1 is introduced to the
hydroprocessing reactor 10. In such embodiments, the one or more
sulphides are added to the hydrocarbon stream 1 in an amount such
that a sulphur content of the hydrocarbon stream 1, after sulphide
addition, is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3
wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt % or more based on the total
weight of the hydrocarbon stream 1. In embodiments, the doping
stream 7 may include components tailored for doping such as
hexadecane and dimethyl disulphide; alternatively, the doping
stream 7 may be a heavier oil (e.g., naphtha, diesel, or both)
which already contains sulphide compounds (or to which sulphides
are doped to achieve the sulphur content disclosed herein) and
which is blended with the hydrocarbon stream 1 to achieve the
sulphur content described above.
[0028] In alternative embodiments, one or more sulphides are
present in the hydrocarbon stream as a result of upstream
processing from which the hydrocarbon stream 1 flows. In such
embodiments, the hydrocarbon stream 1 may contain one or more
sulphides in an amount such that a sulphur content of the
hydrocarbon stream 1, without sulphide doping, is about 0.5 wt %, 1
wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt
%, 5 wt % or more based on the total weight of the hydrocarbon
stream 1.
[0029] In yet other embodiments, the hydrocarbon stream 1 may
contain one or more sulphides in an amount insufficient for
sulphiding (e.g., less than 5,000, 4,000, 3,000, 2,000, 1,000, 900,
800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30,
20, 10, 5, or 1 ppm) the hydroprocessing catalyst contained in the
hydroprocessing reactor 10 (the catalyst is discussed in more
detail below), and doping stream 7 is utilized to raise the
concentration of the one or more sulphides in the hydrocarbon
stream to such that a sulphur content of the hydrocarbon stream 1,
after sulphide addition, is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt
%, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt % or more
based on the total weight of the hydrocarbon stream 1.
[0030] In an embodiment, the sulphur content of the hydrocarbon
stream 1, after sulphide addition using doping stream 7, is up to
about 3 wt % based on the total weight of the hydrocarbon stream 1.
In another embodiment, the sulphur content of the hydrocarbon
stream 1, without sulphide addition using doping stream 7, is up to
about 3 wt % based on the total weight of the hydrocarbon stream
1.
[0031] In embodiments, the hydrocarbon stream 1 may be one or more
pyrolysis oils which contain any of the paraffins, i-paraffins,
olefins, naphthenes, aromatic hydrocarbons, chloride compounds,
sulphides, or combinations thereof as disclosed herein. The one or
more pyrolysis oils may be obtained from pyrolysis of waste
plastics (for example, from a high severity process as disclosed in
U.S. Pat. No. 8,895,790, which is incorporated by reference in its
entirety, or from any low temperature severity pyrolysis process
known in the art with the aid of this disclosure). It is
contemplated that for embodiments having one or more plastic
pyrolysis oils in the hydrocarbon stream 1, at least a portion of
the plastic pyrolysis oils comprises heavy hydrocarbon molecules
(e.g., also referred to as heavy ends of the pyrolysis oils).
Hydrocracking of the heavy ends of the plastic pyrolysis oils to
meet steam cracker 30 specifications is contemplated.
[0032] Other streams which may comprise at least a portion of the
hydrocarbon stream 1 include a reformate stream from catalytic
naphtha reformer, tire pyrolysis oil, and any other chloride
containing hydrocarbon stream.
[0033] In embodiments, the hydrocarbon stream 1 may be one or more
pyrolysis oils as described above which is blended with a heavier
oil (e.g., a naphtha or diesel, via doping stream 7). In such
embodiments, blending the treated hydrocarbon stream 4 with a
non-chlorinated stream 5 as described for embodiments below may
additionally occur; alternatively, the subsequent blending may not
occur.
[0034] The hydroprocessing reactor 10 is configured to hydrocrack,
and in some embodiments, additionally dechlorinate and hydrogenate
components of the hydrocarbon stream 1 fed to the hydroprocessing
reactor 10. In the hydroprocessing reactor 10, the hydrocarbon
stream 1 is contacted with the hydroprocessing catalyst in the
presence of hydrogen to yield a hydrocarbon product in stream 2. It
is contemplated the hydrocarbon stream 1 may be contacted with the
hydroprocessing catalyst in upward flow, downward flow, radial
flow, or combinations thereof, with or without a staged addition of
hydrocarbon stream 1, doping stream 7, a H.sub.2 stream, or
combinations thereof. It is further contemplated the components of
the hydrocarbon stream 1 may be in the liquid phase, a liquid-vapor
phase, or a vapor phase while in the hydroprocessing reactor
10.
[0035] The hydroprocessing reactor 10 may facilitate any reaction
of the components of the hydrocarbon stream 1 in the presence of,
or with, hydrogen. Reactions may occur as the addition of hydrogen
atoms to double bonds of unsaturated molecules (e.g., olefins,
aromatic compounds), resulting in saturated molecules (e.g.,
paraffins, i-paraffins, naphthenes). Additionally, reactions in the
hydroprocessing reactor 10 may cause a rupture of a bond of an
organic compound, resulting in "cracking" of a hydrocarbon molecule
into two or more smaller hydrocarbon molecules, or resulting in a
subsequent reaction and/or replacement of a heteroatom with
hydrogen. Examples of reactions which may occur in the
hydroprocessing reactor 10 include, but are not limited to, the
hydrogenation of olefins, removal of heteroatoms from
heteroatom-containing hydrocarbons (e.g., dechlorination),
hydrocracking of large paraffins or i-paraffins to smaller
hydrocarbon molecules, hydrocracking of aromatic hydrocarbons to
smaller cyclic or acyclic hydrocarbons, conversion of one or more
aromatic compounds to one or more cycloparaffins, isomerization of
one or more normal paraffins to one or more i-paraffins, selective
ring opening of one or more cycloparaffins to one or more
i-paraffins, or combinations thereof.
[0036] In embodiments, the hydroprocessing reactor 10 may be any
vessel configured to contain the hydroprocessing catalyst disclosed
herein. The vessel may be configured for gas phase, liquid phase,
vapor-liquid phase, or slurry phase operation. The hydroprocessing
reactor 10 may include one or more beds of the hydroprocessing
catalyst in fixed bed, fluidized bed, moving bed, ebullated bed,
slurry bed, or combinations thereof, configuration. The
hydroprocessing reactor 10 may be operated adiabatically,
isothermally, nonadiabatically, non-isothermally, or combinations
thereof. The reactions of this disclosure may be carried out in a
single stage or in multiple stages. For example, the
hydroprocessing reactor 10 can be two reactor vessels fluidly
connected in series, each having one or more catalyst beds of the
hydroprocessing catalyst. Alternatively, two or more stages for
hydroprocessing may be contained in a single reactor vessel. In
embodiments having multiple stages, the first stage may
dechlorinate and hydrogenate components of the hydrocarbon stream 1
to yield a first hydrocarbon product having a first level of
chloride compounds and olefins. The first hydrocarbon product may
flow from the first stage to the second stage, where other
components of the first hydrocarbon product are dechlorinated and
hydrogenated to yield a second hydrocarbon product stream (stream 2
in FIG. 1) having a second level of chloride compounds and olefins.
The second hydrocarbon stream may then be treated as described
herein for stream 2.
[0037] In an embodiment, the hydroprocessing reactor 10 may
comprise one or more vessels.
[0038] In embodiments of a single vessel or multiple vessels, the
sulphur present in the hydrocarbon stream 1 is removed as H.sub.2S
to provide a reduced level of sulphur acceptable for downstream
processing in steam crackers and refinery units.
[0039] In an embodiment, hydrogen may feed to the hydroprocessing
reactor 10 in stream 8. The rate of hydrogen addition to the
hydroprocessing reactor 10 is generally sufficient to achieve the
hydrogen-to-hydrocarbon ratios disclosed herein.
[0040] The disclosed hydroprocessing reactor 10 may operate at
various process conditions. For example, contacting the hydrocarbon
stream 1 with the hydroprocessing catalyst in the presence of
hydrogen may occur in the hydroprocessing reactor 10 at a
temperature of 100.degree. C. to 450.degree. C.; alternatively,
100.degree. C. to 350.degree. C.; or alternatively, 260.degree. C.
to 350.degree. C. Contacting the hydrocarbon stream 1 with the
hydroprocessing catalyst in the presence of hydrogen may occur in
the hydroprocessing reactor 10 at a pressure of 1 barg to 200 barg;
or alternatively, 20 barg to 60 barg. Contacting the hydrocarbon
stream 1 with the hydroprocessing catalyst in the presence of
hydrogen may occur in the hydroprocessing reactor 10 at a weight
hourly space velocity (WHSV) of between 0.1 hr.sup.-1 to 10
hr.sup.-1; or alternatively, 1 hr.sup.-1 to 3 hr.sup.-1. Contacting
the hydrocarbon stream 1 with the hydroprocessing catalyst in the
presence of hydrogen may occur in the hydroprocessing reactor 10 at
a hydrogen-to-hydrocarbon (H.sub.2/HC) flow ratio of 10 to 3,000
NL/L; or alternatively, 200 to 800 NL/L.
[0041] It is contemplated that dechlorination using the
hydroprocessing catalyst as described herein is performed in the
hydroprocessing reactor 10 without the use of chlorine sorbents,
without addition of Na.sub.2CO.sub.3 in an effective amount to
function as a dechlorinating agent, or both.
[0042] To prepare the hydrocracking catalyst, any hydroprocessing
catalyst used for hydrogenation (e.g., saturation) of olefins and
aromatic hydrocarbons (e.g., a commercially available hydrotreating
catalyst) may be used. In an embodiment, the hydroprocessing
catalyst is a cobalt and molybdenum catalyst (Co--Mo catalyst) on
an alumina support. In other embodiments, the hydroprocessing
catalyst is a nickel and molybdenum catalyst (Ni--Mo catalyst) on
an alumina support or tungsten and molybdenum catalyst (W--Mo
catalyst) on an alumina support. Other catalyst embodiments may
include platinum and palladium catalyst (Pt--Pd catalyst) on an
alumina support, nickel sulphides suitable for slurry processing,
molybdenum sulphides suitable for slurry processing, nickel and
molybdenum sulphides, or combinations thereof.
[0043] In embodiments where the hydrocarbon stream 1 comprises one
or more sulphides and one or more chloride compounds, contacting
the hydrocarbon carbon stream 1 with the hydroprocessing catalyst
acts to activate the hydroprocessing catalyst by sulphiding and to
acidify the hydroprocessing catalyst by chlorinating. Continuously
contacting the hydroprocessing catalyst with the hydrocarbon stream
1 containing the one or more sulphides, the one or more chloride
compounds, or both, may maintain the catalyst activity on a
continuous basis. Activating and maintaining the activation of the
hydroprocessing catalyst in effect transforms the functionality of
the hydroprocessing catalyst to also exhibit hydrocracking ability,
e.g., the hydroprocessing catalyst transforms to a hydrocracking
catalyst which maintains a hydrogenating ability.
[0044] In embodiments, the hydroprocessing catalyst is activated
and/or the activity is maintained by sulphiding the hydroprocessing
catalyst in-situ. For example, the hydroprocessing catalyst may be
sulphided (i.e., activated) and/or sulphiding (i.e., maintaining
the catalyst activity) of the hydroprocessing catalyst may be
performed (e.g., maintaining the hydroprocessing catalyst in
sulphided form is accomplished) by continuously contacting the
hydrocarbon stream 1 containing one or more sulphides compounds
with the hydroprocessing catalyst. The one or more sulphides may be
included in the hydrocarbon stream 1 in an amount such that the
sulphur content of the hydrocarbon stream 1 is about 0.5 wt %, 1 wt
%, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %,
or 5 wt % based on the total weight of the hydrocarbon stream 1. In
an embodiment, the sulphur content of the hydrocarbon stream 1 is
up to about 3 wt % based on the total weight of the hydrocarbon
stream 1.
[0045] Alternatively, the hydroprocessing catalyst may be sulphided
(i.e., activated) by contacting a catalyst activating stream 9
containing one or more sulphides with the hydroprocessing catalyst
for a period of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,
30 or fewer hours) sufficient to activate the hydroprocessing
catalyst (before contacting the hydrocarbon stream 1 with the
hydroprocessing catalyst). In such embodiments, the catalyst
activating stream 9 may include a hydrocarbon carrier for the one
or more sulphides, such as hexadecane. The one or more sulphides
may be included in the catalyst activating stream 9 in an amount
such that the sulphur content of the catalyst activating stream 9
is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5
wt %, 4 wt %, 4.5 wt %, 5 wt % or more based on the total weight of
the catalyst activating stream 9. In an embodiment, the sulphur
content of the catalyst activating stream 9 is up to about 3 wt %
based on the total weight of the catalyst activating stream 9.
After the hydroprocessing catalyst is activated with the catalyst
activating stream 9, flow of the catalyst activating stream 9 may
be discontinued, and sulphiding (i.e., maintaining the catalyst
activity) of the hydroprocessing catalyst may be maintained (e.g.,
maintaining the hydroprocessing catalyst in sulphided form is
accomplished) by continuously contacting the hydrocarbon stream 1
containing one or more sulphides with the hydroprocessing catalyst.
The one or more sulphides may be included in the hydrocarbon stream
1 in an amount such that the sulphur content of the hydrocarbon
stream 1 is about 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3
wt %, 3.5 wt %, 4 wt %, 4.5 wt %, or 5 wt % based on the total
weight of the hydrocarbon stream 1. In an embodiment, the sulphur
content of the hydrocarbon stream 1 is up to about 3 wt % based on
the total weight of the hydrocarbon stream 1.
[0046] In embodiments, sulphiding and maintaining the catalyst in
sulphided form may use two different concentrations of sulphur
content in the hydrocarbon stream 2. For example, the one or more
sulphides may be included (e.g., provided via spiking stream 7) in
the hydrocarbon stream 2 in an amount such that the sulphur content
of the hydrocarbon stream 1 is about 2 wt % based on the total
weight of the hydrocarbon stream 2 for sulphiding, and the one or
more sulphides may be maintained (e.g., via spiking stream 7) in
the hydrocarbon stream 2 in an amount such that the sulphur content
of the hydrocarbon stream 1 is about 2 wt % based on the total
weight of the hydrocarbon stream 2 for maintaining the
hydroprocessing catalyst in the sulphided form. In another example,
the one or more sulphides may be included in the catalyst
activating stream 9 in an amount such that the sulphur content of
the catalyst activating stream 9 is about 3 wt % based on the total
weight of the catalyst activating stream 9 for sulphiding, and the
one or more sulphides may be included (e.g., via spiking stream 7)
in the hydrocarbon stream 2 in an amount such that the sulphur
content of the hydrocarbon stream 1 is about 2 wt % based on the
total weight of the hydrocarbon stream 2 for maintaining the
hydroprocessing catalyst in the sulphided form.
[0047] In embodiments, catalyst activity is also maintained by
chloriding the hydroprocessing catalyst. The hydroprocessing
catalyst is chlorided using the one or more chloride compounds
provided to the hydroprocessing catalyst by the hydrocarbon stream
1. The one or more chloride compounds which contribute to
acidification of the hydroprocessing catalyst may be included in
the hydrocarbon stream 1 in concentrations disclosed herein.
[0048] Sulphiding and maintaining the hydroprocessing catalyst in
sulphided form result in a catalyst which has hydrogenation sites
(sulphided metal) for hydrogenation of components of the
hydrocarbon stream 1. Chloriding the hydroprocessing catalyst
results in a catalyst which has hydrocracking sites (chlorided
alumina) for hydrocracking components of the hydrocarbon stream 1.
That is, chloriding the hydroprocessing catalyst transforms the
catalyst into a hydrocracking catalyst (in addition to having
hydrogenation capabilities).
[0049] Due to hydrogenation reactions in the hydroprocessing
reactor 10, in embodiments, the hydrocarbon product stream 2 may
contain one or more olefins in a concentration of less than 1 wt %
based on the total weight of the hydrocarbon product stream 2. It
is also contemplated that the concentration of aromatic
hydrocarbons in the hydrocarbon product stream 2 is less than the
concentration of aromatic hydrocarbons in the hydrocarbon stream 1
due to hydrogenation of at least a portion of the aromatic
hydrocarbons in the hydroprocessing reactor 10. For example,
aromatic hydrocarbons may be present in the hydrocarbon product
stream 2 in a concentration of less than 10, 9, 8, 7, 6, 5, 4, 3,
2, or 1 wt % based on the total weight of the hydrocarbon product
stream 2.
[0050] The reaction product flows as effluent from the
hydroprocessing reactor 10 in the hydrocarbon product stream 2 to
the separator 20. Separator 20 may be any vessel which can recover
a treated hydrocarbon stream 4 from the hydrocarbon product 2 which
is fed to the separator 20. In embodiments, the treated hydrocarbon
stream 4 may be recovered by separating a treated product (e.g.,
liquid product or gas product) from sulphur and chlorine-containing
gas in the separator 20, and flowing the treated product in the
treated hydrocarbon stream 4 from the separator 20.
[0051] In an embodiment, the separator 20 is a condenser which
operates at conditions which condense a portion of the hydrocarbon
product stream 2 into the treated product (e.g., liquid product or
treated liquid product) while leaving sulphur and
chlorine-containing compounds in the gas phase. The treated liquid
product flows from the separator 20 in treated hydrocarbon stream
4, and the sulphur and chlorine-containing gas flows from the
separator 20 via stream 3.
[0052] In another embodiment, the separator 20 is a scrubbing unit
containing a caustic solution (e.g., a solution of sodium hydroxide
in water) which removes (e.g., via reaction, adsorption,
absorption, or combinations thereof) sulphur and
chlorine-containing gases from the hydrocarbon product stream 2 to
yield the treated product (e.g., gas product or treated gas
product) which flows from the separator 20 via treated hydrocarbon
stream 4 while the sulphur and chlorine-containing compounds in the
gas phase flow from the separator 20 via stream 3.
[0053] In yet another embodiment, the separator 20 is a condenser
in communication with a scrubbing unit containing a caustic
solution. As described above, the condenser may operate at
conditions which condense a portion of the hydrocarbon product
stream 2 into the mid-treated product (e.g., liquid product or
treated liquid product) while leaving sulphur and
chlorine-containing compounds in the gas phase. The mid-treated
liquid product flows from the condenser and experiences a pressure
reduction (e.g., via a valve or other pressure reducing device
known in the art with the aid of this disclosure) which creates an
effluent gas which flows from the scrubbing unit, leaving the
treated product flowing in treated hydrocarbon stream 4. Sulphur
and chlorine-containing compounds flow from the separator 20 in
stream 3.
[0054] In embodiments disclosed herein, no hydrogen halides and no
halogenated organic compounds are recycled to the hydroprocessing
reactor 10.
[0055] In embodiments, the treated hydrocarbon stream 4 includes
one or more chloride compounds in a concentration of less than 5
ppm, 4 ppm, 3 ppm, 2 ppm, 1 ppm, or 0.5 ppm based on a total weight
of the treated hydrocarbon stream 4. It is contemplated that the
one or more chloride compounds in the treated hydrocarbon stream 4
may be the same as some or all of the one or more chloride
compounds in the hydrocarbon stream 1; alternatively, it is
contemplated that only some of the one or more chloride compounds
in the treated hydrocarbon stream 4 are the same as only some of
the one or more chloride compounds in the hydrocarbon stream 1;
alternatively, it is contemplated that none of the one or more
chloride compounds in the treated hydrocarbon stream 4 are the same
as the one or more chloride compounds in the hydrocarbon stream
1.
[0056] In additional embodiments, the treated hydrocarbon stream 4
includes the one or more olefins in a concentration which is less
than a concentration of the one or more olefins in the hydrocarbon
stream 1 due to hydrogenation of at least a portion of the one or
more olefins from the hydrocarbon stream 1 while the hydrocarbon
stream 1 is contacted with the hydroprocessing catalyst in the
hydroprocessing reactor 10. In yet additional embodiments, the
treated hydrocarbon stream 4 includes the one or more olefins in a
concentration which is less than a concentration of the one or more
olefins in the hydrocarbon stream 1 due to hydrogenation and
hydrocracking of at least a portion of the one or more olefins from
the hydrocarbon stream 1 while the hydrocarbon stream 1 is
contacted with the hydroprocessing catalyst in the hydroprocessing
reactor 10. In an embodiment, the one or more olefins are present
in the treated hydrocarbon stream 4 in a concentration of less than
1 wt % based on the total weight of the treated hydrocarbon stream
4.
[0057] In embodiments, the treated hydrocarbon stream 4 includes
one or more paraffins, and the concentration of the one or more
olefins is less than 1 wt % based on the total weight of the
treated hydrocarbon stream 4. It is also contemplated that the
concentration of aromatic hydrocarbons in the treated hydrocarbon
stream 4 is less than the concentration of aromatic hydrocarbons in
the hydrocarbon stream 1 due to hydrogenation of at least a portion
of the aromatic hydrocarbons in the hydroprocessing reactor 10. For
example, aromatic hydrocarbons may be present in the treated
hydrocarbon stream 4 in a concentration of less than 10, 9, 8, 7,
6, 5, 4, 3, 2, or 1 wt % based on the total weight of the treated
hydrocarbon product stream 4.
[0058] Due to hydrocracking of heavy hydrocarbon molecules when the
hydrocarbon stream 1 is contacted with the hydroprocessing catalyst
in the hydroprocessing reactor 10, the treated hydrocarbon stream 4
may have a boiling end point of 370.degree. C. or less. A
significant reduction in hydrocarbons boiling above 370.degree. C.
is obtained in stream 2 as compared to hydrocarbon stream 1.
[0059] In embodiments where the treated hydrocarbon stream 4
includes one or more chloride compounds in a concentration of less
than 3 ppm, the treated hydrocarbon stream 4 may be fed directly to
the steam cracker 30. In alternative embodiments where the treated
hydrocarbon stream 4 includes one or more chloride compounds in a
concentration of 3 ppm or more (e.g., 3 ppm to 5 ppm), the treated
hydrocarbon stream 4 may be blended with a non-chlorinated
hydrocarbon stream 5 to yield a blended hydrocarbon stream 4'
(streams 4' and 5 having dashed lines to denote the alternative
embodiment) having a concentration of one or more chlorides which
is less than 3 ppm based on a total weight of the blended
hydrocarbon stream 4'. The blended hydrocarbon stream 4' may be fed
to the steam cracker 30.
[0060] Steam cracker 30 generally has feed specification
requirements. First, the steam cracker 30 requires the
concentration of chloride compounds in the feed to the steam
cracker 30 to be less than 3 ppm. Second, the steam cracker 30
requires the concentration of olefins in a stream fed to the steam
cracker 30 to be less than 1 wt %. Third, the steam cracker 30
requires the boiling end point of the stream fed to the steam
cracker 30 to be 370.degree. C. The steam cracker 30 cracks
molecules or cleaves at elevated temperatures carbon-carbon bonds
of the components in the treated hydrocarbon stream 4 or blended
hydrocarbon stream 4' in the presence of steam to yield high value
products such as ethylene, propylene, butene, butadiene, aromatic
compounds, or combinations thereof. The high value products may
flow from the steam cracker 30 via stream 6.
[0061] The disclosed hydrocracking catalyst prepared according to
the techniques disclosed herein both hydrocracks and hydrogenates
components of a hydrocarbon stream fed to a hydroprocessing reactor
10 containing the catalyst. Moreover, chloride compounds contained
in the hydrocarbon stream are removed. In embodiments, simultaneous
hydrogenation, dechlorination, and hydrocracking of a hydrocarbon
stream components is achieved in a single hydroprocessing step
using the hydrocracking catalyst prepared as disclosed herein, with
the treated hydrocarbon product being capable of feeding to a steam
cracker having the feed requirements specified herein, without
further separations or fractionations of the treated hydrocarbon
product. Catalyst activity can be initiated and/or maintained
simultaneously with the simultaneous hydrogenation, dechlorination,
and hydrocracking by using hydrocarbon streams of the compositions
disclosed herein which feed to a hydroprocessing reactor. The use
of chloride compounds in the hydrocarbon stream 1 for activating
and maintaining the activity of the hydrocracking catalyst in
effect transforms the hydroprocessing catalyst to a hydrocracking
catalyst.
[0062] As is demonstrated in the examples below and discussed
above, it has been found that hydrocracking of olefins and heavy
hydrocarbon molecules contained in a hydrocarbon stream occurs
using a hydrocracking catalyst prepared using a hydroprocessing
catalyst under the conditions disclosed herein. Hydrocracking
according to the embodiments disclosed herein can occur over the
operating pressures disclosed herein for hydroprocessing reactor
10, including those low pressures demonstrated in the examples.
Embodiments of the processes disclosed herein meet the boiling end
point of 370.degree. C. required for steam crackers. Moreover, the
disclosed embodiments demonstrate that about 30 wt % of the heavy
hydrocarbon molecules of a hydrocarbon stream can undergo
hydrocracking at the conditions disclosed herein. When the
hydrocarbon stream contains plastic pyrolysis oil, the heavier ends
of the plastic pyrolysis oil are hydrocracked. Increased levels of
paraffins due to the hydrocracking ability of the processes
disclosed herein can result in a higher production of propylene in
steam crackers. LPG gases are not liberated in the disclosed
processes until the temperature of the one or more catalyst beds in
the hydroprocessing reactor 10 reaches about 400.degree. C. Liquid
feed to crackers is maximized, and as a result, gas product
formation is minimized, which is useful for existing plants which
are constrained on the gas flow rate to the gas compressor. In the
disclosed embodiments, the production of methane and ethane is also
low.
[0063] Dechlorination according to the embodiments disclosed herein
can occur over the operating temperature ranges disclosed herein
for the hydroprocessing reactor 10, including operating
temperatures in the low-end of the temperature ranges disclosed
herein. Removal of chloride compounds to less than 1 ppm occurs at
temperatures below 350.degree. C. Moreover, achieving sub-ppm
chloride compound concentrations is possible with initial chloride
content in the hydrocarbon stream 1 of 1,000 ppm or more. Moreover
still, removal of chloride compounds is effective for different
types and classes of chlorides present in the hydrocarbon stream 1.
When the hydroprocessing reaction is conducted at temperatures at
or above 350.degree. C., it has been found that the treated
hydrocarbon product contains 3 ppm or higher chloride content. In
such cases, the treated hydrocarbon product stream can be blended
as described herein with a non-chlorinated stream 5 in such
proportions to make the combined blended hydrocarbon stream 4' meet
the steam cracker feed specifications.
[0064] Operation at low temperatures (e.g., less than 350.degree.
C.) also has an added advantage of corrosion mitigation of the
reactor metallurgy. For most metals and alloys used in the
commercial reactors, corrosion rates start to increase at reactor
temperatures over 300.degree. C. It has been found that the
efficiency of dechlorination according to the disclosed embodiments
is good at reactor temperatures below 350.degree. C., and the
dechlorination process works with a sulphided Co--Mo catalyst on an
alumina support even as low as 260.degree. C., with the chlorides
in the treated product being less than 1 ppm. Thus, the metallurgy
corrosion issue is mitigated and longer equipment life is possible
while achieving dechlorination to levels desirable for feed to
steam cracker 30. The processes disclosed herein have been
demonstrated to work at pressures as low as 20 barg, which is a
less severe condition than the conditions typically employed with a
commercial hydrotreating catalyst. Ability to operate at lower
pressures reduces the required pressure rating for process vessels
(e.g., the hydroprocessing reactor 10) and provides an opportunity
for reduced investment costs.
[0065] The disclosed embodiments also demonstrate olefins in the
hydrocarbon product are reduced typically to less than 1 wt % of
the treated hydrocarbon stream 4 from a feed olefin concentration
of 20 wt % or more in the hydrocarbon stream 1.
[0066] Thus, the disclosed processes achieve the requirements of
chloride content, olefin content, and boiling end point of the feed
for a steam cracker simultaneously.
EXAMPLES
[0067] The subject matter having been generally described, the
following examples are given as particular embodiments of the
disclosure and to demonstrate the practice and advantages thereof.
It is understood that the examples are given by way of illustration
and are not intended to limit the specification of the claims to
follow in any manner.
[0068] Examples 1 to 6 were conducted in a fixed bed reactor
located inside a 3-zone split-tube furnace. The reactor internal
diameter was 13.8 mm and had concentrically located bed thermowell
of 3 mm outer diameter. The reactor was 48.6 cm long. Commercial
hydroprocessing catalyst of Co--Mo on alumina (8 g bone dry weight)
was broken along the length to particles of 1.5 mm long and diluted
with SiC in the ratio of 60% SiC to 40% catalyst to give a mean
particle diameter of 0.34 mm. This was done to avoid slip through
of the chlorides due to wall slip or channeling in the small
diameter reactor. Pre-heating bed and post-catalyst inert beds was
provided in the form of 1 mm glass beads. The catalyst bed
temperature was controlled to isothermal by varying the controlled
furnace zone skin temperatures. The catalyst was sulphided using 3
wt % S in hexadecane (S was introduced as dimethyl disulphide).
Liquid feed (i.e., the hydrocarbon stream) was fed through a
metering pump and H.sub.2 gas was fed using a mass flow controller.
The reactor effluent (i.e., the hydrocarbon product) gases were
cooled to condense out the liquids (i.e., the treated hydrocarbon
stream in the form of a liquid product) under pressure while
allowing non-condensed gases (e.g., containing chloride(s),
chlorine, hydrogen sulphide, or combinations thereof) to separate.
Following liquid condensation, the pressure of the liquids was
reduced and effluent gas flow was scrubbed in a caustic scrubber
and measured using a drum-type wet gas meter. The effluent gas flow
was analyzed using a refinery gas analyzer (a custom gas analyzer
from M/s AC Analyticals BV). The liquid product olefin content was
determined using a Detailed Hydrocarbon Analyzer GC (DHA) and a
boiling point characterization was obtained using a SIMDIS GC. The
liquid product chloride content was measured using a Chlora
M-series analyzer (monochromatic wavelength dispersive X-ray
Fluorescence technique, ASTM D7536).
Example 1
[0069] In Example 1, a hydrocarbon feed mixture was prepared by
mixing 30 wt % n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20
wt % cyclohexane, and 20 wt % ethyl benzene. Dimethyl disulphide,
2-chloropentane, 3-chloro-3-methyl pentane, 1-chlorohexane,
(2-chloroethyl) benzene, and chlorobenzene were then added to give
205 ppm organic chlorides and a sulphur content of 2 wt % S in the
combined feed mixture. This combined feed mixture was used as the
hydrocarbon stream which was contacted with the hydroprocessing
catalyst in the packed bed reactor as mentioned above in the
presence of H.sub.2 at conditions of 280.degree. C. reactor
temperature, 60 barg reactor pressure, 0.92 hr.sup.-1 WHSV, and 414
NL/L H.sub.2/HC flow ratio. The liquid product (i.e., the treated
hydrocarbon stream) was analyzed in a DHA wherein molecules lighter
than C.sub.13 are injected into the GC column and heavier than
C.sub.13 are flushed out. The normalized composition of liquid
product as measured by DHA was paraffins (26.24 wt %), paraffins
(17.28 wt %), olefins (0 wt %), naphthenes (33.61 wt %), and
aromatics (22.88 wt %). SIMDIS analysis of liquid product indicates
that 78 wt % of the liquid product boils at 180.degree. C., and
immediately at 79 wt %, the boiling point shifts to 286.degree. C.;
indicating that 22 wt % (i.e. 100-78=22) of the liquid product is
hexadecane. This implies out of 30 wt % hexadecane in the feed
(calculated based on the feed excluding chloride and sulphides,
since dimethyl disulphide is converted to gases, the chloride
compounds are dechlorinated so as to contribute less than 0.5 wt %
of the product), 8 wt % of hexadecane was hydrocracked to lower
products. As mentioned before, this 22 wt % does not get analyzed
in DHA. This 22 wt % hexadecane unaccounted in DHA composition is
added to the liquid product analyzed by DHA (DHA composition
multiplied by 0.78 fraction that was injected into DHA) and the
resulting composition of the liquid product is 42.47 wt %
paraffins, 13.48 wt % i-paraffins, 0 wt % olefins, 26.21 wt %
naphthenes and 17.84 wt % aromatics. In addition, the chloride
content of the liquid product was 0.09 ppmw.
[0070] Example 1 demonstrates it is possible to simultaneously
dechlorinate, hydrogenate, and hydrocrack a PIONA hydrocarbon
stream containing heavy hydrocarbon molecules (e.g., hexadecane), a
chloride content of more than 200 ppm, and an olefin content of 20
wt % (calculated based on the feed excluding chloride and
sulphides) such that a portion of the heavy hydrocarbon molecules
are hydrocracked, chloride content is reduced to less than 1 ppm,
and olefins are completely removed (0 wt % in the liquid product).
Comparing feed and liquid product compositions, it can be said that
paraffins, i-paraffins, and naphthenes have increased in
concentration, while aromatics have reduced in concentration and
olefins were completely depleted. This clearly indicates
hydrocracking of hexadecane as well as hydrocracking of olefins in
feed. Thus, Example 1 additionally demonstrates olefins are
hydrocracked in addition to being hydrogenated.
[0071] The DHA analysis summary by carbon number for the liquid
product is shown below:
TABLE-US-00001 n-Paraffins, i-Paraffins, Olefins, Naphthenes,
Aromatics, Total, Carbon No. wt % wt % wt % wt % wt % wt % 2 3 4
0.015 0.015 5 0.012 0.012 6 0.016 0.18 27.136 0.048 27.217 7 0 8
0.145 14.226 0.547 21.979 36.896 9 0.079 5.901 0.834 6.814 10 26.01
2.93 0.039 11 12 Total, wt % 26.221 17.268 35.584 22.86 99.933
Unknown 0.053 Heavies 0.013
Example 2
[0072] Example 2 explores the effect of operating pressure on
hydrocracking performance. A hydrocarbon feed mixture was prepared
by mixing 30 wt % n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene,
20 wt % cyclohexane, and 20 wt % ethyl benzene. Dimethyl
disulphide, 2-chloropentane, 3-chloro-3-methyl pentane,
1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene were
then added to give 205 ppm organic chlorides and a sulphur content
of 2 wt % S in the combined feed mixture. This combined feed
mixture was used as a hydrocarbon stream which was contacted with
the sulphided hydroprocessing catalyst in the packed bed reactor as
mentioned above in the presence of H.sub.2 at conditions of
300.degree. C. reactor temperature, 0.92 hr.sup.-1 WHSV, and 414
NL/L H.sub.2/HC flow ratio. Three different pressure conditions
were studied: 60 barg for Example 2A, 20 barg for Example 2B, and
10 barg for Example 2C. The liquid products (i.e., the treated
hydrocarbon streams) for each of Examples 2A to 2C were analyzed
using SIMDIS, and the results are shown below:
TABLE-US-00002 Example 2A Example 2B Example 2C Liquid Product
Liquid Product Liquid Product 60 barg 20 barg 10 barg Cut, T, Cut,
T, Cut, T, wt % .degree. C. wt % .degree. C. wt % .degree. C. 0
61.4 0 52.0 0 61.4 5 72.0 5 61.4 5 72.0 10 72.0 10 72.0 10 72.0 15
72.0 15 72.0 15 72.0 20 72.0 20 72.0 20 72.0 25 72.0 25 72.0 25
72.0 30 87.6 30 72.0 30 72.0 35 87.6 35 72.0 35 87.6 40 87.6 40
87.6 40 87.6 45 87.6 45 87.6 45 132.0 50 87.6 50 134.6 50 137.2 55
129.4 55 137.2 55 139.8 60 134.6 60 139.8 60 139.8 65 139.8 65
142.4 65 161.2 70 170.6 70 163.2 70 173.8 75 176.0 75 175.4 75
177.0 79 177.6 80 179.0 78 178.0 80 278.6 83 180.6 80 271.6 85
289.2 85 279.6 85 288.2 90 292.0 90 291.0 90 291.6 95 294.0 95
294.6 95 294.0 99 295.4 99 296.8 99 295.4 100 295.6 100 297.0 100
295.6
[0073] The DHA analysis summary of the liquid product boiling below
240.degree. C. is shown below:
TABLE-US-00003 n- i- Example Paraffins, Paraffins, Olefins,
Naphthenes, Aromatics, Unknown, Heavies, No. wt % wt % wt % wt % wt
% wt % wt % 2A 22.507 19.415 0.183 31.159 17.912 0.131 0.693 2B
19.544 21.513 0.047 30.490 27.465 0.315 0.626 2C 21.368 21.281
0.000 24.687 30.719 0.355 1.591
[0074] The results provided in the tables above indicate that 20 wt
% or less of the liquid product for each of Examples 2A to 2C boils
in the hexadecane boiling point range. In contrast, the feed
contained 30 wt % hexadecane (calculated based on the feed
excluding chlorides and sulphides). Hence, at all pressures,
hydrocracking of heavy hydrocarbon molecules (e.g., hexadecane)
using a hydrogenation catalyst is demonstrated.
[0075] The corresponding chloride contents of the liquid product
(i.e., treated hydrocarbon stream) at 60 barg, 20 barg, and 10 barg
were respectively 0.11 ppmw, 0.09 ppmw, and 0.12 ppmw.
[0076] The liquid product (analyzed in DHA) for Example 2A (60
barg) contained 0.183 wt % olefins, for Example 2B (20 barg)
contained 0.047 wt %, and for Example 2C (10 barg) contained 0 wt %
olefins. At lower pressures, a significant increase in aromatics is
observed.
[0077] Example 2 demonstrates it is possible to simultaneously
dechlorinate and hydrocrack a PIONA hydrocarbon stream containing
heavy hydrocarbon molecules (e.g., hexadecane) and a chloride
content of more than 200 ppmw such that a portion of the heavy
hydrocarbon molecules are hydrocracked and chloride content is
reduced to less than 1 ppm for all pressures tested.
Example 3
[0078] In Example 3, a hydrocarbon feed mixture was prepared to
contain 30 wt % n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene,
20 wt % cyclohexane and 20 wt % ethyl benzene. To this the organic
chlorides mentioned in Example 2 above were added along with
dimethyl disulphide to give 205 ppm organic chlorides and 2 wt % S
in the mixture. This feed was used as a hydrocarbon stream which
was contacted with the sulphided hydroprocessing catalyst in the
packed bed reactor as mentioned above in the presence of H.sub.2 at
conditions of 260.degree. C. reactor temperature, 60 barg reactor
pressure, 0.92 hr.sup.-1 WHSV and 414 NL/L H.sub.2/HC flow ratio.
The liquid product (i.e., the treated hydrocarbon stream) contained
0.1 ppmw chloride.
[0079] Example 3 demonstrates the effective removal of chloride
compounds from a hydrocarbon stream at very low temperatures.
Example 4
[0080] In Example 4, a feed was prepared by mixing plastic
pyrolysis oil (36.3 g) with n-hexadecane (240 g), and then adding
dimethyl disulphide (the sulphide) and 1-chlorohexane (the chloride
compound) to give a sulphur content of 2.34 wt % and 836 ppm
chloride in the feed. This feed was used as a hydrocarbon stream
which was contacted with the hydroprocessing catalyst in the packed
bed reactor as mentioned above in the presence of H.sub.2 under
several operating conditions as provided in the table below:
TABLE-US-00004 T, P, WHSV, H.sub.2/HC, Cl, ppm in .degree. C. barg
hr.sup.-1 NL/L liquid product 300 60 0.92 414 0.32 300 40 0.92 414
0.87 350 40 0.92 414 3.42 400 40 0.92 414 3.15
[0081] The gas composition for the reactor effluents is shown
below.
TABLE-US-00005 Cl, ppm n- i- T, P, WHSV, H.sub.2/HC, in liquid
H.sub.2, CH.sub.4, C.sub.2H.sub.6, C.sub.3H.sub.8, C.sub.4H.sub.10,
C.sub.4H.sub.10, .degree. C. barg hr.sup.-1 NL/L product mole %
mole % mole % mole % mole % mole % 300 40 0.92 414 0.87 96.63 3.25
0.12 -- -- -- 350 40 0.92 414 3.42 95.32 4.48 0.2 -- -- -- 400 40
0.92 414 3.15 93.96 5.21 0.45 0.23 0.08 0.07
[0082] As can be seen, the data indicates LPG gases are formed at
temperatures close to 400.degree. C.
[0083] Example 4 demonstrates it is possible to dechlorinate a
hydrocarbon stream containing plastic pyrolysis oil and having
chloride compounds from a chloride content of more than 800 ppmw
chlorides to less than 5 ppmw in the liquid product. As can be seen
from the above table, the chloride content of the liquid product
(i.e., the treated hydrocarbon stream) increases when the reactor
bed temperature is increased to at or above 350.degree. C. At
temperatures below 350.degree. C., Example 4 demonstrates removal
of chloride compounds to chloride contents less than 3 ppmw, and
even sub-ppm levels.
Example 5
[0084] In Example 5, a hydrocarbon feed mixture was prepared by
mixing 30 wt % n-hexadecane, 10 wt % i-octane, 20 wt % 1-decene, 20
wt % cyclohexane, and 20 wt % ethyl benzene. Dimethyl disulphide,
2-chloropentane, 3-chloro-3-methyl pentane, 1-chlorohexane,
(2-chloroethyl) benzene, and chlorobenzene were then added to give
1100 ppm organic chlorides and a sulphur content of 2 wt % S in the
combined feed mixture. This combined feed mixture was used as the
hydrocarbon stream which was contacted with the hydrogenating
catalyst in the packed bed reactor as mentioned above in the
presence of H.sub.2 at conditions of 300.degree. C. reactor
temperature, 40 barg reactor pressure, 0.92 hr.sup.-1 WHSV, and 414
NL/L H.sub.2/HC flow ratio. The liquid product contained 0.23 ppmw
chlorides and paraffins of 22.569 wt %, paraffins of 19.752 wt %,
olefins of 0.114 wt %, naphthenes of 33.242 wt %, aromatics of 23.7
wt %, unknowns of 0.16 wt % and heavies of 0.463 wt % as per DHA
analysis. This again demonstrates the dechlorination of liquid at
much higher chloride concentrations.
[0085] The SIMDIS of liquid product resulted in the following
distribution and also indicated hydrocracking:
TABLE-US-00006 Cut, T, wt % .degree. C. 0 61.4 5 72 10 72 15 72 20
72 25 72 30 72 35 72 40 87.6 45 87.6 50 132 55 134.6 60 137.2 65
142.4 70 170.6 75 175.4 80 177 85 287 90 290 95 292.2 99 293.4 100
293.8
[0086] DHA Group type analysis of the liquid product by carbon
number (in wt %) is as below:
TABLE-US-00007 n-Paraffins, i-Paraffins, Olefins, Naphthenes,
Aromatics, Total, Carbon No. wt % wt % wt % wt % wt % wt % 2 0 3 0
4 0.008 0.056 0.064 5 0.033 0.021 0.054 6 0.035 0.05 26.925 0.072
27.082 7 0.013 0.008 0.012 0.033 8 0.287 13.892 0.951 21.97 37.1 9
0.172 0.114 5.265 1.623 7.174 10 22.161 5.553 0.089 0.035 27.838 11
0.025 0.025 12 0.007 0.007 Oxygenates Heavies 0.464 Unknown 0.16
Total, wt % 100.001
[0087] In this example, the yield of liquid products was 95.5 wt %
of the total products. The balance was gas products.
Example 6
[0088] In Example 6, a n-hexadecane feed mixture was prepared by
mixing n-hexadecane with dimethyl disulphide, 2-chloropentane,
3-chloro-3-methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene,
and chlorobenzene to give 1,034 ppm of chlorides and 2 wt % Sulphur
in the feed. This combined feed mixture was used as the hydrocarbon
stream which was contacted with the hydrogenating catalyst in the
packed bed reactor as mentioned above in the presence of H.sub.2 at
conditions of 300.degree. C. reactor temperature, 40 barg reactor
pressure, 0.92 hr.sup.-1 WHSV, and 414 NL/L H.sub.2/HC flow ratio.
The liquid product contained 0.3 ppmw chlorides and paraffins of
22.569 wt %, i-paraffins of 19.752 wt %, olefins of 0.114 wt %,
naphthenes of 33.242 wt %, aromatics of 23.7 wt %, unknowns of 0.16
wt % and heavies of 0.463 wt % as per DHA analysis. This again
demonstrates the dechlorination of liquid at high chloride
concentrations to sub-ppm levels.
[0089] The SIMDIS of liquid product resulted in the following
distribution and also indicated hydrocracking to the extent of
about 15 wt % on a chloride and sulphide-free feed basis:
TABLE-US-00008 Cut, T, wt % .degree. C. 0 61.4 5 129.4 10 161.2 13
170.6 14 260.2 15 272.4 20 285.2 25 287.4 30 289 35 290.2 40 291.2
45 292.2 50 293 55 293.8 60 294.4 65 295 70 295.6 75 296.2 80 297
85 297.4 90 297.8 95 298.2 99 298.8 100 310.8
[0090] DHA Group type analysis of the liquid product by carbon
number (in wt %) is as below and indicates conversion of
n-hexadecane to various PIONA components:
TABLE-US-00009 n-Paraffins, i-Paraffins, Olefins, Naphthenes,
Aromatics, Total, Carbon No. wt % wt % wt % wt % wt % wt % 2 0.005
0.005 3 0.006 0.006 4 0.019 0.098 0.118 5 0.068 0.064 0.132 6 0.072
0.133 25.607 0.11 25.922 7 0.016 0.034 0.051 8 0.401 13.31 1.268
21.179 36.157 9 0.133 0.136 5.53 2.449 8.248 10 19.165 8.19 0.213
0.049 27.617 11 0.03 0.03 12 0.011 0.011 Oxygenates Heavies 1.413
Unknown 0.29 Total, wt % 100
Example 7
[0091] Example 7 demonstrates a process for sulphiding a
hydroprocessing catalyst. The particular steps of the process are
shown in FIG. 2. The time of 0 hours (zero time) in FIG. 2
corresponds to a time after the hydroprocessing catalyst is
introduced into the hydroprocessing reactor.
[0092] At ambient temperature, the hydroprocessing reactor (having
previously been loaded with the hydroprocessing catalyst) was
purged with hydrogen for 30 to 60 minutes at a set operating
pressure (e.g., 40 to 60 barg). The set operating pressure was
maintained by venting the reactor when the pressure of the reactor
during hydrogen purging increased above the set operating pressure
(e.g., due to a hydrogen source pressure greater than the set
operating pressure).
[0093] After purging the hydroprocessing reactor for 30-60 minutes
at ambient temperature, the hydrogen purge was stopped.
[0094] Still at the ambient temperature, the sulphiding feed was
then introduced into the reactor using a high pressure pump against
the set reactor pressure at a weight hourly space velocity (WHSV)
of 3 hr.sup.-1 (on bone-dry catalyst basis). The sulphiding feed
(e.g., for use in doping stream 7 of FIG. 1) was prepared by mixing
n-hexadecane with dimethyl disulphide in appropriate quantity to
give 3 wt % sulphur based on total weight of the sulphiding feed.
For the sulphiding feed, as per catalyst sulphiding protocol
followed, cracked feedstock cannot be used. Hence, n-hexadecane is
used. In place of n-hexadecane, straight-run naphtha, diesel, or
vacuum gas oils can also be used.
[0095] FIG. 2 indicates the hydroprocessing catalyst was soaked
with a sulphiding feed without a flow of hydrogen in the reactor
and at ambient temperature for a period of 3 hours (ending at time
3.5 hours after zero time in FIG. 2). Catalyst soaking provides for
complete wetting of the hydroprocessing catalyst; however, soaking
is optional. Liquid was drained from the bottom of a downstream gas
liquid separator.
[0096] After introducing the sulphiding feed to the reactor, the
hydroprocessing reactor bed temperature was raised to 250.degree.
C. at a rate of 30.degree. C. per hour with a flow of H.sub.2 at a
ratio of 200NL H.sub.2/L liquid feed. As shown in FIG. 2, the
temperature was increased from a time of 3.5 hours to a time of
10.8 hours after zero time.
[0097] The hydroprocessing reactor bed temperature was then held at
250.degree. C. for a period of 8 hours. As shown in FIG. 2, the
temperature was held from a time of 10.8 hours to a time of 18.8
hours after zero time.
[0098] After holding the bed temperature, the bed temperature was
further increased to 320.degree. C. to 350.degree. C. at a rate of
20.degree. C. per hour without any temperature overshoot at the
final temperature. As shown in FIG. 2, the temperature was
increased from a time of 18.8 hours to a time of 22.3 hours after
zero time.
[0099] The hydroprocessing reactor bed temperature was then
maintained at 320.degree. C. to 350.degree. C. for a period of 8
hours. As shown in FIG. 2, the temperature was maintained at
320.degree. C. to 350.degree. C. from a time of 22.3 hours to a
time of 30.0 hours after zero time.
[0100] During the step of maintaining the temperature at
320.degree. C. to 350.degree. C. for 8 hours, after 5 hours of
maintaining the temperature at 320.degree. C. to 350.degree. C.,
gas sampling began, and a first gas sample was obtained from the
reactor effluent. A second gas sample was obtained close to 8 hours
while the bed temperature is maintained at 320.degree. C. to
350.degree. C. The first and second gas samples were analyzed in a
refinery gas analyzer (RGA) gas chromatograph and constancy of
H.sub.2S concentration in reactor effluent gases in the first and
second samples signified further uptake of sulphur on the catalyst
did not take place. This marked the completion of the catalyst
sulphiding process. If the first and second samples had not
exhibited constancy in H.sub.2S concentration, additional samples
would have been taken and the temperature maintained until two
successive samples exhibited constancy in H.sub.2S
concentration.
[0101] The present disclosure is further illustrated by the
following embodiments, which are not to be construed in any way as
imposing limitations upon the scope thereof. On the contrary, it is
to be clearly understood that resort can be had to various other
aspects, embodiments, modifications, and equivalents thereof which,
after reading the description herein, can be suggest to one of
ordinary skill in the art without departing from the spirit of the
present invention or the scope of the appended claims.
Additional Disclosure
[0102] The following are enumerated embodiments which are provided
as non-limiting examples:
[0103] A first embodiment, which is a process for activating and
maintaining a catalyst for use in hydrotreating a hydrocarbon
stream to simultaneously reduce heavier boiling components,
chlorides, and olefins, comprising:
[0104] continuously contacting the hydrocarbon stream with a
hydroprocessing catalyst in the presence of hydrogen, wherein the
hydrocarbon stream comprises one or more chloride compounds and one
or more sulphides.
[0105] A second embodiment, which is the process of the first
embodiment, wherein the one or more sulphides comprise dimethyl
disulphide, mercaptans, carbon disulphide, hydrogen sulphide, or
combinations thereof.
[0106] A third embodiment, which is the process of any one of the
first through the second embodiments, wherein the one or more
sulfides of the hydrocarbon stream are present in an amount such
that a sulphur content of the hydrocarbon stream is about 0.5 wt %
to about 5 wt % based on a total weight of the hydrocarbon
stream.
[0107] A fourth embodiment, which is the process of any of the
first through the third embodiments, wherein the one or more
sulfides of the hydrocarbon stream are present in an amount such
that a sulphur content of the hydrocarbon stream is about 2 wt %
based on a total weight of the hydrocarbon stream.
[0108] A fifth embodiment, which is the process of any one of the
first through the fourth embodiments, further comprising:
[0109] before the step of continuously contacting the hydrocarbon
stream with the hydroprocessing catalyst in the presence of
hydrogen, contacting a catalyst activating stream with the
hydroprocessing catalyst, wherein the catalyst activating stream
comprises one or more sulphides.
[0110] A sixth embodiment, which is the process of the fifth
embodiment, wherein the catalyst activating stream further
comprises one or more hydrocarbons.
[0111] A seventh embodiment, which is the process of the sixth
embodiment, wherein the one or more hydrocarbons comprise
hexadecane.
[0112] An eighth embodiment, which is the process of any one of the
fifth through the seventh embodiments, wherein the one or more
sulfides of the catalyst activating stream are present in an amount
such that a sulphur content of the catalyst activating stream is
about 0.5 wt % to about 5 wt % based on a total weight of the
catalyst activating stream.
[0113] A ninth embodiment, which is the process of any one of fifth
through the eighth embodiments, wherein the one or more sulfides of
the catalyst activating stream are present in an amount such that a
sulphur content of the catalyst activating stream is about 3 wt %
based on a total weight of the catalyst activating stream.
[0114] A tenth embodiment, which is the process of any one of the
fifth through the ninth embodiments, wherein after the step of
contacting and during the step of continuously contacting, the
hydroprocessing catalyst has hydrogenation sites and hydrocracking
sites.
[0115] An eleventh embodiment, which is the process of any one of
the fifth through the tenth embodiments, wherein the step of
contacting a catalyst activating stream with the hydroprocessing
catalyst is performed for a period of 30 hours or less, wherein the
step of continuously contacting a hydrocarbon stream with a
hydroprocessing catalyst initiates after the period elapses.
[0116] A twelfth embodiment, which is the process of any one of the
fifth through the eleventh embodiments, wherein the step of
contacting a catalyst activating stream with the hydroprocessing
catalyst is performed ex-situ of a hydroprocessing reactor.
[0117] A thirteenth embodiment, which is the process of any one of
the first and the twelfth embodiments, wherein the step of
continuously contacting a hydrocarbon stream with a hydroprocessing
catalyst is performed ex-situ of the hydroprocessing reactor.
[0118] A fourteenth embodiment, which is the process of any one of
the fifth through the thirteenth embodiments, wherein the step of
contacting a catalyst activating stream with the hydroprocessing
catalyst is performed in-situ of a hydroprocessing reactor.
[0119] A fifteenth embodiment, which is the process of any one of
the first and the fourteenth embodiments, wherein the step of
continuously contacting a hydrocarbon stream with a hydroprocessing
catalyst is performed in-situ of the hydroprocessing reactor.
[0120] A sixteenth embodiment, which is the process of any one of
the first through the fifteenth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a temperature of
100.degree. C. to 450.degree. C.
[0121] A seventeenth embodiment, which is the process of any one of
the first through the sixteenth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a temperature of
100.degree. C. to 350.degree. C.
[0122] An eighteenth embodiment, which is the process of any one of
the first through the seventeenth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a temperature of
260.degree. C. to 350.degree. C.
[0123] A nineteenth embodiment, which is the process of any one of
the first through the eighteenth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a weight hourly space
velocity of 0.1 to 10 hr.sup.-1.
[0124] A twentieth embodiment, which is the process of any one of
the first through the nineteenth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a hydrogen to hydrocarbon
ratio of 10 to 3,000 NL/L.
[0125] A twenty-first embodiment, which is the process of any one
of the first through the twentieth embodiments, wherein the step of
continuously contacting the hydrocarbon stream with the
hydroprocessing catalyst is performed at a pressure of 1 to 200
barg.
[0126] A twenty-second embodiment, which is the process of any one
of the first through the twenty-first embodiments, wherein the
hydrocarbon stream comprises the one or more chloride compounds in
a concentration of greater than 200 ppmw based on a total weight of
the hydrocarbon stream.
[0127] A twenty-third embodiment, which is the process of any one
of the first through the twenty-second embodiments, wherein the
hydrocarbon stream further comprises one or more olefins.
[0128] A twenty-fourth embodiment, which is the process of the
twenty-third embodiment, wherein the one or more olefins are
present in the hydrocarbon stream in a concentration of 20 wt % or
more based on the total weight of the hydrocarbon stream.
[0129] A twenty-fifth embodiment, which is the process of any one
of the twenty-third through the twenty-fourth embodiments, wherein
the hydrocarbon stream further comprises heavy hydrocarbon
molecules, wherein the at least a portion of the one or more
olefins comprises at least a portion of the heavy hydrocarbon
molecules.
[0130] A twenty-sixth embodiment, which is the process of any one
of the first or the twenty-third embodiment, wherein the
hydrocarbon stream further comprises paraffins.
[0131] A twenty-seventh embodiment, which is the process of the
twenty-sixth embodiment, wherein the hydrocarbon stream further
comprises heavy hydrocarbon molecules, wherein the at least a
portion of the one or more paraffins comprises at least a portion
of the heavy hydrocarbon molecules.
[0132] A twenty-eighth embodiment, which is the process of any one
of the first through the twenty-seventh embodiments, wherein the
hydrocarbon stream further comprises heavy hydrocarbon
molecules.
[0133] A twenty-ninth embodiment, which is the process of the
twenty-eighth embodiment, wherein a concentration of the heavy
hydrocarbon molecules in the hydrocarbon stream is 10 wt % to 90 wt
% based on the total weight of the hydrocarbon stream.
[0134] A thirtieth embodiment, which is the process of any of the
twenty-fifth and twenty-seventh through the twenty-ninth
embodiments, wherein the heavy hydrocarbon molecules comprise
C.sub.16 and larger hydrocarbons.
[0135] A thirty-first embodiment, which is the process of the
thirtieth embodiment, wherein the C.sub.16 and larger hydrocarbons
comprise paraffins, i-paraffins, olefins, naphthenes, aromatic
compounds, or combinations thereof.
[0136] A thirty-second embodiment, which is the process of any one
of the first through the thirty-first embodiments, wherein the
hydrocarbon stream is one or more of a plastic pyrolysis oil and a
tire pyrolysis oil.
[0137] A thirty-third embodiment, which is the process of any one
of the first through the thirty-second embodiments, wherein the
hydroprocessing catalyst comprises cobalt and molybdenum on an
alumina support, nickel and molybdenum on an alumina support,
tungsten and molybdenum on an alumina support, or nickel and
molybdenum sulphides.
[0138] A thirty-fourth embodiment, which is the process of any one
of the first through the thirty-third embodiments, wherein the
hydroprocessing catalyst comprises platinum and palladium on an
alumina support.
[0139] While embodiments of the disclosure have been shown and
described, modifications thereof can be made without departing from
the spirit and teachings of the invention. The embodiments and
examples described herein are exemplary only, and are not intended
to be limiting. Many variations and modifications of the invention
disclosed herein are possible and are within the scope of the
invention.
[0140] Accordingly, the scope of protection is not limited by the
description set out above but is only limited by the claims which
follow, that scope including all equivalents of the subject matter
of the claims. Each and every claim is incorporated into the
specification as an embodiment of the present invention. Thus, the
claims are a further description and are an addition to the
detailed description of the present invention. The disclosures of
all patents, patent applications, and publications cited herein are
hereby incorporated by reference.
* * * * *