GB2060686A - Concurrent shift-methanation process - Google Patents

Concurrent shift-methanation process Download PDF

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Publication number
GB2060686A
GB2060686A GB8033717A GB8033717A GB2060686A GB 2060686 A GB2060686 A GB 2060686A GB 8033717 A GB8033717 A GB 8033717A GB 8033717 A GB8033717 A GB 8033717A GB 2060686 A GB2060686 A GB 2060686A
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gas
stream
mixture
synthesis gas
methanation
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GB2060686B (en
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Conoco Inc
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Conoco Inc
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Priority to US15271980A priority
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08Production of synthetic natural gas

Abstract

A methane-containing substitute natural gas is made from a primary synthesis gas containing hydrogen and carbon monoxide in a mol ratio (H2/CO) less than 3, by: (a) heating but adding substantially no water directly to said synthesis gas; (b) dividing said synthesis gas into at least two portions; (c) mixing a cooled recycle diluent gas stream from the product gas of a concurrent shift and methanation reaction with a first portion of said synthesis gas to produce a first mixture; (d) subjecting said first mixture to concurrent shift and methanation reactions over a catalyst in a first reaction zone to produce a first product gas; (e) cooling said first product gas; (f) mixing a second portion of said synthesis gas with at least a portion of said cooled first product gas as a diluent stream to produce a second mixture; (g) subjecting said second mixture to concurrent shift and methanation reactions over a catalyst in a second reaction zone to produce a second product gas; and, (h) recycling at least a portion of the cooled product gas from the last concurrent shift and methanation reaction zone as said recycle stream to mixture with said first portion of said synthesis gas after addition of water to said recycle stream; (i) liquid water being added to at least a portion of said diluent stream after cooling to further cool said diluent stream by vaporizing said liquid water. The process gives improved steam recovery efficiency and increased flexibility of process control.

Description

SPECIFICATION Concurrent shift - methanation process This invention relates to a process for producing a substitute natural gas, and more particularly relates to a process for producing a substitute natural gas from a gaseous stream containing hydrogen and carbon monoxide in a mol ratio H2/CO less than 3 wherein a diluent stream is mixed with the synthesis gas to provide a reaction mixture for reaction in a plurality of reaction zones.
In recent years, a considerable amount of effort has been directed to the development of processes for producing substitute natural gas from fuels such as coal of various grades, heavy residual oils and the like. The conversion of coals has been of particular interest and one approach has been the conversion of coal into raw synthesis gas in slagging gasifiers and the like. One such process is disclosed in U.S. Patent 4,071,329 issued January 31, 1978. The use of such vessels produces a synthesis gas which is relatively high in carbon monoxide and relatively low in water. Conventional methanation processes such as disclosed in U.S. Patent 3,854,895 issued Decemper 1 7, 1 974, U.S.
Patent 3,890,113 issued June 17, 1975 and U.S. Patent 3,922,148 issued November 1975 have been found to be less desirable for the production of methane from such streams, It has been found desirable to conduct the shift reaction i.e.
and the methanation reaction, i.e.
concurrently in the same reaction vessel when such feedstreams are used. Some processes wherein such concurrent shift-methanation is practiced are U.S. Patent 3,938,968 issued February 17, 1976, U.S. Patent 3,958,956 issued May 25, 1976, U.S. Patent 4,017,274 issued April 12, 1977 and U.S.
Patent 4,133,825 issued January 9, 1979. The present specification may be more fully comprehended if these references as well as those cited previously are studied by the reader in their entirety.
U.S. Patent 3,938,968 discloses the use of a high temperature reaction zone wherein a concurrent shift-methanation reaction is accomplished over a unique catalyst as described in columns 3 and 4 of the reference. The process does not use a product recycle to the process feed stream and the process operates at high temperatures (9O00F inlet to 1 6O00F outlet).
U.S. Patent 3,958,956 discloses a process wherein a closed loop system is used for charging water to the synthesis feed gas to the process. The process shown does not appear to use a product recycle stream and an isothermal methanation zone is used.
U.S. Patent 4,017,274 discloses a process for the methanation of scrubbed raw gases containing in excess of 3 mol % carbon monoxide and a methane concentration of less than 25 mol %. The reference process adds water or steam to the feedstream to the concurrent shift-methanation reaction zones and uses a steam reforming catalyst in the concurrent shift-methanation reaction zone. The reference process does not appear to use a product recycle.
U.S. Patent 4,133,825 relates to a process wherein a portion of the product from a concurrent shift-methanation reaction zone is recycled as a diluent to the synthesis gas feedstream passing to the inlet of a concurrent shift-methanation zone. The reference process adds water to the synthesis gas feedstream.
In view of the processes disclosed, it is clear that a continuing effort is being directed to the improvement of processes for the conversion of carbon monoxide into methane for use as a substitute natural gas. It has now been found that an improvement is accomplished in such processes wherein the water required for the concurrent shift-methanation reactions is added to the diluent or recycle streams mixed with the synthesis gas prior to charging the resulting mixture to a reaction zone.
Thus our invention provides a process for producing a methane-containing substitute natural gas from a primary synthesis gas containing hydrogen and carbon monoxide in a mol ratio (HCO) less than 3, the process including the steps of: (a) heating but adding substantially no water directly to said synthesis gas; (b) dividing said synthesis gas into at least two portions; (c) mixing a cooled recycle diluent gas stream from the product gas of a concurrent shift and methanation reaction with a first portion of said synthesis gas to produce a first mixture; (d) subjecting said first mixture to concurrent shift and methanation reactions over a catalyst in a first reaction zone to produce a first product gas; (e) cooling said first product gas;; (f) mixing a second portion of said synthesis gas with at least a portion of said cooled first product gas as a diluent stream to produce a second mixture; (g) subjecting said second mixture to concurrent shift and methanation reactions over a catalyst in a second reaction zone to produce a second product gas; and, (h) recycling at least a portion of the cooled product gas from the last concurrent shift and methanation reaction zone as said recycle stream to mixture with said first portion of said synthesis gas after addition of water to said recycle stream; (i) liquid water being added to at least a portion of said diluent stream after cooling to further cool said diluent stream by vaporizing said liquid water.
The recycle or diluent streams each comprise a portion of the product stream from a concurrent shift-methanation reactor and are cooled prior to use as a recycle or diluent stream. The product streams from the concurrent shift-methanation reaction zones are at a relatively high temperature and provide a high differential temperature in heat exchangers used to cool such streams and generate steam. The cooling can be to a temperature such that upon the injection of liquid water, which vaporizes into the stream, sufficient cooling is provided to bring the stream used as a recycle or diluent stream to the desired temperature for combination with additional primary synthesis gas.
The accompanying drawing is a schematic diagram of an illustrative embodiment of the process of the present invention, given by way of example only.
In the drawing, a desulfurized synthesis gas feed is supplied to the process through a feed inlet line 10, a heat exchanger 11 and a line 1 2 which conveys the feed to the inlet of a plurality of concurrent shift-methanation reactors 20,30, 40, 50 and 60. A portion of the feed flowing through line 12 is passed through a line 1 8 to a line 17 and thus into shift-methanation reactor 20. The feed is mixed with a recycle stream from a line 1 4 to provide a reaction mixture having a suitable composition for use as a feedstream to reaction zone 20.The reaction mixture is charged to reactor 20 at a temperature from about 500 to about 65O0F with the feed composition being adjusted to accomplish a temperature increase across reactor 20 from about 250 to about 5500 F. While typical ranges have been given, temperatures as low as 450"F at the inlet and as high as 1 5000F in the product stream discharged through a line 21 are possible. The product stream discharged through line 21 is passed through a heat exchanger 22 and mixed with water from a line 29.The cooling in heat exchanger 22 is sufficient to result in a stream which upon the addition of water from line 29 is cooled to a desired temperature as it flows through a line 21' to mix with a portion of the feed flowing from line 12 through a line 28, a valve 13 and a line 23 to reactor 30. The feed gas from line 28 and product stream diluent from line 21' is mixed and passed through line 23 into reactor 30. The inlet and outlet temperatures of reactor 30 are substantially the same as those for reactor 20 with the reactor product from reactor 30 flowing through a line 31 to a heat exchanger 32 and then to a line 31' after blending with water from a line 35. The product stream diluent flowing through line 31 ' is passed to mixture with a portion of the feed gas charged to reactor 40 through a line 38, a valve 13 and a line 33.The inlet and outlet temperatures in reactor 40 are substantially the same as in reactors 20 and 30 with the product gas being recovered from reactor 40 through a line 41 and passed to a heat exchanger 42 where the stream is cooled and passed to a line 41 ' where it is mixed with water charged through a line 44. The resulting mixture flows through line 41' to mix with a flow of feed gas from line 12 via a line 48 and a valve 13 to produce a reaction mixture in a line 43 which is charged to reactor 50.The inlet and outlet temperatures in reactor 50 are substantially the same as those in reactors 20, 30 and 40 with the product gas from reactor 50 being recovered through a line 51 and passed to a heat exchanger 52 where it is cooled and thereafter passed through a line 51' to mixture with an additional amount of feed gas flowing through a line 58 and a valve 1 3 to form a reaction mixture in a line 53 for charging to reactor 60. The reaction product from reactor 60 flows through a line 61 to a heat exchanger 62 where it is cooled and then through a line 61' which passes the stream to division into a portion flowing through a line 62 and a portion flowing through a line 67.The water required in heat exchangers 22, 32, 42, 52 and 62 is supplied through a line 24 with the low being regulated as required by valves 25 to produce high temperature steam. The high temperature steam is recovered through a line 26 and passed to use in the process or the like. The water supplied through lines 29, 35 and 44 is supplied via a line 34 desirably from a condensate source or the like with flow to lines 21 31' and 41' being regulated by valves 29', 35' and 44'.
The portion of the product gas flowing through line 62' is at a temperature such that an additional quantity of water injected through a line 63 and a valve 64 is vaporized prior to compression of recycle stream 62' in a compression 70 for recycle to reactor 20. A knockout pot 65 including a water discharge line 66 is shown in line 62 to prevent the passage of liquid water into compressor 70.
Compressor 70 compresses the recycle gas stream and discharges it at an elevated pressure through a line 71 to a heat exchanger 72 where the recycle stream is heated. The heated recycle stream then passes through a line 73 and is mixed with steam introduced through a line 1 5 and a valve 1 6 to produce a mixture which flows through line 14.
The other portion of the product gas from reactor 60 passes through a line 67 to a heat exchanger 68 where substantial quantities of water are condensed and removed via a line 69 with the resulting gaseous stream passing through a line 67' to a CO2 removal vessel 80 where substantial quantities of carbon dioxide are removed via a line 81 with the resulting gas passing through a line 82 where it is divided into two portions with a first portion passing through a line 84 and a heat exchanger 85 to a clean-up methanation reactor 90 where the carbon monoxide content of the gaseous stream is reduced by the formation of additional quantities of methane.The product gas from reactor 90 is recovered through a line 91 and mixed with the other portion of the stream flowing from line 82 through a line 83 with the resulting mixture passing through a line 92 to a second clean-up methanation reactor 100 where additional quantities of carbon monoxide are converted to methane to further reduce the carbon monoxide content of the gaseous stream. The product gaseous stream from reactor 100 is recovered through a line 101, passed through a heat exchanger 11 and discharged to a product pipeline, further treatment or the like through a line 102.
In the practice of the process of the present invention it will be'observed that process flexibility in the amount of water added to each of the streams used as a diluent with the feed gas passed to reactors 20, 30, 40 and 50 is possible since water is added to each of these streams by an independent system. By contrast, when water is added to the feed gas mixture the composition of the feed gas mixture is constant to all reactors with the amount of water added being fixed by the amount of feed gas added. Further, the amount of water added to the recycle stream is also flexible since the amount of water added is not dependent upon any other stream, but rather is simply determined by the amount of water desired in the stream flowing through line 14.Further, it has been found that water addition ahead of compressor 70 results in improved efficiency in the operation of the process. The addition of water via a line 64 results in a cooler stream flowing to compressor 70 and a lower horsepower requirement for compressor 70. The use of steam in the recycle system is also desirable with respect to the stream passing to reactor 20, i.e. the first concurrent shift-methanation reactor.
A further advantage accomplished by the process of the present invention lies in the production of high pressure steam. A substantial cost associated with processes for the conversion of carbon monoxide to methane is the cost of the heat exchangers required. By the improvement of the present invention the highest temperature product streams are used to produce high pressure steam with the cooling from lower temperatures to the reaction temperature being accomplished at least in part by the vaporization of liquid water rather than by heat change means, i.e. the differential temperature in heat exchangers 22, 32, 42, 52 and 62 is optimized since the cooling is of a high temperature stream to a temperature in excess of that used in the next reactor.In other words, the final cooling is accomplished by the vaporization of water from lines 29, 35 and 44. Such results in the ability to use smaller heat exchangers since with a greater temperature differential the heat exchanger surface area required is greatly reduced. Further, the total heat removal accomplished in the heat exchanger is reduced by the injection of liquid water thus further reducing the heat exchanger surface area required. Thus, a substantial improvement is achieved in the production of a high grade of steam more efficiently.
It will be observed that no water is added to stream 51' since it is undesirable to add additional water to this stream since reactor 60 does not operate at the same conditions as do reactors 20, 30, 40 and 50. In particular, reactor 60 is used to begin the clean-up reactions, i.e. reactor 60 is used to begin to reduce the amount of carbon monoxide in the feedstream and as a result reactor 60 operates at an inlet temperature from about 500 to about 6500F but at an outlet temperature generally lower than reactors 20,30,40 and 50. Higher temperatures may occur in product line 61 dependent upon the amount of carbon monoxide available for reaction in reactor 60 or the like.In any event, the process stream flowing through line 61 to heat exchanger 62 does not require cooling to a low temperature since it is passed either to recycle or to further treatment to produce the product methane containing stream.
EXAMPLE A computer simulation of the present process was conducted and the temperatures, pressures and compositions of the streams shown in the FIGURE were determined to be as set forth below in Table I. TABLE I Stream No. 15 73 12 18 17 21 29 28 23 31 35 38 33 41 44 Temperature ( F) 750 625 453 453 605 1000 400 453 590 1000 400 453 490 1000 400 Pressure (psia) 565 375 375 375 375 369 450 375 363 357 450 375 350 344 450 Composition (Mol/Hr) 465 4067 6699 1102 5634 5306 805 1238 7349 6876 1041 1601 9518 8908 1351 H2O Mol % 100 42.8 1.0 39.3 36.8 100 37.6 36.7 100 37.6 36.6 100 H2 Mol% 3.2 28.5 28.5 7.9 7.1 28.5 9.9 7.2 28.5 10.0 7.4 CH4 Mol % 21.7 6.9 6.9 17.0 21.3 6.9 16.6 21.3 6.9 16.5 21.2 CO Mol % 0.4 60.3 60.3 12.1 1.7 60.3 11.4 1.7 60.3 11.4 1.7 CO2 Mol % 31.4 2.4 2.4 23.1 32.6 2.4 24.0 32.6 2.4 24.0 32.6 CnHmMol % 0.3 0.3 0.1 0.3 Tr - 0.3 Tr N2 Mol % 0.5 0.6 0.6 0.5 0.5 0.6 0.5 0.5 0.6 0.5 0.5 Stream No. 48 43 51 58 53 61 62' 63 71 67 69 67' 82 101 Temperature F 453 590 1000 453 590 850 535 196 407 535 294 220 703 Pressure (psia) 375 338 332 375 326 320 308 450 385 308 324 279 268 Composition (Mol/Hr) 2077 12336 11546 681 12227 11625 3677 389 4067 7948 548 7400 2460 2336 H2O Mol % 37.6 36.6 34.6 36.7 36.7 100 42.8 36.7 100 32.0 6.1 10.2 H2 Mol% 28.5 10.1 7.5 28.5 8.6 3.6 3.6 3.2 3.6 3.8 11.4 2.9 CH4 Mol % 6.9 16.5 21.1 6.9 20.4 24.0 24.0 21.7 24.0 25.8 77.6 84.4 CO Mol % 60.3 11.4 1.8 60.3 5.0 0.5 0.5 0.4 0.5 0.5 1.5 Tr CO2 Mol % 2.4 23.9 32.5 2.4 30.9 34.7 34.7 31.4 34.7 37.3 1.7 0.7 CnHm Mol % 0.3 Tr - 0.3 Tr N2 Mol % 0.6 0.5 0.5 0.6 0.5 0.5 0.5 0.5 0.5 0.6 1.7 1.8 It will be observed that by the method of the present invention substantially the same reaction conditions are obtained in reactors 30, 40 and 50, i.e. in the second and subsequent reaction zones up to the penultimate reaction zone. Such is highly desirable since it results in the ability to optimize catalyst life and effectiveness. A slightly higher inlet temperature is used in reactor 20 since it is desirable to have a slightly higher inlet temperature in vessel 20 to guard against the higher potential for the formation of nickel carbonyl. The formation of nickel carbonyl is not as likely in reactors 30, 40 and 50 therefore slightly lower inlet temperatures are used.
In sum mary, it is pointed out that by the improvement of the present invention an increased efficiency in the production of high temperature steam from the product streams from the concurrent shift-methanation reaction zones is accomplished and greater process flexibility is accomplished by the addition of water to the recycle or diluent streams in the process. By the practice of the present invention, substantially no water is added to the feed gas stream since all process water is added to the recycle or diluent streams. Recycle as used herein refers to the recycling of a portion of the product stream from reactor 60 back to reactor 20 as a diluent in contrast to the use of the product streams from the various reactors as a diluent in the following reactor.
Having thus described the invention by reference to certain of its preferred embodiments, it is respectfully pointed out that the embodiments described are illustrative rather than limiting in nature and that many variations and modifications are possible within the scope of the present invention. Such variations and modifications may appear obvious and desirable to those skilled in the art upon a review of the foregoing description of preferred embodiments and the example.

Claims (9)

1. A process for producing a methane-containing substitute natural gas from a primary synthesis gas containing hydrogen and carbon monoxide in a mol ratio (HCO) less than 3, the process including the steps of: (a) heating but adding substantially no water directly to said synthesis gas; (b) dividing said synthesis gas into at least two portions; (c) mixing a cooled recycle gas stream from the product gas of a concurrent shift and methanation reaction with a first portion of said synthesis gas to produce a first mixture; (d) subjecting said first mixture to concurrent shift and methanation reactions over a catalyst in a first reaction zone to produce a first product gas; (e) cooling said first product gas; (f) mixing a second portion of said synthesis gas with at least a portion of said cooled first product gas as a diluent stream to produce a second mixture;; (g) subjecting said second mixture to concurrent shift and methanation reactions over a catalyst in a second reaction zone to produce a second product gas; and, (h) recycling at least a portion of the cooled product gas from the last concurrent shift and methanation reaction zone as said recycle stream to mixture with said first portion of said synthesis gas after addition of water to said recycle stream; (i) liquid water being added to at least a portion of said diluent stream after cooling to further cool said diluent stream by vaporizing said liquid water.
2. The process of claim 1 wherein said diluent stream is cooled to a temperature such that upon vaporizing said liquid water into said diluent stream the resulting steam-containing diluent stream is at a desired temperature for combination with additional primary synthesis gas.
3. The process of claim 1 or 2 wherein liquid water is added to said recycle stream to said first reaction zone after cooling said recycle stream to further cool said recycle stream by vaporizing said liquid water.
4. The process of any of claims 1 to 3 wherein water is added as steam to said recycle stream prior to mixture with said first portion of said synthesis gas.
5. The process of any of claims 1 to 4 wherein said process includes more than two concurrent shift and methanation reactions zones.
6. The process of claim 5 wherein substantially no water is added to the diluent stream to the last of said concurrent shift and methanation reaction zone.
7. The process of claim 6 wherein said process includes five concurrent shift and methanation reaction zones.
8. The process of any of claims 5 to 7 wherein the composition of the mixture of said primary synthesis gas and said diluent charged to the second and subsequent reaction zones up to the penultimate reaction zone is substantially the same.
9. The process of claim 1, substantially as described herein.
1 0. A process for producing a methane-containing substitute natural gas from a primary synthesis gas, substantially as illustrated in the accompanying drawing.
GB8033717A 1979-10-22 1980-10-20 Concurrent shift-methanation process Expired GB2060686B (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089105A2 (en) * 1982-03-12 1983-09-21 British Gas Corporation Multi stage methanation
EP2110425A1 (en) * 2008-04-16 2009-10-21 Methanol Casale S.A. Process and plant for substitute natural gas
CN101885994A (en) * 2009-01-06 2010-11-17 通用电气公司 Heat integration in coal gasification and methanation reaction process
CN103740423A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas from synthesis gas
CN103740426A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas by methanation of synthesis gas
CN103740427A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas from synthesis gas
CN103773526A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Method for producing substitute natural gas
CN103897758A (en) * 2012-12-26 2014-07-02 浦项产业科学研究院 Equipment and method for producing synthesized gas with low H2/CO ratio
CN103952198A (en) * 2014-04-02 2014-07-30 新地能源工程技术有限公司 Method for producing natural gas by coal-based synthetic gas
CN105623762A (en) * 2016-01-20 2016-06-01 中国海洋石油总公司 Method for preparing natural gas by carbon dioxide sectionalized methanation
CN105779048A (en) * 2016-04-26 2016-07-20 中国华能集团清洁能源技术研究院有限公司 Methanation method for preparing synthetic natural gas at low temperature
GB2537220A (en) * 2015-03-03 2016-10-12 Johnson Matthey Davy Technologies Ltd Process
GB2537219A (en) * 2015-03-03 2016-10-12 Johnson Matthey Davy Technologies Ltd Process

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089105A2 (en) * 1982-03-12 1983-09-21 British Gas Corporation Multi stage methanation
EP0089105A3 (en) * 1982-03-12 1984-03-28 British Gas Corporation Multi stage methanation
EP2110425A1 (en) * 2008-04-16 2009-10-21 Methanol Casale S.A. Process and plant for substitute natural gas
CN101560423A (en) * 2008-04-16 2009-10-21 卡萨尔甲醇公司 Process and plant for substitute natural gas
CN105018166A (en) * 2008-04-16 2015-11-04 卡萨尔甲醇公司 Process and apparatus for producing substitute natural gas
US8039519B2 (en) 2008-04-16 2011-10-18 Methanol Casale S.A. Process and plant for substitute natural gas
RU2495091C2 (en) * 2008-04-16 2013-10-10 Метанол Касале С.А. Method and apparatus for producing natural gas substitute
EP2390474A1 (en) * 2009-01-06 2011-11-30 General Electric Company Heat Integration In Coal Gasification And Methanation Reaction Process
CN101885994A (en) * 2009-01-06 2010-11-17 通用电气公司 Heat integration in coal gasification and methanation reaction process
CN104910985A (en) * 2009-01-06 2015-09-16 通用电气公司 Heat integration in coal gasification and methanation reaction process
CN103740423A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas from synthesis gas
CN103740426A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas by methanation of synthesis gas
CN103740427A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of producing substitute natural gas from synthesis gas
CN103740426B (en) * 2012-10-17 2015-12-09 中国石油化工股份有限公司 The method substituting Sweet natural gas is produced in synthetic gas methanation
CN103740427B (en) * 2012-10-17 2015-07-08 中国石油化工股份有限公司 Method of producing substitute natural gas from synthesis gas
CN103773526A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Method for producing substitute natural gas
CN103897758A (en) * 2012-12-26 2014-07-02 浦项产业科学研究院 Equipment and method for producing synthesized gas with low H2/CO ratio
CN103952198A (en) * 2014-04-02 2014-07-30 新地能源工程技术有限公司 Method for producing natural gas by coal-based synthetic gas
CN107087415A (en) * 2015-03-03 2017-08-22 庄信万丰戴维科技有限公司 The method that production substitutes natural gas
GB2537219B (en) * 2015-03-03 2017-04-26 Johnson Matthey Davy Technologies Ltd Process for producing substitute natural gas
GB2537220A (en) * 2015-03-03 2016-10-12 Johnson Matthey Davy Technologies Ltd Process
GB2537220B (en) * 2015-03-03 2017-04-26 Johnson Matthey Davy Technologies Ltd Processfor producing substitute natural gas
GB2537219A (en) * 2015-03-03 2016-10-12 Johnson Matthey Davy Technologies Ltd Process
CN107087415B (en) * 2015-03-03 2020-06-30 庄信万丰戴维科技有限公司 Process for producing substitute natural gas
CN105623762A (en) * 2016-01-20 2016-06-01 中国海洋石油总公司 Method for preparing natural gas by carbon dioxide sectionalized methanation
CN105623762B (en) * 2016-01-20 2018-04-13 中国海洋石油总公司 A kind of method that natural gas is produced in carbon dioxide segmentation methanation
CN105779048A (en) * 2016-04-26 2016-07-20 中国华能集团清洁能源技术研究院有限公司 Methanation method for preparing synthetic natural gas at low temperature
CN105779048B (en) * 2016-04-26 2018-07-10 中国华能集团清洁能源技术研究院有限公司 A kind of low temperature produces the methanation process of synthetic natural gas

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FR2467834B1 (en) 1983-04-15
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DE3032123A1 (en) 1981-04-30
GB2060686B (en) 1983-05-05
IT1133885B (en) 1986-07-24

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