GB2187751A - Integrated synthesis gas production - Google Patents
Integrated synthesis gas production Download PDFInfo
- Publication number
- GB2187751A GB2187751A GB08605921A GB8605921A GB2187751A GB 2187751 A GB2187751 A GB 2187751A GB 08605921 A GB08605921 A GB 08605921A GB 8605921 A GB8605921 A GB 8605921A GB 2187751 A GB2187751 A GB 2187751A
- Authority
- GB
- United Kingdom
- Prior art keywords
- synthesis gas
- reformer
- heat
- heat regenerator
- partial oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
An organic compound is converted into synthesis gas by endothermic reaction with steam and/or CO2. The heat of this reaction is provided by the exoethermic partial oxidation of a hydrocarbon containing fuel. The apparatus comprises a partial oxidation zone 1 and two steam and/or CO2 reforming zones 2,3. In one stage of the process, gas from zone 1 is used to supply heat to gas from zone 2 in zone 3 and in another stage gas from zone 1 and gas from zone 3 are supplied to zone 2. <IMAGE>
Description
SPECIFICATION
Integrated synthesis gas production
The present invention relates to the production of gas mixtures containing hydrogen and carbon monoxide (synthesis gas) by noncatalytic endothermic reaction of organic compounds with steam and/or carbon dioxide (reforming) utilizing thermal energy recovered from the partial oxidation of hydrocarbon containing fuels to carbon monoxide and hydrogen. The endothermic reaction of organic compounds with steam is known to those skilled in the art and will not be described in detail.
Endothermic thermal reaction of organic compounds, especially hydrocarbons, in the presence of steam and/or carbon dioxide to produce carbon monoxide and hydrogen is an established reaction which is operated industrially using various processes. Such a process can be carried out in a tubular reactor, the necessary heat of reaction being supplied via heat transport through the walls of the tubes or in a medium of externally heated solid heat exchanger material e.g. fine grained solid.
which is used in a fluidized bed.
The known processes necessitate involved technology and exhibit low thermal efficiency.
In the exothermic partial oxidation of hydrocarbon containing fuels, the necessary thermal energy is supplied by the process itself via partial combustion of the feedstock. This technique is also technically involved as well as requiring oxygen.
An object of the invention is to increase the thermal efficiency of the conversion of hydrocarbons into synthesis gas thereby enabling the reaction of the carbon compounds with an optimal or near optimal consumption of energy and materials in the manufacture of synthesis gas from gaseous fuels. It is another object of the invention to provide a process for producing synthesis gas having a suitable H2-CO ratio which for example can be used for middle distillates synthesis processes.
The present invention therefore provides a semi-continous process fdr producing a gas mixture containing hydrogen and carbon monoxide (synthesis gas) comprising an endothermic non-catalytic reaction of an organic compound with steam and/or carbon dioxide; and partial oxidation of a hydrocarbon containing fuel with an oxygen-containing gas whereby a gaseous product is produced and thermal energy for said endothermic reaction is provided, said process comprising the steps of
a) producing continuously synthesis gas by the said partial oxidation in a partial oxidation zone;
b) producing synthesis gas by the said endothermic reaction in a first heat regenerator/reformer;
c) feeding the synthesis gas thus obtained in the partial oxidation zone and in the first heat regeneratqr/reformer respectively to a second heat regenerator/reformer;;
d) exchanging heat between the said two synthesis gases in the second heat regenerator/reformer;
e) terminating the production of synthesis gas in the first heat regenerator/reformer;
f) discharging the synthesis gas after heat exchange from the second heat regenerator/reformer;
g) subsequently producing synthesis gas in the second heat regenerator/reformer by the said endothermic reaction;
h) feeding the synthesis gas thus obtained in the second heat regenerator/reformer to the first heat regenerator/reformer wherein heat exchange takes place with the synthesis gas produced by the partial oxidation in the partial oxidation zone;
i) terminating the production of synthesis gas in the second heat regenerator/reformer;
j) discharging the synthesis gas after heat exchange from the first heat regenerator/reformer; and
k) repeating the above steps b)-j) periodically.
In an advantageous embodiment of the invention hydrocarbons are used as organic feed stock. For example, gaseous, liquid or solid hydrocarbons or mixtures thereof can be used.
More advantageously, methane is used. Byproducts and waste products from chemical synthesis and natural gas can also be employed as the organic compounds and/or the hydrocarbon containing fuels.
The oxygen-containing gas used in the partial oxidation may be pure oxygen, mixtures of oxygen and steam, air or mixtures of pure oxygen, air and steam.
In view of the depletion of oil reserves, the production of synthesis gas, which is a feedstock for many chemicals, is a subject of growing interest.
The partial oxidation of hydrocarbon containing fuels can take place according to various established processes. Gaseous, liquid or solid hydrocarbons or mixtures thereof can be used.
Advantageously, methane is used as fuel.
More advantageously, the partial oxidation may take place in the presence of steam.
These processes include the Shell Gasification Process. A comprehensive survey of this process can be found in the Oil and Gas Journal, September 6, 1971, pp. 85-90.
The partial oxidation of gaseous fuels is usually carried out at temperatures around 900 to roughly 1600"C, advantageously 1100 to 1500"C and pressures up to 100 bar, advantageously 5 to 100 bar.
As a consequence of the high partial oxidation temperature and the use of gaseous fuels as feedstocks, the resulting synthesis gas contains no ash, slag, soot or tar, thereby eliminating, the necessity of using expensive
purification. steps. Raised pressure, high tem peratuKe' and a gaseous feed lead to a high
degree of conversion and relative to the vol
ume of the- gasification chamber, they effect a
high specific throughput. In the majority of
plants in which synthesis gas converted into
products such as ammonia, oxo compounds,
methanol or products from the Fischer-
Tropsch synthesis or the coal hydrogenation
and which operate under pressure, a consider
able part of the investment required for the
compression can be saved on partial oxidizing
gaseous fuels under pressure.Compared to
the established gasification processes in which
ash-containing fuel is employed or which oper
ate under normal pressure, the pressure partial
oxidation of gaseous fuel- permits a consider
able saving in the manufacturing costs of syn
thesis gas.
The invention will now be described by way
of example in more detail by reference to the
accomponying drawing, in which the figure
represents a flow diagram of the integrated
synthesis gas production according to the in
vention.
Referring now to the figure, a partial oxida
tion zone 1, a first heat regenerator/reformer
2 and a second heat regenerat-or/reformer 3
are represented. The construction of such re
generators/reformers is known to those skilled
in the art and will not be described in detail.
Hydrocarbon containing fuel, for example
methane, and an oxygen-containing stream are
introduced through any means 4,4' suitable for
the purpose and at any suitable temperature,
for example 300 C, into the partial oxidation
zone 1 and the methane is partially oxidized to synthesis gas, which leaves the zone 1 through- a line 5 and having a temperature of, for example 1500-1700'C. This partial oxida
tion process is operating continuously.Further,
an organic compound, for example methane, and steam are introduced through any means
6,6' suitable for the purpose into- the first heat
regenerator/reformer 2 at any suitable temper
ature, for example 300"C and under appropriate conditions the methane is steam-reformed
non-catalytically to synthesis gas, which leaves the first regenerator reformer 2 through a line 7 at a temperature of, for example, 1550+50 C. As already discussed in the fore
going the steam-reforming process as such is
known to those skilled in the art and will not be described in detail.
The synthesis gases thus obtained are fed through any means 8 suitable for the purpose to the second heat regenerator/reformer 3
having a temperature of, for example, 1550+50"C and have a mutual heat exchange in the second heat regenerator/reformer 3.
The flow direction of the heat exchanging synthesis gases is opposite to that of the- synthesis gas when produced in the respective regenerator/reformer. After heat exchange, the synthesis gas which is cooled to 325+25 C is discharged through any suitable means 9.
Subsequently the - production of synthesis
gas in the first reformer 2 is terminated by
closing the valves 10,10' and 13, and the
production of synthesis gas in the second re
generator reformer 3 is started by opening the
valves 1-1,11' and 12.
Methane and steam are now introduced through any means 14,14' suitable for the
purpose into the second regenerator reformer
3 and under appropriate conditions synthesis
gas is produced in the second regenerator reformer 3 by non-catalytic conversion of the
methane-steam mixture. The synthesis gases from. the second regenerator/reformer and from the partial oxidation zone 1 respectively are now fed via the line 7 to the first regenerator/reformer 2, in which after mutual heat exchange the synthesis gas is discharged via a
line 15. Subsequently the production of synthesis gas in the second regeneratorlreformer is terminated by closing the valves 11, 11',
12 and the non-catalytic- production of synthesis gas under appropriate conditions- in the first regenerator/reformer is started again by opening the valves 10, 10', 13.The synthesis gas from the continuous partial oxidation process is switched again to the second regenerator/reformer 3 and the cyclical procedure is repeated. The cyclical operations may for example be carried out every 5 to 30 minutes.
Heat-up of the integrated synthesis gas production- installation may be carried out by burning methane-air in the partial oxydationzone 1 Heat-up usually takes one or two days. By supplying flue gas from the zone- 1 to the regenerators/reformers 2 and 3 respectively their appropriate structures may be heated as well. The accumulated heat might be recovered in the methane-reformer step.
-In an advantageous embodiment the feed gases such as methane, steam and oxygen which usually are at ambient temperature are fed to the partial oxidation zone and the regenerator/reformers respectively through a re recuperative heat exchanger 16 in order to be heated-up.
In another advantageous embodiment the discharged synthesis gas from the regenera toreformers can be fed through the recuperative heat exchanger 16 in order to be cooled down to ambient temperature. The recuperative heat exchanger 16 can be provided with an additional low temperature heat source for preheating the said feed gases (not shown).
Preheating of the feed gases in the recuperator by an- additional low temperature heat source can be used to vary the syngas composition and flowrate of gas produced via endothermic reactions: for example, the partial oxidation temperature can be increased. Consequently more heat can be accumulated in the appropriate structure of the regenerators for reforming. Further, for higher inlet temperatures of the methane and steam less heat ad dition is required per unit mass methanesteam to achieve the same conversion level.
In this case more heat becomes available to reform a higher flow rate of methane-steam.
A decrease of the H2-CO ratio can be achieved by net extraction of heat from the recuperator and/or from the regenerators.
It will be appreciated that the respective heat regenerator/reformer in which the synthesis gas production should terminate when carrying out the cyclical procedure of the invention, is purged. This may be done by means of steam and/or oxygen.
It will also be appreciated that the invention is not restricted to the use of two heat regenerators/reformers. More than two heat regenerators/reformers can be applied.
It will further be appreciated that the invention is not restricted to steam reforming. The invention can also be applied with CO2 reforming, wherein under appropriate conditions the reaction between an organic compound for example methane and CO2 can be carried out, resulting in a H2-CO ratio which is different from the H2-CO ratio which is different from the H2-CO ratio obtained in steam-reforming.
Various modifications of the present invention will become apparent to those skilled in the art from the foregoing description and accompaying drawing. Such modifications are intended to fall within the scope of the ap
Claims (15)
1. A semi-continuous process for producing a gas mixture containing hydrogen and carbon monoxide (synthesis gas) comprising an endothermic non-catalytic reaction of an organic compound with steam and/or carbon dioxide; and partial oxidation of a hydrocarbon containing fuel with an oxygen-containing gas whereby a gaseous product is produced and thermal energy for said endothermic reaction is provided, said process comprising the steps of
a) producing continuously synthesis gas by the said partial oxidation in a partial oxidation zone;
b) producing synthesis gas by the said endothermic reaction in a first heat regenerator/reformer;
c) feeding the synthesis gas thus obtained in the partial oxidation zone and in the first heat regenerator/reformer respectively to a second heat regenerator/reformer;;
d) exchanging heat between the said two synthesis gases in the second heat regenerator/reformer;
e) terminating the production of synthesis gas in the first heat regenerator/reformer;
f) discharging the synthesis gas after heat exchange from the second heat regenerator/reformer;
g) subsequently producing synthesis gas in the second heat regenerator/reformer by the said endothermic reaction;
h) feeding the synthesis gas thus obtained in the second heat regenerator/reformer to the first heat regenerator/reformer wherein heat exchange takes place with the synthesis gas produced by the partial oxidation in the partial oxidation zone;
i) terminating the production of synthesis gas in the second heat regenerator/reformer;
j) discharging the synthesis gas after heat exchange from the first heat regenerator/reformer; and
k) repeating the above steps b)-j) periodically.
2. The process as claimed in claim 1 wherein the organic compound consists of gaseous hydrocarbons or liquid hydrocarbons or solid hydrocarbons or mixtures thereof.
3. The process as claimed in claim 2 wherein the organic compound is methane.
4. The process as claimed in claim 2 wherein the organic compound is natural gas.
5. The process as claimed in claim 1 wherein the hydrocarbon containing fuel consists of gaseous hydrocarbons or liquid hydrocarbons or solid hydrocarbons or mixtures thereof.
6. The process as claimed in claim 5 wherein the hydrocarbon containing fuel is methane.
7. The process as claimed in claim 5 wherein the hydrocarbon containing fuel is natural gas.
8. The process as claimed in any one of claims 1-7 wherein the flow direction of the heat exchanging synthesis gases is opposite to that of the synthesis gas when produced in the respective heat regenerator/reformer.
9. The process as claimed in any one of claims 1-8 wherein the heat regenerator/reformer in which the production of synthesis gas should terminate, is purged.
10. The process as claimed in claim 9 wherein the said purging is carried out with steam and for oxygen.
11. The process as claimed in any one of claims 1-10 wherein the feed gases to the partial oxidation zone and the heat regenerator/reformers are fed through a recuperative heat exchanger.
12. The process as claimed in any one of claims 1-11 wherein the discharged synthesis gas is fed through a recuperative heat exchanger.
13. The process as claimed in claim 11 wherein the feed gases are preheated in the recuperative heat exchanger.
14. The process as claimed in claim 13 wherein the feed gases are preheated by an additional low temperature heat source.
15. Process substantially as described in the specification by reference to the accompanying drawing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08605921A GB2187751A (en) | 1986-03-11 | 1986-03-11 | Integrated synthesis gas production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08605921A GB2187751A (en) | 1986-03-11 | 1986-03-11 | Integrated synthesis gas production |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8605921D0 GB8605921D0 (en) | 1986-04-16 |
| GB2187751A true GB2187751A (en) | 1987-09-16 |
| GB2187751B GB2187751B (en) | 1989-05-10 |
Family
ID=10594359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08605921A Granted GB2187751A (en) | 1986-03-11 | 1986-03-11 | Integrated synthesis gas production |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2187751A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102645A (en) * | 1990-06-21 | 1992-04-07 | Liquid Carbonic Corporation | Method for manufacture of high purity carbon monoxide |
| US5181937A (en) * | 1985-06-27 | 1993-01-26 | Stone & Webster Engineering Corp. | Apparatus for production of synthesis gas using convective reforming |
| EP0578218A2 (en) * | 1992-07-08 | 1994-01-12 | Air Products And Chemicals, Inc. | Reformation in a plate-fin heat exchanger |
| EP1136443A1 (en) * | 2000-03-23 | 2001-09-26 | DANIELI & C. OFFICINE MECCANICHE S.p.A. | Gas and oxygen reactor and method for the production of reducing elements |
| WO2003035545A1 (en) * | 2001-10-26 | 2003-05-01 | Renault S.A.S | Method and device for generating hydrogen by high temperature conversion with water vapour |
| WO2007002911A1 (en) * | 2005-06-29 | 2007-01-04 | Exxonmobil Research And Engineering Company | Synthesis gas production and use |
| EP1813572A2 (en) | 2006-01-31 | 2007-08-01 | Linde BOC Process Plants LLC | Process and apparatus for synthesis gas |
| US8828107B2 (en) | 2006-01-31 | 2014-09-09 | Linde Process Plants, Inc. | Process and apparatus for synthesis gas heat exchange system |
-
1986
- 1986-03-11 GB GB08605921A patent/GB2187751A/en active Granted
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5181937A (en) * | 1985-06-27 | 1993-01-26 | Stone & Webster Engineering Corp. | Apparatus for production of synthesis gas using convective reforming |
| US5102645A (en) * | 1990-06-21 | 1992-04-07 | Liquid Carbonic Corporation | Method for manufacture of high purity carbon monoxide |
| WO1992015524A1 (en) * | 1991-02-28 | 1992-09-17 | Liquid Carbonic Corporation | Method for manufacture of high purity carbon monoxide |
| EP0578218A2 (en) * | 1992-07-08 | 1994-01-12 | Air Products And Chemicals, Inc. | Reformation in a plate-fin heat exchanger |
| EP0578218A3 (en) * | 1992-07-08 | 1994-10-26 | Air Prod & Chem | Reformation in a plate-fin heat exchanger. |
| EP1136443A1 (en) * | 2000-03-23 | 2001-09-26 | DANIELI & C. OFFICINE MECCANICHE S.p.A. | Gas and oxygen reactor and method for the production of reducing elements |
| WO2003035545A1 (en) * | 2001-10-26 | 2003-05-01 | Renault S.A.S | Method and device for generating hydrogen by high temperature conversion with water vapour |
| FR2831532A1 (en) * | 2001-10-26 | 2003-05-02 | Armines Ass Pour La Rech Et Le | METHOD AND DEVICE FOR GENERATING HYDROGEN BY HIGH TEMPERATURE CONVERSION WITH WATER VAPOR |
| WO2007002911A1 (en) * | 2005-06-29 | 2007-01-04 | Exxonmobil Research And Engineering Company | Synthesis gas production and use |
| US7740829B2 (en) | 2005-06-29 | 2010-06-22 | Exxonmobil Research & Engineering Company | Synthesis gas production and use |
| EP1813572A2 (en) | 2006-01-31 | 2007-08-01 | Linde BOC Process Plants LLC | Process and apparatus for synthesis gas |
| EP1813572A3 (en) * | 2006-01-31 | 2011-01-26 | Linde BOC Process Plants LLC | Process and apparatus for synthesis gas |
| CN101059317B (en) * | 2006-01-31 | 2012-07-11 | 林德加工工厂有限公司 | Synthesis gas heat exchange process and apparatus |
| CN102650501A (en) * | 2006-01-31 | 2012-08-29 | 林德加工工厂有限公司 | Process and apparatus for synthesis gas heat exchange system |
| US8828107B2 (en) | 2006-01-31 | 2014-09-09 | Linde Process Plants, Inc. | Process and apparatus for synthesis gas heat exchange system |
| CN102650501B (en) * | 2006-01-31 | 2015-04-01 | 林德加工工厂有限公司 | Process and apparatus for synthesis gas heat exchange system |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8605921D0 (en) | 1986-04-16 |
| GB2187751B (en) | 1989-05-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |