U.S. patent number 3,904,386 [Application Number 05/410,118] was granted by the patent office on 1975-09-09 for combined shift and methanation reaction process for the gasification of carbonaceous materials.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the. Invention is credited to Ernest E. Donath, Michael S. Graboski.
United States Patent |
3,904,386 |
Graboski , et al. |
September 9, 1975 |
Combined shift and methanation reaction process for the
gasification of carbonaceous materials
Abstract
A process for the gasification of coal and other carbonaceous
materials to produce a methane rich fuel gas includes the
combination of the shift and methanation reactions in a single
reactor system. A hot raw synthesis gas comprising methane,
hydrogen, hydrogen sulfide, and oxides of carbon passes from a coal
gasification system into a combined shift and methanation reactor
system where the shift reaction between steam and the product gas
adjusts the hydrogen/carbon monoxide ratio. Simultaneously with the
occurrence of the shift reaction in the combined reactor system,
carbon monoxide and hydrogen are converted to methane and water.
Steam formed by the methanation reaction promotes the shift
reaction to, in turn, produce the hydrogen necessary to carry out
the methanation reaction. After purification to remove the acid
gases, the methane rich product gas is reacted in a cleanup
methanator in the presence of a nickel catalyst to reduce the
carbon monoxide content and increase the methane content to the
pipeline standards required for synthetic natural gas.
Inventors: |
Graboski; Michael S.
(Stahlstown, PA), Donath; Ernest E. (St. Croix, VI) |
Assignee: |
The United States of America as
represented by the Secretary of the (Washington, DC)
|
Family
ID: |
23623303 |
Appl.
No.: |
05/410,118 |
Filed: |
October 26, 1973 |
Current U.S.
Class: |
48/197R; 48/210;
423/656; 518/703; 518/704; 518/705; 518/711; 518/712; 518/714;
518/715; 518/717 |
Current CPC
Class: |
C10K
3/04 (20130101); C10L 3/08 (20130101); C07C
1/0485 (20130101); C07C 1/0485 (20130101); C07C
9/04 (20130101); C07C 2523/75 (20130101); C07C
2523/30 (20130101); C07C 2523/28 (20130101); C07C
2523/745 (20130101); C07C 2523/883 (20130101); C07C
2523/86 (20130101); C07C 2523/888 (20130101); Y02P
20/129 (20151101); C07C 2523/26 (20130101); C07C
2523/882 (20130101); C07C 2523/755 (20130101) |
Current International
Class: |
C10K
3/04 (20060101); C10K 3/00 (20060101); C10K
003/02 () |
Field of
Search: |
;48/197R,210,214,215
;260/449M ;423/655,656 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
165,746 |
|
Sep 1953 |
|
AU |
|
705,623 |
|
Mar 1954 |
|
GB |
|
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Kratz; Peter F.
Attorney, Agent or Firm: Price, Jr.; Stanley J.
Claims
We claim:
1. In a process for gasification of carbonaceous materials to
produce high methane content gas, including a water gas shift
reaction and a methanation reaction comprising,
gasifying carbonaceous materials and generating a hot synthesis gas
comprising a mixture of methane, hydrogen sulfide, hydrogen and
oxides of carbon,
cooling said hot synthesis gas,
adding steam to said cooled synthesis gas when the hydrogen to
carbon monoxide ratio of said cooled synthesis gas is less than 1.0
to produce a mixture of steam and cooled synthesis gas having a
steam/gas ratio of about 0.5,
introducing said cooled synthesis gas into a combined water gas
shift and methanation reactor into contact with a catalyst at a
temperature between 550.degree.F. and 1050.degree.F. and at a
pressure between 500 psig. and 2000 psig. whereby simultaneously
the hydrogen/carbon monoxide ratio is increased by carbon monoxide
reacting with water produced from the methanation reaction and
methanation of carbon monoxide and hydrogen is accomplished,
recovering from said reactor a methane rich product gas which
includes above 40% by volume methane, said methane rich product gas
also including hydrogen sulfide, carbon oxides and other higher
hydrocarbons such as ethane and propane,
passing said methane rich product gas through a waste heat boiler
to thereby cool and dry said methane rich product gas and
thereafter,
introducing said methane rich gas into a purification unit for
removal of acid gas such as hydrogen sulfide and carbon dioxide to
produce a purified methane rich product gas, and
recycling a portion of said cooled and dried methane rich product
gas for mixture with said mixture of steam and cooled synthesis gas
introduced into said combined water gas shift and methanation
reactor in an amount which is not more than three volumes for each
one volume of said mixture of steam and cooled synthesis gas.
2. The process as set forth in claim 1 in which said catalyst is
selected from the group consisting of chromium oxide, molybdenum
oxide, molybdenum sulfide, iron oxide; mixtures of nickel oxide
with oxides of chromium, molybdenum or tungsten; and mixtures of
cobalt oxide with oxides of chromium, molybdenum or tungsten.
3. The process as set forth in claim 1 comprising, passing said
mixture of cooled synthesis gas in said combined water gas shift
and methanation reactor over a fluidized catalyst bed having
internal cooling coils arranged therewith to generate high pressure
steam from the heat of the combined water gas shift and methanation
reaction.
4. The process as set forth in claim 3 wherein said fluidized
catalyst bed includes a catalytic material selected from the group
consisting of Groups I-B, VI-B and VIII plus alkali-type promoters
selected from the group consisting of Groups I-A, II-A and the
period seven rare earths.
5. The process as set forth in claim 1 wherein said catalyst is
supported on an alumina base having a density of 30 to 60 lb. per
cubic foot and a mean particle size of about 65 microns.
6. The process as set forth in claim 1 wherein the said catalyst
includes an alkali salt selected from the group consisting of
potassium or rubidium salts.
7. The process as set forth in claim 1 comprising,
introducing said purified methane rich product gas into a fixed bed
methanator having a nickel catalyst therein to reduce the carbon
monoxide level of said purified methane rich product gas to yield a
final product gas comprising methane and carbon monoxide in a
concentration acceptable for synthetic pipeline gas quality.
8. The process as set forth in claim 1 wherein said purification
unit for removal of acid gas from said methane rich product gas
includes,
contacting said methane rich product gas with a selective solvent
system to form a hydrogen sulfide rich solvent stream,
withdrawing said hydrogen sulfide solvent stream from said methane
rich product gas,
contacting said methane rich product gas with a selective solvent
system to form a carbon dioxide rich solvent stream, and
withdrawing said carbon dioxide rich solvent stream from said
methane rich product gas.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the gasification of carbonaceous
materials, and more particularly to a combined shift and
methanation reaction process for providing a methane rich pipeline
gas as the principal product.
2. Description of the Prior Art
The production of methane rich fuel gas by the gasification of coal
or other carbonaceous materials is widely known in the art.
Pyrolysis techniques are used to carbonize coal wherein coal is
heated in the absence of air to obtain a solid char and gaseous
products such as hydrogen, methane, and ammonia. The Lurgi process
utilizes pressure and high temperature to recover synthetic natural
gas from carbonaceous solids. All these processes yield product gas
that contains carbon monoxide and hydrogen which can be methanated
after the hydrogen to carbon monoxide ratio has been adjusted to
about a 3 to 1 ratio to obtain high Btu. heating fuels having
suitable pipeline quality. Generally the gasification processes use
coal in fixed beds, fluidized beds or beds in suspension. Steam,
hydrogen, and oxygen are used as the gasification media.
A two-stage gasification process, developed at Bituminous Coal
Research, Inc., at Pittsburgh, Pa. combines the processes of coal
gasification, shift conversion, acid gas removal and methanation to
produce a methane rich fuel gas which meets the specification of a
high Btu. pipeline gas. Particulate coal and steam are reacted in
the second stage of the gasifier vessel with synthesis gas from the
first stage of the gasifier vessel to produce char and a product
gas containing hydrogen, hydrogen sulfide, methane and oxides of
carbon. The char is recycled to the first gasification stage for
reaction with steam and oxygen to produce a synthesis gas for
reaction in the second gasification stage. The separated product
gas is mixed with steam prior to entering a shift converter wherein
the product gas passes over the shift catalyst. The shift converter
adjusts the hydrogen to carbon monoxide ratio from about 1/1 to
3.1/1. The shift reaction raises the temperature of the product gas
and the product gas flows to a waste heat broiler which supplies
process steam and cools the product gas prior to removel of the
acid gas in the purification unit.
In the purification unit the acid gas comprising principally
hydrogen sulfide and carbon dioxide is removed from the product gas
which is then reheated to, or above, 600.degree.F. and fed to the
methanator. The catalytic methanation unit converts the hydrogen
and carbon monoxide of the product gas to methane which is suitable
for use as a high Btu. pipeline gas.
U.S. Pat. No. 3,600,145 describes a process for production of
methane as a substitute natural gas by passing carbon monoxide and
steam into contact with a metal catalyst supported on an alumina
support and promoted with a barium salt. Prior to the conversion pf
carbon monoxide and steam to form methane, substantially all the
impurities contained in the feedstock are removed. Consequently,
the shift reaction and the methanation reactions must be performed
separately to permit removal of the carbon dioxide from the
feedstock before the conversion process takes place.
There is need to provide a process for gasification of carbonaceous
materials, including water gas shift reaction and a methanation
reaction, to produce high methane content gas suitable for use as a
pipeline gas in which the high costs of the process may be reduced
and the process in general simplified. Specifically, by combining
the shift and methanation reaction processes the volume of gas from
which acid gas is removed may be reduced thereby reducing the size
and cost of the acid gas removal unit associated therewith.
Furthermore, by combining the water gas shift and methanation
reaction processes, a methane rich fuel gas would be produced more
efficiently at a lower unit cost.
SUMMARY OF THE INVENTION
The hereinafter described invention relates to a process for the
gasification of carbonaceous materials that includes the
combination of the shift reaction and methanation reaction in a
single reactor system to ultimately produce methane rich fuel gas
of pipeline quality. Hot synthesis gas comprising methane, hydrogen
sulfide, hydrogen and oxides of carbon pass from a coal gasifier to
a waste heat boiler for cooling. The cooled synthesis gas is
introduced into a combined water gas shift and methanation system
where the mixture comes on contact with a catalyst at a temperature
between 500.degree.F. and 1050.degree.F. and at a pressure between
500 psig. and 2000 psig. to thereby increase the hydrogen/carbon
monoxide ratio of the mixture and to accomplish methanation of
carbon oxides, especially carbon monoxide and hydrogen. Thereafter,
the methane rich product gas is recovered from the reactor.
The methane rich product gas then passes from the combined shift
and methanation reactor to a purification unit having a selective
solvent system to remove principally hydrogen sulfide and carbon
dioxide. The purified product gas is treated in a final methanator
containing a nickel based catalyst to reduct the carbon monoxide
level in the product gas to less than 0.1% by volume and increase
the methane content of the product gas to over 90% by volume and
preferably over 95% by volume.
The combined shift and methanation reactor system can be
characterized as a fixed bed catalytic reactor system or a reactor
system which uses a catalyst suspended in a liquid. Preferably, a
reactor system having a fluidized catalyst bed with internal
cooling coils is used for the combined shift and methanation
reactions.
In the catalytic system the shift and methanation reactions occur
more or less simultaneously. The shift reaction increases the
hydrogen/carbon monoxide ratio above that of the raw feed gas. The
water produced as a result of the methanation reaction promotes the
shift reaction by reacting with the carbon monoxide to increase
hydrogen concentration required for the methanation reaction. The
shift and methanation reactions which take place in the combined
reactor system can yield a methane rich product gas comprising
above 40% by volume methane. The catalytic material utilized may be
selected from various metallic oxides or sulfides and is supported
on an alumina base. Other catalyst supports such as sulica,
magnesia, aluminum silicates, silica gel, magnesium silicate, or
mixed silicates such as magnesium-aluminum silicate or molecular
sieves can be used. It may be promoted with alkalai materials to
retard carbon deposition.
Accordingly, the principal object of this invention is to combine
the shift and methanation reaction processes in a single reactor
system to produce methane plus higher hydrocarbons, principally
ethane and propane.
Another object of this invention is to provide a combined shift and
methanation reaction process in the gasification of carbonaceous
materials which utilizes a fluidized catalyst bed comprising either
a sulfur resistant catalyst or a sulfur sensitive catalyst.
Another object of this invention is to combine the shift and
methanation reactions for the gasification of carbonaceous
materials in a single reactor system for the purpose of reducing
steam consumption and the operating costs associated therewith.
A further object of this invention is to provide a combined shift
and methanation reaction process for the gasification of
carbonaceous materials which permits sulfur recovery in a small
unit with a high yield of sulfur and low emission of residual
hydrogen sulfide.
These and other objects of this invention will be more completely
disclosed and described in the following specification,
accompanying drawing and appended claims.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a diagrammatic illustration of a combined shift and
methanation reaction process used in the gasification of coal
according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Throughout the specification, coal is utilized in the gasification
process. It should be understood that the term "coal" is intended
to designate carbonaceous material including all ranks of coal,
lignite and the like, and further, that the gasification process is
not limited to the gasification of coal and could also be used with
oil shale, heavy oil residues, tars and the like.
The term "gasification" means the heating of coal in the presence
of reacting agents, whereby all or part of the volatile portion of
coal is liberated and the carbon in residual char is reacted with
those agents or with other reactants present in the gasification
process.
The term "synthesis gas" means a carbon monoxide, hydrogen and
preferably methane containing gas such as the gas produced in the
second stage of the two-stage gasification process described
herein.
The term "product gas" means a methane enriched gas produced in the
combined shift and methanator.
Referring to the drawing, preheated coal is injected into the upper
portion 10 of a two-stage gasification vessel generally designated
by the numeral 12 as a reactant in the second stage of the
gasification process. The practice of this invention is not limited
to the use of a two-stage gasification process for the production
of a synthesis gas containing hydrogen, hydrogen sulfide, methane
and oxides of carbon, to be treated in a combined shift and
methanator reactor system, ultimately yielding methane rich fuel
gas of synthetic pipeline gas quality. any gasification process in
which carbonaceous materials are converted to a synthesis gas
containing hydrogen and oxides of carbon is acceptable for
incorporation in the present invention. Therefore, reference in the
present invention to a two-stage gasification process for the
production of synthesis gas is made for the purposes of
illustration and example only.
Steam and oxygen are introduced into the vessel lower portion 14
and are reacted with the preheated char in the first stage of the
gasification process to produce a synthesis gas containing hydrogen
and carbon oxides. The synthesis gas flows upwardly through the
gasifier vessel 12 for reaction in the upper portion 10 as the
second stage of the gasification process. The coal introduced in
the vessel upper portion 10 is pulverized to sufficient particle
size to permit entrainment of the pulverized coal with the
synthesis gas flowing upwardly from the first stage to the second
stage. The reaction in the second stage of the gasification is
conducted at a temperature in excess of 1600.degree.F. and a
pressure in excess of 50 atmospheres with residence time for the
reactants in the second stage portion of the vessel 12 maintained
to assure reaction of the coal.
The product of the reaction in the second stage between the
preheated coal and synthesis gas comprises a low sulfur char
entrained in a synthesis gas containing methane, hydrogen and
carbon oxides. The sulfur content of the char is maintained at a
minimum level by reacting the pulverized coal with the synthesis
gas in the presence of hydrogen and steam at elevated temperatures
and pressures.
The low sulfur char entrained in the synthesis gas is withdrawn
from the upper portion of the vessel 12 and fed through conduit 16
into the cyclone separator 18. The partially gasified char
separated in the cyclone separator 18 is withdrawn therefrom and
fed through conduit 20 into the lower portion 14 of gasifier vessel
12 as a reactant in the first stage of the gasification process.
Steam and oxygen are introduced into the vessel lower portion 14
and are reacted with char in the first stage of the gasification
process procedure the to produce gas containing hydrogen and carbon
oxides. The synthesis gas reacts in the upper portion 10 with the
preheated coal as stage two of the gasification process. The
reaction in the first stage is conducted at temperatures in excess
of 2500.degree.F. and at a pressure in excess of 50 atmospheres.
The molten slag formed in gasifier vessel 12 gravitates to the
bottom of the vessel where the molten slag is cooled and withdrawn
through conduit 22.
The hot synthesis gas exits from the top of the separator 18
through conduit 24 to a waste heat boiler 26 where the synthesis
gas temperature is reduced from 1700.degree.F. to a temperature
below 650.degree.F. During the cooling process in the boiler 26,
feed water may be sprayed into the synthesis gas sufficiently to
raise the moisture content within the product gas to a steam to dry
gas ratio sufficient to provide hydrogen for the methanation
synthesis. In cases when the hydrogen to carbon monoxide ratio of
the cooled synthesis gas is less than 1.0, furhter provision
further made for adding steam to the cooled synthesis gas in
conduit 28 after is has left the boiler 26. The additional steam
added to the cooled synthesis gas in conduit 28 produces a mixture
of steam and cooled synthesis gas having a steam-gas ratio of about
0.5. Synthesis gases with hydrogen to carbon monoxide ratios of one
or greater require no steam for combined shift and methanation.
The cooled synthesis gas passing through conduit 28 is fed
thereafter to a combined shift and methanation reactor vessel 30.
The vessel 30 may be one of a plurality of vessels within the
combined shift and methanation reactor system which utilizes fixed
or fluidized catalyst beds or a catalyst suspended in a liquid.
Preferably, the reactor vessel 30 includes a fluidized catalyst bed
with internal cooling coils 31 for generation of high pressure
steam as a by-product of the heat generated from the reaction. The
combined shift and methanation process in the reactor vessel 30 is
conducted at a temperature between the range of 550.degree.F. to
1050.degree.F. Preferably, the temperature is maintained in the
range from 650.degree.F. to 850.degree.F. and a pressure from 500
to 2000 psig. Under these conditions the main methanation product
is methane; however, significant amounts of ethane and higher
hydrocarbons may be formed. Such formation improves the efficiency
of the process. In the fluidized bed process, the synthesis gas fed
into the reactor vessel 30, which is cooler than the catalyst bed,
is heated to the desired reaction temperature, thus absorbing a
portion of the heat liberated near the inlet distribution area
affording protection from hot spots in this region of the vessel
30.
The catalyst employed in the reactor vessel 30 may be composed of
various metals and their oxides or sulfides and supported in the
reactor vessel 30 on an alumina or mixed alumina-silica base having
a bulk density of preferably between 30 and 60 lb./cf. and a mean
particle size of preferably 65 microns. A suitable catalyst
employed in the combined shift and methanation reaction process may
be selected from the group consisting of chromium oxide, molybdenum
oxide or sulfide and iron oxide; mixtures of nickel oxide with
oxides of chromium, molybdenum or tungsten; or mixtures of cobalt
oxide with oxides of chromium, molybdenum or tungsten. In general,
single metals, oxides, sulfides, or carbonates, or combinations of
these selected from the group consisting of Groups I-B, VI-B or
VIII, plus alkali-type promoters from Group I-A, II-A, or the
Period 7 rare earths are suitable for use as catalysts in the
present invention. Pursuant to the practice of this invention,
carbon deposition in the reactor vessel 30 is preferably suppressed
by providing catalysts containing oxides or sulfides or molybdenum
with nickel or cobalt supported on alumina and activated with an
alkali salt, such as potassium carbonate.
For successful conversion of the synthesis gas to methane having
acceptable pipeline quality, the product gas entering the reactor
vessel 30 must have a minimum hydrogen to carbon monoxide ratio of
1 to 1. In gas mixtures containing less than the requisite hydrogen
to carbon monoxide ratio, steam is fed into the reactor vessel 30
along with the synthesis gas for the combined shift and methanation
process. Thus, the optimum steam rate for a synthesis gas with a
hydrogen to carbon monoxide ratio equal to or greater than one is
zero. In the presence of the catalyst in the vessel 30 conversion
of hydrogen and carbon monoxide takes place producing methane and
water. At the same time the hydrogen to carbon monoxide ratio is
altered by the shift reaction. The increased ratio of hydrogen to
carbon monoxide provides for the hydrogenation of carbon monoxide
to yield a methane rich product gas in the presence of the
catalyst. The water present as a result of hydrogenation of carbon
monoxide in the methanation reaction permits the shift reaction to
occur. Accordingly, the shift reaction increases the concentration
of free hydrogen for reaction with carbon monoxide in the
methanation reaction.
The resultant product gas of the combined shift and methanation
reaction process can contain more than 40% methane by volume and is
withdrawn from the reactor 30 through conduit 32 to a waste heat
boiler 34. The methanation reaction in the vessel 30 is highly
exothermic, and a large amount of process heat is recovered as high
pressure steam from the boiler 34 and the cooling coils 31 in the
reactor vessel 30. To control the combined shift and methanation
reactions and further to increase the methane content of the
product gas, a portion of the dry product gas is recycled through
conduit 35 to conduit 28 for mixture with the synthesis gas fed to
the vessel 30. Preferably, not more than three volumes of dry
product gas is added to one volume of synthesis gas fed to the
reactor 30. The optimum recycle ratio of dry product gas to
synthesis gas is determined on the basis of the highest methane
yield for the lowest catalyst volume in the reactor vessel 30.
Table I, as shown below, indicates the percentage increase in the
methane content of the product gas as a result of the recycle of
the dry product gas to the synthesis gas for a 3 to 1
hydrogen/carbon monoxide ratio and a reactor vessel temperature of
800.degree.F.
TABLE I ______________________________________ Methane in Dry
Carbon Monoxide Product Gas (% by volume) (% by volume) Recycle
Ratio ______________________________________ 6.5 35.5 -- 3.4 55.0
1/1 2.3 67.0 2/1 ______________________________________
After recycling, the dry product gas containing a high
concentration of acid gases, principally hydrogen sulfide and
carbon dioxide, is conducted through conduit 36 to heat exchanger
38 for further cooling and passes thereafter through conduit 39 to
cooler 40 for additional cooling to a temperature suitable for the
selective removal of the acid gases. The product gas from the
cooler 40 is conducted through conduit 42 to a hydrogen sulfide
removal unit 44. The hydrogen sulfide mixed with the product gas
contacts a selective solvent system for forming a hydrogen sulfide,
rich stream. The solvent utilized in unit 44 for selectively
removing hydrogen sulfide from the gaseous stream is preferably an
organic compound containing basic groups, such as amino acids. The
concentrated hydrogen sulfide stream is withdrawn from the bottom
of the unit 44 through conduit 45 for routing to further recovery
processes. The product gas, substantially free of hydrogen sulfide,
passes from the unit 44 through conduit 46 for introduction into
the carbon dioxide removal unit 48. In a similar manner, the
product gas is contacted with a suitable solvent fed to the unit 48
for removing carbon dioxide from the product gas in the form of a
carbon dioxide, rich solvent stream extracted from the bottom of
the unit 48 through conduit 50 for routing to subsequent recovery
processes. The purified product gas supplied from the removal unit
48 to conduit 52 realizes the essential complete hydrogen sulfide
removal and up to 99% carbon dioxide removal as a result of the
purification process and contains more than 90% methane by
volume.
The washed product gas is passed to heat exchanger 38 through
conduit 52 and passes thereafter through conduit 53 to heat
exchanger 54 for additional heating before the methane rich product
gas is fed through conduit 56 to a guard chamber (not shown)
containing pelleted zinc oxide for the removal of traces of sulfur
compounds that remained in the gas and then to a final conventional
fixed bed methanator 58. The fixed bed methanator 58 uses a nickel
catalyst for reacting the remaining carbon monoxide in the product
gas with the available excess hydrogen. The methanator 58 converts
approximately 95% of the remaining carbon monoxide and 50% of the
remaining carbon dioxide to yield a pipeline gas containing over
90% methane and less than 0.1% carbon monoxide by volume. The fuel
gas from the methanator 58 is passed to heat exchanger 54 through
conduit 60 and after further cooling and drying is ready for
delivery to the pipeline.
The composition of the synthesis gas leaving the gasification
vessel 12 at the gas flow rate of 10,000 mols per hour having a
steam to dry gas ratio of 0.5 was analyzed at various portions
along the combined shift and methanation reaction process. The date
compiled from the example shown in Table II indicates that a
product gas rich in methane content is produced by the combined
shift and methanation reaction process.
TABLE II ______________________________________ mol % mol/hr
______________________________________ Gas Composition before
combined shift methanator reactor Carbon dioxide 16.7 1670 Carbon
monoxide 40.1 4010 Methane 14.7 1470 Hydrogen 26.4 2640 Nitrogen
0.7 70 Hydrogen sulfide 1.4 140 Total 100.0 10,000 Water 5,000 Gas
composition after combined shift and methanator reactor Carbon
dioxide 53.8 4035 Carbon monoxide 0.2 15 Methane 41.2 3090 Hydrogen
2.0 150 Nitrogen 0.9 70 Hydrogen sulfide 1.9 140 Total 100.0 7500
Water 4255 Gas composition after acid gas removal Carbon dioxide
1.2 40 Carbon monoxide 0.4 15 Methane 91.8 3090 Hydrogen 4.5 150
Nitrogen 2.1 70 Hydrogen sulfide 0.0 0 Total 100.0 3365 Pipeline
gas after final methanation Carbon dioxide 0.6 20 Carbon monoxide
0.0 1 Methane 96.3 3124 Hydrogen 0.9 28 Nitrogen 2.2 70 Hydrogen
sulfide 0.0 0 Total 100.0 3243
______________________________________
The following Table III is a compilation of experimental data
illustrating various product conversions as the result of the
combined shift and methanation of the product feed gas, having
various hydrogen/carbon monoxide ratios, at a preselected space
velocity into the reactor vessel operating at preselected
temperatures and a pressure of 1000 psig. with an 11% molybdenum
trioxide (MoO.sub.3) and an 89% alumina (Al.sub.2 O.sub.3)
catalyst.
TABLE III
__________________________________________________________________________
RUN A B C D
__________________________________________________________________________
Temperature (.degree.F.) 850 820 850 980 Pressure (psig) 1000 1000
1000 1000 Space velocity 1500 1250 1350 1250 (standard volumes feed
volume catalyst/hr.) Synthesis gas composition (% vol.) Carbon
monoxide 25.69 14.35 39.62 14.38 Carbon dioxide 0.07 30.12 16.41
29.94 Hydrogen 73.85 42.87 43.23 42.38 Nitrogen 0.22 1.35 0.36 1.58
Methane 0.17 11.31 0.38 10.95 Hydrogen sulfide 0.00 0.00 0.00 0.77
Useful conversion of carbon monoxide and hydrogen (% (CO+H.sub.2
.fwdarw.hydrocarbons) ) (CO+H.sub.2 FED) 61.0 38.4 73.0 16.5
Selective conversions of carbon monoxide to higher hydrocarbons (%
(CO.fwdarw.C.sub.1 .sup.+)/(CO.fwdarw.hydrocarbons) ) 24.0 23.8
41.7 8.8
__________________________________________________________________________
Reference in the above Table III to useful conversion of carbon
monoxide and hydrogen to hydrocarbons, expressed by percentage,
indicates the percentage of carbon monoxide and hydrogen which was
converted to methane, ethane and traces of other hydrocarbons. The
selective conversion of carbon monoxide to higher hydrocarbons,
expressed by percentage, represents the amount of carbon monoxide
in the synthesis gas converted to hydrocarbons more complex than
methane compared to the total carbon in the synthesis gas converted
to hydrocarbons. As illustrated in Runs B and D, the increase in
the percentage of carbon dioxide added to the synthesis gas reduced
the conversion of carbon monoxide and hydrogen to hydrocarbons to
38.4% and 16.5% respectively. Even with a content of 0.77% of
hydrogen sulfide in the synthesis gas for Run D, a conversion of
16.5% of carbon monoxide and hydrogen to hydrocarbons was achieved.
Thus, it is possible to provide a catalyst which will function in a
sulfided environment and combine the shift and methanation
reactions. Furthermore, the result was achieved without the
addition of an alkali promotor, such as potassium salt, to the
catalyst.
An economic survey was made comparing the operating costs of the
combined shift and methanation reaction process with the
conventional separate shift and methanation process in a plant
having a capacity of 250 million s.c.f.d. of pipeline gas. The
operating costs of the overall gasification process is
substantially reduced by replacing separate shift and methanator
reactors by a single shift and methanation reactor system.
Furthermore, the size of the acid gas removal units are
substantially reduced when the product gas is purified after
completion of the combined shift and methanation process as
compared to purifying the product gas after the shift conversion
and prior to entry in the methanator. The capacity requirements of
the acid removal units decrease as a result of the volumetric
shrinkage from the methanation reaction to produce a smaller
quantity of the gas stream for acid gas purification treatment.
Also, the steam requirements of the combined process are
substantially reduced in comparison with those of the separate
process thereby providing additional savings in operating costs. A
net investment savings of 17 million dollars is realized for the
combination process over the separate process resulting in a
reduction of 6.0 cents/MM Btu. in pipeline gas cost, based upon
economic study prepared by Air Products and Chemicals, Inc., as
reported in "Engineering Study and Technical Evaluation of the
Bituminous Coal Research, Inc. Two-stage Super Pressure
Gasification Process," (R&D Report No. 60) prepared for the
Office of Coal Research, Department of the Interior, 1971.
According to the provisions of the patent statutes, we have
explained the principle, preferred construction and mode of
operation of our invention and have illustrated and described what
we now consider to represent its best embodiments. However, we
desire to have it understood that, within the scope of the appended
claims, the invention may be practiced otherwise than as
specifically illustrated and described.
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