U.S. patent number 3,904,389 [Application Number 05/497,023] was granted by the patent office on 1975-09-09 for process for the production of high btu methane-containing gas.
Invention is credited to David L. Banquy.
United States Patent |
3,904,389 |
Banquy |
September 9, 1975 |
Process for the production of high BTU methane-containing gas
Abstract
A process for the production of high Btu methane containing
gases by dividing the effluent, having a substantial CO content,
from fossil fuel gasification (preferably at a much higher
temperature than 500.degree.C) from which C and S have been removed
into a plurality of fractions; subjecting one effluent fraction to
shift conversion and CO.sub.2 removal; subjecting another effluent
fraction to a methanation step; joining the effluents from the
shift conversion and methanation steps and subjecting them to a
second methanation step, utilizing therein the N.sub.2 --H.sub.2
--CH.sub.4 mixture from the shift conversion; and separating the
excess nitrogen from the product methane gas by cryogenic
removal.
Inventors: |
Banquy; David L. (75006 Paris,
FR) |
Family
ID: |
23975153 |
Appl.
No.: |
05/497,023 |
Filed: |
August 13, 1974 |
Current U.S.
Class: |
48/215; 48/197R;
518/703; 518/705; 518/706; 518/708 |
Current CPC
Class: |
F25J
3/0219 (20130101); C01B 3/386 (20130101); F25J
3/0233 (20130101); C10L 3/00 (20130101); F25J
3/0257 (20130101); C01B 3/50 (20130101); F25J
2200/02 (20130101); C01B 2203/0288 (20130101); F25J
2205/02 (20130101); F25J 2235/60 (20130101); Y02P
30/40 (20151101); C01B 2203/0877 (20130101); F25J
2200/74 (20130101); C01B 2203/147 (20130101); C01B
2203/0475 (20130101); C01B 2203/0445 (20130101); C01B
2203/0495 (20130101); C01B 2203/0883 (20130101); C01B
2203/046 (20130101); C01B 2203/0261 (20130101); C01B
2203/045 (20130101); C01B 2203/145 (20130101); C01B
2203/0485 (20130101); C01B 2203/0894 (20130101); C01B
2203/1247 (20130101); C01B 2203/0415 (20130101); Y02P
20/151 (20151101) |
Current International
Class: |
C10L
3/00 (20060101); C10G 11/00 (20060101); C10G
11/22 (20060101); C01B 3/50 (20060101); C01B
3/38 (20060101); C01B 3/00 (20060101); C01B
002/14 () |
Field of
Search: |
;48/197R,215,214
;260/449M |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Serwin; R. E.
Claims
What is claimed is:
1. A process for producing a high Btu, methane-rich gas from a
suitable carbon- or hydrocarbon-containing feedstock, comprising
(a) generating a gaseous effluent having a substantial CO content
from said feedstock and purifying said gaseous effluent to remove
the impurities therefrom comprising the residual carbon and sulfur
impurities; (b) dividing the resulting gaseous effluent into a
plurality of fractions; (c) subjecting a first effluent fraction to
methanation; (d) subjecting a second effluent fraction to the
successive steps of shift conversion and CO.sub.2 removal; (e)
mixing the resulting effluents from steps (c) and (d) and
subjecting the resulting mixture to methanation; and (f) separating
the excess nitrogen present from the methane-rich product.
2. A process according to claim 1, wherein the feedstock is a
fossil fuel.
3. A process according to claim 1, wherein the generation of said
gaseous effluent is conducted in the presence of an oxidant
selected from the group consisting of air and oxygen enriched air
and the resulting nitrogen contained in the methane-rich final gas
stream is separated therefrom by cryogenic means.
4. A process according to claim 1, wherein the feedstock is one
heavier than naphtha and the gaseous effluent from said feedstock
is generated at a temperature between about 650.degree.C and
1000.degree.C under adiabatic conditions.
5. A process according to claim 4, wherein the pressure is between
30 and 100 atmospheres.
6. A process according to claim 1 wherein the gas generation step
is conducted under adiabatic conditions in the presence of a
catalyst.
7. A process according to claim 1, wherein at least substantially
all the hydrogen in the first effluent fraction is reacted with the
carbon oxides present therein.
8. A process according to claim 2, wherein a
humidifier-dehumidifier system is used to supply at least a part of
the steam required for shift conversion.
9. A process according to claim 1, wherein the mixture of effluents
from steps (c) and (d) contains a ratio of hydrogen to carbon
oxides substantially stoichiometric to that required for
substantially complete methanation of said carbon oxides.
Description
BACKGROUND OF THE INVENTION
The present invention generally relates to the production of high
Btu methane-containing gases having a heating value in the range of
about 800 to about 1000 Btu/SCF, and more particularly to a process
for producing such gases from the gaseous effluent resulting from
the gasification of fossil fuels such as gas, oil, etc. By means of
this invention, the effluent from gasification, upon removal of
carbon and sulfur therefrom, can be divided into a plurality of
fractions or streams, whereby, in a first fraction or stream, the
hydrogen contained therein is used to methanate part of the CO and
CO.sub.2 ; whereby, another or second effluent fraction or stream
is subjected to shift conversion, followed by CO.sub.2 removal, to
result in a H.sub.2 --N.sub.2 --CH.sub.4 mixture; and whereby the
effluents of the first and second fractions or streams can be
joined, with the hydrogen in said mixture serving to methanate the
remaining carbon oxides from said first fraction stream, and the
excess nitrogen removed from the resulting methane product by
cryogenic separation.
Heretofore, those attempting to produce a methane gas product such
as substitute natural gas from the effluent of oil or coal
gasification have been confronted with the problem of having to
convert the rich CO content thereof (e.g., 50% CO) into methane in
the face of the fact that said conversion is a highly exothermic
one. Traditional solutions to this problem have employed alternate
heating and cooling treatments; used extensive recycle streams as a
diluent to absorb some of the exothermic heat evolved; and employed
other conventional methods, etc.
However, these previous methods have been costly, essentially
because the methanation is carried out under conditions which
require a high recycle gas rate and/or very large heat removal,
which is not the case with respect to the first and second
methanation steps of the present invention. Furthermore, in order
to get a high Btu value in the final gas, the previous processes
have used oxygen in their gasification step, produced in a costly
air separation unit, whereas air or oxygen enriched air can be used
in the gasification step of the present invention.
In another area of substitute natural gas production, several known
processes are based on the reaction of steam with a light
hydrocarbon, in a catalytic reactor operating adiabatically around
500.degree.C. The operating temperature is such that enough methane
is synthesized in the reactor (exothermic reaction) to supply heat
for the endothermic steam reforming reaction. The main drawback of
such processes is that the feedstock must not be heavier than
naphtha. In order to gasify feedstocks heavier than naphtha, it is
recognized that much higher temperatures are needed, even if a
catalyst is used. At such higher temperature, however, much less
methanation is taking place in the reactor, and consequently an
additional source of heat is required to supply the heat needed for
the steam reforming reaction. In the present invention, however,
this can be accomplished by the injection of air or oxygen enriched
air in the reactor, which is also operating adiabatically.
Methods relating generally to the production of substitute natural
gas are well known. For example, U.S. Pat. No. 3,347,647 discloses
a process for the conversion of solid fossil fuel to high Btu
pipeline gas which includes a two-stage hydrogasification reactor
as well as a hydrogen plant for producing hydrogen from char
residue by the so-called Texaco partial oxidation process. In this
system, coal supplies all process feedstock requirements for the
product gas and the reaction hydrogen, and countercurrent flow of
the char and hydrogen in combination with dual reaction temperature
zones enable the raw feed coal to enter the low temperature end of
the reactor and mix with an atmosphere with a relatively high
concentration of methane while hydrogen enters the high temperature
end of the reactor and reacts with the partially gasified char
where the methane concentration is relatively low, thereby
providing for continuous production of high Btu methane. U.S. Pat.
No. 3,347,647, however, is not cognizant of splitting its
gasification effluent into a plurality of fractions each of which
is subjected to a different treatment (methanation as opposed to
shift conversion), whereby the effluents of the different
treatments are combined and methanated, and the excess nitrogen
removed from the product methane or substitute natural gas. Nor is
U.S. Pat. No. 3,347,647 aware of the benefits to be derived from
methanation of its carbon oxides in two separate steps.
Catalytic methanation is disclosed in U.S. Pat. No. 3,511,624
wherein a mixture of carbon oxides, hydrogen, steam and at least
25% volume of methane is passed, in a first stage, over a
methanation catalyst after which the steam is partially removed
from the mixture and the resulting mixture is passed, in a second
stage, over a methanation catalyst which is at a temperature within
a range lower than the temperature of the mixture leaving the first
stage. However, while U.S. Pat. No. 3,511,624 discloses a two-stage
catalytic methanation process, it is to be noted that such stages
involve taking a feed gas already containing from 25-50% methane
and 5-20% CO.sub.2, with little CO (0-5%) present and subjecting it
to two consecutive methanation stages. Subjecting such a feed gas
to such methanation steps is the means this patent teaches to avoid
the vast amount of heat released that accompanies the exothermic
reaction between hydrogen and the carbon oxides of more
conventional feed gases which are rich in both of these gases such
as the effluents of oil or coal gasification. Thus, the process of
U.S. Pat. No. 3,511,624 is totally unlike that of the present
invention which is capable of utilizing various feedstocks and
which has two non-consecutive methanation steps involving
feedstocks of different composition and other distinguishing
process features.
Although individual process features or steps of the present
invention are perhaps known such as, e.g., the cryogenic separation
of natural gas, as shown, for example, in U.S. Pat. No. 3,616,652,
none of the foregoing patents or the prior art have heretofore been
aware of or appreciated the significant advance in the art to be
associated with the process of the present invention and its
combination and sequential arrangement of process steps.
SUMMARY OF THE INVENTION
The present invention relates generally to a process for producing
a methane-rich gas or substitute natural gas from any conventional
carbon or hydrocarbon-containing feedstock such as oil or coal
comprising generating a gas effluent from said feedstock and
removing the carbon solids and sulfur impurities (e.g., H.sub.2 S
and COS) therefrom; dividing the gas effluent into a plurality of
fractions, and methanating one fraction while concurrently shift
converting another and removing the CO.sub.2 therefrom; combining
or mixing the resulting effluents from methanation and shift
conversion and subjecting the consequent mixture to methanation;
and separating the excess nitrogen present from the methanerich, or
substitute natural gas product.
BRIEF DESCRIPTION OF THE DRAWINGS
The process of the present invention is illustrated schematically
in the drawings by means of flow diagrams, showing each step or
stage of said process, wherein:
FIG. 1 is a block diagram showing the process steps of the present
invention in their proper sequence;
FIG. 2 is a flow diagram of the gas generation step;
FIG. 3 is a flow diagram of the sulfur removal step;
FIG. 4 is a flow diagram of the first methanation step;
FIG. 5 is a flow diagram of the shift conversion step;
FIG. 6 is a flow diagram of the carbon dioxide removal step;
FIG. 7 is a flow diagram of the second methanation step; and
FIG. 8 is a flow diagram of the cryogenic separation step.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Shown in FIG. 2 are the essential features of the gas generation
step, utilizing, as a feedstock, a liquid hydrocarbon. However, any
hydrocarbon- or carbo-containing material can be used as a
feedstock in the present gas generation step provided that such
material can react with oxygen or a source of oxygen at high
temperatures of upwards of 500.degree.C, preferably in the range of
650.degree.C to 1000.degree.C, to produce a gas mixture containing
hydrogen, carbon oxides and methane. Thus, utilizable in the gas
generation step are such feedstocks as coal; synthetic polymers
such as waste polymeric materials, shale oil; naphtha or heavier
hydrocarbon feedstocks, etc.
As an oxidant for use in the present gas generation, suitable
oxygen sources such as air per se, air enriched with oxygen, steam,
and/or mixtures thereof can be employed. Introduction of air, of
course, involves addition of nitrogen to the process. The process
step of "gas generation" should be understood to be applicable to a
wide diversity of types, including, e.g., non-catalytic adiabatic
gas generation, catalytic adiabatic gas generation, etc., and is
intended to refer to any process that is able to convert a
carboncontaining feedstock into a gas mixture, capable of being
processed eventually into a methane-rich gas, preferably of high
Btu content, in an adiabatic reactor, with the aid of air or
oxygen-enriched air. A conventional catalyst can be utilized in the
gas generation step, if desired, and such use enables the outlet
temperature and corresponding nitrogen content of the exiting
gaseous effluent to be lowered.
The gas generation step may also be denoted as "partial oxidation";
however, should a conventional catalyst be utilized therein, such
step would then be generally denoted as "air reforming".
The hydrocarbon- or carbon-containing feedstock can be completely
gasified, if desired; however, where heavier feedstocks are used,
such as those heavier than gas oil, the feedstock may only be
partially gasified; consequently the liquid hydrocarbon mixture
would have to be separated by condensation before purification
thereof by the subsequent sulfur removal step.
In the present gasification step, the hydrocarbon feedstock is
pumped to the desired operating pressure through pump 1, and then
is mixed with steam and preheated in the heater 2 to a temperature
as high as possible, preferably in the range indicated above.
Air or oxygen-enriched air, for partial oxidation, or, if a
conventional catalyst is used, air reforming, of the carbon or
hydrocarbon feedstock, is compressed in a compressor 3 and
preheated by means of heating apparatus 4 to a very high
temperature that may range between 500.degree.C and 1000.degree.C.
Alternative means for achieving this high preheat temperature of
the air stream include such apparatus as fired heaters, fixed or
moving bed pebble type heat exchangers, or heat exchange with the
gas effluent, etc.
In an alternative embodiment of gas generation according to the
present process, some steam may also be added to the air stream
before preheating.
The preheated air or air-oxygen mixture and the preheated steam
feedstock mixture are then fed into reactor 5, which is adapted to
operate adiabatically, and reacted. Reactor 5 is entirely lined
with refractory material and designed to operate at high
temperatures, preferably ranging between 650.degree. and
1000.degree. C. This reactor can be an empty vessel such as that
used in the so-called Texaco and Shell partial oxidation processes,
or the reactor can be filled with a fixed or fluid bed
catalyst.
It is preferred that the operating pressure in the gas generator be
as high as is technologically feasible. Preferred pressures are
those in the range of 30 to 100 atmospheres.
The effluent gas mixture leaving reactor 5 contains a substantial
amount of CO, as is known in the art, e.g., amounts generally in
the range of 15 to 50%, and is ordinarily at a temperature between
650.degree.C and 1000.degree.C; hence, it is directed to a waste
heat boiler 6, so as to enable the recovery of its evolved heat as
high pressure steam for use elsewhere in the present process, and
for driving the various plant apparatus. Alternatively, part or all
of this heat can be used to preheat the steam feedstock mixture
introduced into the gas generator.
In the event that the feedstock has been completely gasified in
reactor 5, the effluent gas is further cooled in heat exchanger 7
(for recovery of its heat) and then in final cooler 8.
Since in some gasification processes, however, the feedstock is
only partially gasified, in such cases, after heat recovery in
waste heat boiler 6, it is usually preferable to achieve a final
cooling in a tower having coutercurrent water and liquid
hydrocarbon circulation.
Since the gaseous effluent produced by gasification includes
impurities, e.g., hydrogen sulfide and carbonyl sulfide, these
impurities must be removed therefrom in a purification step denoted
herein as sulfur removal. A number of feasible alternative means
are suitable for this purpose, among these being the use of an
absorption stripping system, which is preferred means. As shown in
FIG. 3, a "sour" or impure gaseous effluent obtained from the
gasification step shown in FIG. 2 is contacted with a conventional
liquid solvent such as NaOH, KOH, diethanolamine, etc., in an
absorption tower 9. Hydrogen sulfide and other sulfur bearing
gases, together with part of the carbon dioxide, are absorbed
selectively or non-selectively by the solvent. Acid gases are
recovered from the solvent in a stripping tower 10.
The regenerated liquid solvent is then recycled to the absorption
tower 9 through pump 11. The regeneration heat, if required, is
supplied by a reboiler (not shown).
Alternatively, regeneration can be effected by flashing the solvent
from the high pressure of absorption tower 9 to the low pressure of
stripping tower 10, or by using an inert gas for stripping in
stripping tower 10.
In the event the acid gases leave the stripping tower 10 at a
temperature appreciably higher than the absorption temperature in
absorption tower 9, it is usually preferable to cool these gases in
cooler 12 and condense the liquid in condenser or heat exchanger 13
for reflux to stripping tower 10, thus obtaining the final
concentrated acid gas that can be subsequently treated in a
conventional sulfur plant for sulfur recovery.
In accordance with the composition of the effluent gas leaving the
sulfur removal step, the gas can be split into a plurality of
fractions or streams following the criteria previously described.
In a preferred embodiment of this invention, the effluent gas is
split into two fractions or streams of about 50% each. (The
material balance, set forth in Example I below, it will be noted,
showed a 45-55% split).
A first stream undergoes a methanation reaction shown in a
schematic flow diagram in FIG. 4. The main purpose of this reaction
is to methanate, as much as possible, the carbon oxides contained
in the desulfurized gas effluent, by consuming virtually all the
hydrogen present, which represents 37% in the particular case of
the aforesaid material balance. In view of the fact that the
residual carbon oxides content of the effluent from the first
methanation step has no appreciable effect on the following step of
the process, it is likely that one catalyst bed is sufficient to
perform this reaction, but due to the high content of hydrogen and
carbon oxides in the methanation feed, it is preferred that this
goal be achieved by recycling an appreciable part of the gas
effluent from the first methanation, after cooling. The amount of
recycled gas can be adjusted in accordance with the gas composition
from the sulfur removal step in such a way so as to maintain the
maximum temperature in the methanation reactor at a level
consistent with a total consumption of hydrogen in the reaction to
form methane.
In one embodiment of this invention, some amount of steam may be
mixed with the feed gas to the first methanation step in order to
achieve some degree of shift conversion at the same time as the
methanation reaction is proceeding. This mode of operation may be
desirable in some cases, especially when the catalyst used does not
have the proper inhibitors to avoid carbon formation due to the
high CO partial pressure. In fact, it is possible to adjust this
steam injection to the rate required for substantially eliminating
the presence of carbon monoxide in the effluent of the fist
methantation step, thus minimizing the risk of carbon formation.
This process variation, although not represented in the aforesaid
material balance, is within the spirit of the present invention,
and should be taken into consideration for the proper split of the
gas fractions after the sulfur removal step.
As shown in FIG. 4, the feed gas from the sulfur removal step is
first mixed with the gas recycled from compressor 24, and the
mixture is preheated in heat exchanger 25 and then fed into the
methanation reactor 26. The preferred inlet temperature to the
reactor is in the range of 240 to 300.degree.C, while the preferred
outlet temperature is in the range of 450 to 700.degree.C.
The gas leaving the reactor 26 is first cooled in heat exchanger 27
so as to recover the high temperature heat either in generating
steam, or in any other way compatible with the other sections of
the plant. The gas is then cooled in heat exchanger 25 to preheat
the reactor feed and finally is further cooled in heat exchanger 28
for heat recovery to a lower level and in cooler 29 to about
ambient temperature. The water produced in the methanation reaction
is condensed and separated before proceeding to the following stage
of the process.
The second desulfurized effluent gas fraction is subjected to shift
conversion, so as to convert CO contained in said effluent gas
fraction to CO.sub.2. This reaction requires an appreciable amount
of steam, whereas the gas effluent from the sulfur removal step is
usually at a temperature close to ambient temperature and contains
very little or no steam. Thus, for optimum heat recovery around the
shift reactor, it is preferred to use a humidifier-dehumidifier
system to convey the heat to the shift reactor, in the form of
steam, flowing from downstream to upstream.
As shown in FIG. 5, the cold, second desulfurized effluent gas
fraction is first contacted countercurrently in the humidifier
tower 30 with hot water coming from the dehumidifier tower 31 and
then is mixed with an additional amount of steam, and then
preheated in heat exchanger 32 to a temperature of between 350 and
400.degree.C.
The gas then enters the first shift converter (reactor 33) which
preferably uses a conventional high temperature shift catalyst to
expedite or otherwise render more efficient the shift conversion
operation. In one embodiment of this invention, shift conversion
can be conducted with two or more catalyst beds within reactor 33,
with a quench or heat exchanger in between the beds to achieve a
greater part of the conversion duty in said reactor 33. The gas
leaving the reactor 33 is cooled in exchanger 34 or quenched to
bring down the temperature to a lower level in a second shift
converter 35. The catalyst used in the latter can be any
conventional low temperature shift catalyst that is operable within
the range of 200.degree. to 250.degree.C. However, in those
instances where the gasification pressure is very high, it would
not be possible to use a low temperature shift reactor because of
the risk of condensation over such a conventional catalyst, unless
a new catalyst were developed to withstand these operating
conditions.
The carbon monoxide content of the gas leaving the low temperature
shift reactor 35 is in the range of about 0.2 to about 0.8% dry
basis, whereas the gas leaving the high temperature shift converter
has a residual CO content of between about 2 and about 5%.
The gas leaving the final shift converter can be cooled, if
necessary, in heat exchanger 36 before entering the dehumidifier
tower 31. In this tower, the cold water flow coming from humidifier
tower 30 is preheated countercurrent to the hot gas, and the heat
thus gained by the water is later released in humidifier tower 30
to the feed gas.
The gas leaving the dehumidifier tower 31 is further cooled in heat
exchanger 37 before being conveyed to the CO.sub.2 removal
step.
The heat recovery in the various heat exchangers 32, 34, 36, 37 can
preferably be optimized in each particular case for best efficiency
by combining the streams either in the shift conversion step
itself, or by combining such streams with gas or liquid streams
from other process steps.
The effluent gas resulting from the shift conversion of the second
gas fraction is subjected to a CO.sub.2 removal step in order to
eliminate virtually all the CO.sub.2 present and thus obtain a
hydrogen-rich stream with which to methanate the residual carbon
oxides in the first effluent gas stream resulting from first
methanation upon combination of the hydrogen-rich stream with said
first methanation effluent stream. The hydrogen-rich stream is
typically, e.g., a hydrogen-nitrogen-methane mixture containing
small amounts of CO and CO.sub.2, much of the nitrogen having been
introduced during gasification.
While there are several conventional means that can be used for the
removal of CO.sub.2 from this gas stream, such as by scrubbing with
appropriate solvents such as various amines, potassium carbonate,
methanol, various other organic solvents, etc., the means most
preferred for the present process would be the one most suited
to:
(a) take maximum advantage of the high partial pressure of CO.sub.2
available; (b) utilize minimum amounts of heat or other forms of
energy for regeneration of the solution; (c) allow, if necessary, a
small amount of CO.sub.2 leakage in the gas leaving the scrubber,
in view of the fact that it will be further methanated downstream
in the second methanation step; and to (d) avoid use of any
chemical harmful to the methanation catalyst downstream.
Generally, those carbon dioxide removal processes using absorption
and regeneration above ambient temperature operate along the lines
indicated in the schematic flow diagram illustrated in FIG. 6.
As shown in FIG. 6, the gas leaving the shift conversion step is
scrubbed countercurrent to the regenerated solution in the scrubber
40, and the purified gas leaving the top of the scrubber goes
directly to the second methanation step after being mixed with the
effluent gas fraction from the first methanation step.
The rich solvent leaving the bottom of scrubber 40 is flashed to
near atmospheric pressure into the regeneration tower 41,
preferably after having been preheated by the hot regenerated
solvent extracted from the bottom of regeneration tower 41 and
pumped by pump 42.
Reboiling heat can be supplied at the bottom of regeneration tower
41 through heat exchanger 43. The gas leaving the top of the
regenerator tower 41 is cooled in cooler 44, and the condensed
solvent is separated in separator 45 and recycled to the system
through pump 46, whereas the concentrated CO.sub.2 stream is
evacuated from separator 45 to the atmosphere or for any downstream
use desired.
In the second methanation step of the present process, the effluent
stream exiting from the CO.sub.2 removal step is combined with the
effluent stream exiting from the first methanation step. Thus, the
combined gas stream to be subjected to methanation in the second
methanation step of the present process has approximately the
stoichiometric amount of hydrogen required to methanate all the CO
and CO.sub.2 contained therein. It should be recognized, however,
that a very slight excess of hydrogen, above the stoichiometric
ratio, may be desirable in the combined gas feed to the second
methanation, in order to achieve a complete methanation of the
carbon oxides. On the other hand, a deficiency of hydrogen in the
second methanation feed will lead to a small amount of CO.sub.2 and
only traces of CO in the second methanation effluent. Either
deviation, whether above or below the stoichiometric ratio of
hydrogen to carbon oxides, may be justified under certain economic
conditions, at the option of the process operator, and although
such deviations have not been set forth in the subsequent typical
material balance, they are nevertheless within the spirit and scope
of the present invention, and should be taken into consideration
for the proper split of the gas fractions after the sulfur removal
step.
It is preferred that this second step stage methanation be effected
in a manner slightly more elaborate than in the first methanation,
since the complete elimination of carbon oxides in the product gas
is intended. To achieve this goal, it is preferred that the second
methanation step be effected in two stages, as illustrated by the
flow diagram contained in FIG. 7, wherein the first stage is
conducted in reactor 50 at a very high temperature, with a
correspondingly high leakage of carbon oxides; whereas, in the
second stage, conducted in reactor 51, the reaction proceeds at a
very moderate temperature so as to result in a complete conversion
to methane.
Since the content of the carbon oxides in the gas mixture is quite
appreciable, it is important that there be a gas recycle through
compressor 52 in order to maintain the reaction temperature in
reactor 50 within reasonable limits.
The gas mixture from the first methanation and CO.sub.2 removal
steps is first mixed with the recycled gas, then preheated in feed
product exchanger 53 by the effluent gas from the second reactor
51, and then fed into the first stage of reactor 50 at a
temperature of from about 240.degree. to about 300.degree.C. The
outlet temperature from reactor 50 is kept between about
450.degree. and about 700.degree.C. The gas effluent from the first
reactor 50 is first cooled in heat exchanger 54, where high
temperature heat can be recovered either to produce high pressure
steam or to supply heat to other parts or stages of the
process.
If desired, the inlet temperature to the second bed can be adjusted
by injecting some cold fresh gas by-passing the first reactor 50.
This procedure has the advantage of requiring less recycle gas to
achieve a given temperature rise in the first reactor. The inlet
temperature to the second reactor 53 is preferably adjusted between
about 240.degree. and about 300.degree.C and the resulting outlet
temperature is preferably in the range of about 270.degree. to
about 400.degree.C.
The gas effluent from reactor 51 is first cooled in the feed
product exchanger 53 and in another heat exchanger 55 and then in
the final cooler 56. Part of the gas produced is recycled through
compressor 52 and the rest is conveyed to the cryogenic stage or
step of the present process.
It is preferred that cryogenic separation take place at a very low
temperature in order to obtain a liquid methane fraction that is
separable from the nitrogen gas stream. Therefore, it is important
to separate the traces of water vapor and carbon dioxide that are
still present in the gas. This can be done in several ways. For
example, a switch exchanger system can be employed at the inlet of
the cryogenic separation system. When the deposition of ice and dry
ice becomes important in the first feed exchanger to the point
where it becomes inoperable, the feed gas is switched to the other
parallel exchanger, and the fouled exchanger can then be rendered
utilizable during the time the other exchanger is in service.
Alternatively, the gas can be treated with molecular sieves which
would act as absorbents to remove the traces of water and CO.sub.2
from the gas. As an additional alternative, a chemical treatment
can also be employed, whereby the final traces of H.sub.2 O and
CO.sub.2 can be removed by scrubbing with a suitable solvent such
as ethylene glycol.
The drying of the feed gas to the present cryogenic separation step
is not shown in the overall schematic flow diagram illustrated in
FIG. 8.
As utilized herein, the basic concept underlying the present
cryogenic separation is to obtain a methane-rich mixture, while
leaving a minimum of methane in the nitrogen stream to be vented to
the atmosphere. It should be realized that the particular scheme to
be followed in this cryogenic separation can vary appreciably
depending on the following variables:
a. the nitrogen content of the feed coming from the second
methanation stage;
b. the nitrogen content desired in the final methane-rich gas or
substitute natural gas;
c. the efficiencies required in terms of the methane content of the
nitrogen stream vented to the atmosphere; and
d. the available pressure of the feed gas from the second
methanation stage.
In any event, it is believed preferable to attain a methane
concentration in the waste nitrogen stream that is vented to the
atmosphere, of between about 0.4 and about 1.0% by volume, and a
nitrogen concentration in the methane-rich product gas of between
about 1.0 and about 8.0% by volume.
In FIG. 8, there is shown a typical cryogenic separation
contemplated for application in the present process. In this
figure, the feed gas from the second methanation step is fed into a
heat exchanger at the full operating pressure of the gas production
train. The feed gas is cooled by the waste nitrogen stream to the
atmosphere and also by the methane-rich gas. Part of the methane
contained in the feed gas is condensed in heat exchanger 60. The
feed gas and the condensed liquid, together or separately, are then
held at a pressure slightly below the partial pressure of the
methane in the feed gas, whereby the resultant gas at such pressure
in tower 61 undergoes a separation such that there results a liquid
methane stream in the bottom and a gas nitrogen stream in the top
of tower 61. The latter is again "throttled" (through valve or
expander) into a flash drum 62, wherein the extra liquid methane
that has condensed is collected and is pumped through pump 63 to
the same pressure as in tower 61, and mixed with the liquid
extracted therefrom. The pressure in flash drum 62 is usually that
required to meet the requirements of the whole system, depending
upon the nitrogen content of the feed gas from the second
methanation. Whenever possible, the waste nitrogen stream is
recovered at a pressure above atmospheric and used to supply power
wherever needed in the process, through a gas expander.
The cold nitrogen stream leaving the top of tower 62 is first
reheated in a reflux condenser at the top of tower 61 and then in a
feed-product exchanger not shown.
Any excess hydrogen or CO present in the gas after the second
methanation step, as mentioned above, will be evacuated with the
waste nitrogen stream from the cryogenic separation.
In Example I below, there is set forth a typical example of the
present invention, illustrated by a material balance, obtained by
carrying out the present process, as illustrated in FIG. 1. The
block diagram of FIG. 1 represents the main process steps, using a
gas oil feedstock and air in the gas generator. The material
balance of Example I specifically applies to the process streams as
numbered on FIG. 1 on the block diagram.
__________________________________________________________________________
EXAMPLE I MATERIAL BALANCE PRODUCTION OF SNG BY GASIFICATION OF GAS
OIL C15.86 H 29.68 S 0.0344 BASED ON 100 MOLES OF
__________________________________________________________________________
FEED MOLES GAS OIL STEAM AIR GAS EFFL. TOTAL GAS GAS FRACTION GAS
FRACTION TO TO TO FROM AFTER TO HTS* TO FIRST GENERATOR GENERATOR
GENERATOR GENERATOR SULFUR AND LTS** METHANATION REMOVAL 1 2 3 4 5
6 7
__________________________________________________________________________
GAS OIL 100 -- -- -- -- -- -- H.sub.2 -- -- -- 1084.40 1084.40
490.95 593.45 CO -- -- -- 667.54 667.54 302.22 365.32 CO.sub.2 --
-- -- 245.70 122.85 55.62 67.23 CH.sub.4 -- -- -- 672.76 672.76
304.58 368.18 H.sub.2 S -- -- -- 3.44 -- -- -- O.sub.2 -- -- 104.79
-- -- -- -- N.sub.2 + A -- -- 395.22 395.22 395.22 178.93 216.29
H.sub.2 O -- 1376.43 -- 427.07 -TOTAL 100.00 -- 500.01 3069.06
2942.77 1332.30 1610.47 MOLES DRY MOLES GAS FRACTION GAS FRACTION
GAS FRACTION COMBINED TOTAL GAS AFTER 1st AFTER AFTER CO.sub.2 GAS
TO 2nd TO CRYOGENIC NITROGEN FINAL METHANATION *HTS LTS** REMOVAL
METHANATION SEPARATION STREAM SNG 8 9 10 11 12 13 14
__________________________________________________________________________
GAS OIL -- -- -- -- -- -- -- H.sub.2 -- 787.73 787.73 787.73 -- --
-- CO 177.24 5.43 5.43 182.68 -- -- -- CO.sub.2 59.93 352.40 --
59.93 -- -- -- CH.sub.4 563.56 304.58 304.58 868.14 1110.75 1.5
1103.25 H.sub.2 S -- -- -- -- -- -- -- O.sub.2 -- -- -- -- -- -- --
N.sub.2 +A 216.29 178.93 178.93 395.22 395.22 360.92 34.30 H.sub. 2
O -- -- -- TOTAL 1017.02 1629.07 1276.67 2293.7 1505.97 362.42
1148.55 MOLES DRY
__________________________________________________________________________
*HTS= high temperature shift conversion **LTS = low temperature
shift conversion
It should be noted that the split between the two streams, after
sulfur removal, is such that the combined gas to the second
methanation step contains the stoichiometric ratio of hydrogen to
carbon oxides.
While particular embodiments of the present invention have been
described, it will be understood, of course, that this invention is
not limited thereto since many modifications may be made, and it
is, therefore, contemplated to cover by the appended claims any and
all such modifications as may fall within the true spirit and scope
of this invention.
* * * * *