CA2058246A1 - Process for the production of highly pure hydrogen (h2) at high output pressures - Google Patents
Process for the production of highly pure hydrogen (h2) at high output pressuresInfo
- Publication number
- CA2058246A1 CA2058246A1 CA002058246A CA2058246A CA2058246A1 CA 2058246 A1 CA2058246 A1 CA 2058246A1 CA 002058246 A CA002058246 A CA 002058246A CA 2058246 A CA2058246 A CA 2058246A CA 2058246 A1 CA2058246 A1 CA 2058246A1
- Authority
- CA
- Canada
- Prior art keywords
- high pressure
- gas
- psa
- synthesis
- highly pure
- 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.)
- Abandoned
Links
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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- 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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
ABSTRACT
In the disclosed process, molecular sieves are used in a pressure swing adsorption (PSA) process under high pressure for the production of highly pure hydrogen at high output pressures within synthesis gases producing installations including integrated high pressure syntheses. In order to make the overall process more flexibly operable and more energy efficient, the high pressure molecular sieves are used in the PSA process at starting pressures of 100 to 220 and preferably 150 to 200 bar. Therefore, synthesis gas may be energy efficiently directly fed to the PSA process for the production of high pressure highly pure hydrogen at the reaction pressure of a subsequent high pressure synthesis wherein the highly pure hydrogen is used, thereby obviating the depressurization of the synthesis gas before the PSA process and pressurization of the obtained pure hydrogen gas before input to the high pressure synthesis.
In the disclosed process, molecular sieves are used in a pressure swing adsorption (PSA) process under high pressure for the production of highly pure hydrogen at high output pressures within synthesis gases producing installations including integrated high pressure syntheses. In order to make the overall process more flexibly operable and more energy efficient, the high pressure molecular sieves are used in the PSA process at starting pressures of 100 to 220 and preferably 150 to 200 bar. Therefore, synthesis gas may be energy efficiently directly fed to the PSA process for the production of high pressure highly pure hydrogen at the reaction pressure of a subsequent high pressure synthesis wherein the highly pure hydrogen is used, thereby obviating the depressurization of the synthesis gas before the PSA process and pressurization of the obtained pure hydrogen gas before input to the high pressure synthesis.
Description
2~82~
PROCESS FOR THE PRODUCTION OE HIGHLY PURE ~IYDROGEN (~12) AT HIGH OUTPUT PRESSURES
The invention relates to a process for the production of highly pure hydrogen (H2) at high output pressures for use in high pressure synthesis, for example, ammonia (NH3) synthesis, included in synthesis gas producing operations. More particu]arly, the invention relates to the use of molecular sieves under hlgh pressure in pressure ~swing adsorption ~PSA) systems of such synthe~lis gas producing operations.
The use of PSA technology for the purification of hydrogen is well known in the art. PSA systems are generally integrated into operations for the production of synthesis gases for high pressure syntheses, such as ammonia synthesis gas. The PSA process is a highly desirable process for the purification of hydrogen, since a ~ery high purity level (e.g. in excess of 99%) is achievable and there is only little pressure drop between the feed gas stream and the product gas stream. However, it is suggested in the art that PSA systems includlng molecular sieves cannot be run efficiently at the same pressures as the subsequent high pressure synthesis in which the purified feed gas is used.
British patents 2,154,566 and 2,191,185 describe process and apparatus for ammon~a synthesis gas production with typical input pressures into the PSA system of 5 or 6 bar and disclose the use of the highly pure hydrogen produced at such pressures in an ammonia synthesisO
In an improved process for the production of ammonia described in published European application EP O 115 752, the pressures used for the operation of a PSA system are 300 to 1,000 psia (20.4 to 68 bar) pressure adsorption pressure and 60 to 100 psia (4.1 to ~.8 bar) of purge gas or desorbate pressure.
It is disclosed in European published application 0 092 969 that, despite the advantages of the PSA system, certain disadvantages result when the PSA process is used under high adsorption pressures, for example above about 600 psig (40.8 bar). For the solution of the problems encountered at higher pressures, the application teaches sub~ecting a high pressure input stream which has a hydrogen content of up to 90 mol % to a membrane separation process before feeding it ' ' ' ', .
-`
2 ~
to the PSA syste~, which membrane separation proces~ ~electively retains impurities. The hydrogen-rich permeate gas is subject to an appreciable pressure drop in passing through the membrane 90 that it can be directly fed to a PSA system at lower pressure.
Thus, in prior art systems, the purified hydrogen gas is obtained at relatively low pressures and must be compressed before it may be used in a high pressure synthesis, whlch significantly increases the operation costs of the overall synthesis process.
It is now an a~pect of the present invention to provide highly pure nitrogen more energy efficiently than before for use in high pressure syntheses or for the sale to consumers.
Applicants performed high pressure tests with molecular sieves and have surprisingly found that molecular sieves may be used in PSA
systems at pressures much higher than the possible pressures suggested in the art.
Accordingly, the invention now provides a process for the production of highly pure hydrogen at high output pressures, which includes the use of molecular sieves in PSA systems under input pressure~ of 100 to 220, preferably 150 to 200 bar.
In a preferred embodiment, a crude synthesis gas is produced and purified in a synthesis gas producing operation by a process in accordance with the invention, which crude synthesis gas is produced by thermal cracking of hydrocarbon containing materials with oxygen and/or oxygen enxiched air and in the presence of steam in an autotherm non-catalytic reaction, by a subsequent first hydrogen sulfide scrubbing with cold methanol, a pressure conversion of the sulfur free gas, a second scrubbing with cold methanol, a third scrubbing with liquid nitrogen, and compression of the purified synthesis gas obtained by way of a turbo compressor to a pressure of 30 100 to 220, the turbo compressor being driven by high pressure steam, the synthesis gas being fed to the high pressure PSA process for the production of highly pure hydrogen gas at high pressure. The hydrocarbon containing materials are prPferably selected from the group of crude oil, light or heavy fuel oil, residue oils, tar oils, heavy gasoline, light gasoline, liquid gas, refinery gas and natural gas.
:
:~:
, . ~ .. : ., , 2~2~
-- 3 ~
In a synthesis gases producing operation including integrated ammonia and methanol (MeOH) syntheses as well as hydrocracking operations, a series of economical advantages may be shown when a process ln accordance with the inventlon is used. For example, the compression cost are reduced, since the purified hydrogen is obtained from the PSA system at much higher pressures than in prior art processes. Furthermore, logistic advantages may be shown. For example, load changes in the ammonia and methanol syntheses of such an operation may be achieved more easily without falling below the minimal output limits or the pump limits of turbo compressors used for the compression of the synthesis gases.
The use of a process in accordance with the invention in the production of synthesis gases for high pressure syntheses is further described in the following b~ way of an exemplary process and with reference to the drawings, wherein Figure 1 illustrates a flow diagram of a preferred process in accordance with the invention; and Figure 2 illustrates schematically the PSA system included in the proce3s illustrated in Figure 1.
Pressure stability tests were performed with appropriate molecular sieves of type 4 A grade lot number 135-1-9-110 at between lO and 40C ambient temperature and in 500 ml autoclaves in order to gain experience with molecular sieves at pressures above 65 bar. The tests consisted of pressure load experiments including five phases per cycle and 10 cycles overall as follows:
1st Phase: Pressurization with nitrogen to 50 bar within 4 to 5 minutes, 2nd Phase: Pressurization with hydrogen to 150 bar within further 8 to 10 minutes, 3rd Phase: Maintaining the pressure at 150 bar for about 5 minutes, 4th Phase: Depressurization to ambient pressure within 12 to 15 minutes, and 5th Pha~e: 5 minute pause.
Subsequent examinations of the mechanical properties of the molecular sieve bodies surprisingly showed that the molecular sieves are able to mechanically withstand the higher input pressures so that 2~2~6 their applicability in high pressure PS~ systems may be assumed ensured.
In a preferred embodiment of the process in accordance with the invention for the production of highly pure hydrogen gas at high output pressures for use in subsequent high pressure syntheses as illustrated in Figure l, a crude synthesis gas is produced under pressure by thermal cracking of hydrocarbons with oxygen in an autotherm non-catalysed reaction step lO. The heat required for this reaction is obtained from gasification steam which is generated in a steam superheater 40 and recycled thereto after passage through the hydrocarbon crac~ing reaction setup. The pressure gasification gas obtained is subsequently scrubbed under pressure with cold methanol in a first scrubbing step 12 to bring the contained hydrogen gas to synthesis purity for use in ammonia and methanol syntheses in hydrocracking processes. The first scrubbing step 12 is preferably subdivided so that in a primary hvdrogen sulfide (~12S) scrubbing a sulfur free gas is produced, which may be directly used in a methanol synthesis step 20 followed by a methanol distillation step 22 for the production of pure methanol. The removed hydrogen sulfide rich gas is transported, for example, to a Claus installation for further processing. A conventional carbon monoxide pressure conversion step 14 is in~erted after the first scrubbing step 12 for the production of input gas for ammonia synthesis and for the production of purified hydrogen gas. The carbon dioxide of the converted crude gas is either removed as lye by hot potash scrubbing or by ethanolamine scrubbing with monoethanolamine in a second scrubbing step 16, or the converted crude gas is directly adjusted in an additional step (not illustrated) with cold methanol to the synthesis purity required for methanol synthesis. The pre-purified hydrogen obtained is cleaned of remaining carbon monoxide and methane (CH4) with high pressure liquid nitrogen (HP-N2) at -180C by cryogen scrubbing in a third scrubbing step 18.
Simultaneously, the nitrogen and hydrogen contents required for the ammonia synthesis are ad~usted to 26% nitrogen and 74~/0 hydrogen. The hydrogen/nitrogen mixture resulting from the cryogenic scrubbing is used in an ammonia synthesis step 50 after compression to 200 bar by a turbo compressor/turbine combination 30, for example. In the alternative, the hydrogen/nitrogen mixture is selectively fed at the :
2~5~2~
same input preSs~lre to the ammonia synthesis step 50 and to a high pressure PSA system 70. Turning now to Figure 2, a PSA system is preferably used in a process in accordance with the invention inlcudes 5 parallel operating adsorbers 72 which include appropriate high pressure molecular sieves 74 (type 4 A grade from ~nlon Carbide).
Molecular sleves 74 are poured solid bed sieves. Synthesis gas is supplied through conduit 74 to all absorbers 72 and highly pure high pressure hydrogen is removed from the PSA system through line 76.
Depending on the degree of purity, highly pure hydrogen is produced by the PSA system 70 at a discharge pressure of about 150 bar. The feed of synthesis gas to adsorbers 72 is controlled by valves 78 which permit the selective feeding of an excess supply of synthesis gas to a nitrogen liquifaction installation 60 (see Fig. l). Thus, a hydrogen/nitrogen mixture is supplied at a ratio of 70:30 volume ~O and at a pres3ure of for example 50 bar to the nitrogen liquifaction installation 60. Finally, a waste gas is produced at about 2 bar which contains only little hydrogen and may be used, for example for the heating of the steam superheater 40.
Returning to Figure 1, the turbo compressor/turbine combination 30 which is used to compress the hydrogen/nitrogen gas mixture to the reaction pressure required ln the ammonia synthesis step 50, is driven by superheated steam generated in steam superheater ~0. The throughput of the nitrogen scrubbing step 18 must be controlled, in this embodiment, to remain within the throughput limits of step 18 and turbo compressor 30 when the input of the ammonia synthesis changes.
The throughput must be especially controlled to remain above the lower throughput limit of scrubbing step 18 and to avoid a lowering of the turbo compressor output below the minimum output limit or below the minimum pump limit. If the throughput in the nitrogen scrwbbing step 18 fell below the lower throughput limit, the beds would dry up, which would lead to a breakthrough of carbon monoxide to the ammonia synthesis resulting in irreversible catalyst damage. Thus, in order to avoid these difficulties, the throughput of nitrogen scrubbing step 18 is maintained above a lower limit, which may lead to the production of excess compressed ammonia synthesis gas, when the throughput of the ammonia synthesis step 50 is reduced. This excess gas, however, is advantageously fed at pressures of 100 to 220 bar to the PSA system 70 . .
20~2~
which includes high pressure molecular sleves (not shown) for the production of highly pure high pressure hydrogen tHP-H2).
The highly pure high pressure hydrogen may be used without additional compression costs for example, in hydrocracking processes commonly used in refineries. However, ~he highly pure high pressure hydrogen may also be directly used in high pressure hydrocracking processes at, for example, 170 bar without additiona]. compression in contrast to hydrogen obtained from reformer installations which is produced at about 15 bar and must be compressed.
As discussed above, a nitrogen/hydrogen mixture may be supplied to nitrogen liquifaction step 60 whereby this mixture is advantageously passed through a depressurization turbine (not shown) for the recovery of compression energy.
Also, the highly pure high pressure hydrogen may be advantageously used for other hydrations such as white oil hydration, or naphtha hydration, or may be directly filled into pressurized tanks for sale.
Thus, it i9 apparent that synthesis gas producing installations may be operated more flexibly and with more efficiency with a process in accordance with the invention in that the synthesis gas may be very energy efficiently provided to an additional production step for the production of high pressure highly pure hydrogen.
PROCESS FOR THE PRODUCTION OE HIGHLY PURE ~IYDROGEN (~12) AT HIGH OUTPUT PRESSURES
The invention relates to a process for the production of highly pure hydrogen (H2) at high output pressures for use in high pressure synthesis, for example, ammonia (NH3) synthesis, included in synthesis gas producing operations. More particu]arly, the invention relates to the use of molecular sieves under hlgh pressure in pressure ~swing adsorption ~PSA) systems of such synthe~lis gas producing operations.
The use of PSA technology for the purification of hydrogen is well known in the art. PSA systems are generally integrated into operations for the production of synthesis gases for high pressure syntheses, such as ammonia synthesis gas. The PSA process is a highly desirable process for the purification of hydrogen, since a ~ery high purity level (e.g. in excess of 99%) is achievable and there is only little pressure drop between the feed gas stream and the product gas stream. However, it is suggested in the art that PSA systems includlng molecular sieves cannot be run efficiently at the same pressures as the subsequent high pressure synthesis in which the purified feed gas is used.
British patents 2,154,566 and 2,191,185 describe process and apparatus for ammon~a synthesis gas production with typical input pressures into the PSA system of 5 or 6 bar and disclose the use of the highly pure hydrogen produced at such pressures in an ammonia synthesisO
In an improved process for the production of ammonia described in published European application EP O 115 752, the pressures used for the operation of a PSA system are 300 to 1,000 psia (20.4 to 68 bar) pressure adsorption pressure and 60 to 100 psia (4.1 to ~.8 bar) of purge gas or desorbate pressure.
It is disclosed in European published application 0 092 969 that, despite the advantages of the PSA system, certain disadvantages result when the PSA process is used under high adsorption pressures, for example above about 600 psig (40.8 bar). For the solution of the problems encountered at higher pressures, the application teaches sub~ecting a high pressure input stream which has a hydrogen content of up to 90 mol % to a membrane separation process before feeding it ' ' ' ', .
-`
2 ~
to the PSA syste~, which membrane separation proces~ ~electively retains impurities. The hydrogen-rich permeate gas is subject to an appreciable pressure drop in passing through the membrane 90 that it can be directly fed to a PSA system at lower pressure.
Thus, in prior art systems, the purified hydrogen gas is obtained at relatively low pressures and must be compressed before it may be used in a high pressure synthesis, whlch significantly increases the operation costs of the overall synthesis process.
It is now an a~pect of the present invention to provide highly pure nitrogen more energy efficiently than before for use in high pressure syntheses or for the sale to consumers.
Applicants performed high pressure tests with molecular sieves and have surprisingly found that molecular sieves may be used in PSA
systems at pressures much higher than the possible pressures suggested in the art.
Accordingly, the invention now provides a process for the production of highly pure hydrogen at high output pressures, which includes the use of molecular sieves in PSA systems under input pressure~ of 100 to 220, preferably 150 to 200 bar.
In a preferred embodiment, a crude synthesis gas is produced and purified in a synthesis gas producing operation by a process in accordance with the invention, which crude synthesis gas is produced by thermal cracking of hydrocarbon containing materials with oxygen and/or oxygen enxiched air and in the presence of steam in an autotherm non-catalytic reaction, by a subsequent first hydrogen sulfide scrubbing with cold methanol, a pressure conversion of the sulfur free gas, a second scrubbing with cold methanol, a third scrubbing with liquid nitrogen, and compression of the purified synthesis gas obtained by way of a turbo compressor to a pressure of 30 100 to 220, the turbo compressor being driven by high pressure steam, the synthesis gas being fed to the high pressure PSA process for the production of highly pure hydrogen gas at high pressure. The hydrocarbon containing materials are prPferably selected from the group of crude oil, light or heavy fuel oil, residue oils, tar oils, heavy gasoline, light gasoline, liquid gas, refinery gas and natural gas.
:
:~:
, . ~ .. : ., , 2~2~
-- 3 ~
In a synthesis gases producing operation including integrated ammonia and methanol (MeOH) syntheses as well as hydrocracking operations, a series of economical advantages may be shown when a process ln accordance with the inventlon is used. For example, the compression cost are reduced, since the purified hydrogen is obtained from the PSA system at much higher pressures than in prior art processes. Furthermore, logistic advantages may be shown. For example, load changes in the ammonia and methanol syntheses of such an operation may be achieved more easily without falling below the minimal output limits or the pump limits of turbo compressors used for the compression of the synthesis gases.
The use of a process in accordance with the invention in the production of synthesis gases for high pressure syntheses is further described in the following b~ way of an exemplary process and with reference to the drawings, wherein Figure 1 illustrates a flow diagram of a preferred process in accordance with the invention; and Figure 2 illustrates schematically the PSA system included in the proce3s illustrated in Figure 1.
Pressure stability tests were performed with appropriate molecular sieves of type 4 A grade lot number 135-1-9-110 at between lO and 40C ambient temperature and in 500 ml autoclaves in order to gain experience with molecular sieves at pressures above 65 bar. The tests consisted of pressure load experiments including five phases per cycle and 10 cycles overall as follows:
1st Phase: Pressurization with nitrogen to 50 bar within 4 to 5 minutes, 2nd Phase: Pressurization with hydrogen to 150 bar within further 8 to 10 minutes, 3rd Phase: Maintaining the pressure at 150 bar for about 5 minutes, 4th Phase: Depressurization to ambient pressure within 12 to 15 minutes, and 5th Pha~e: 5 minute pause.
Subsequent examinations of the mechanical properties of the molecular sieve bodies surprisingly showed that the molecular sieves are able to mechanically withstand the higher input pressures so that 2~2~6 their applicability in high pressure PS~ systems may be assumed ensured.
In a preferred embodiment of the process in accordance with the invention for the production of highly pure hydrogen gas at high output pressures for use in subsequent high pressure syntheses as illustrated in Figure l, a crude synthesis gas is produced under pressure by thermal cracking of hydrocarbons with oxygen in an autotherm non-catalysed reaction step lO. The heat required for this reaction is obtained from gasification steam which is generated in a steam superheater 40 and recycled thereto after passage through the hydrocarbon crac~ing reaction setup. The pressure gasification gas obtained is subsequently scrubbed under pressure with cold methanol in a first scrubbing step 12 to bring the contained hydrogen gas to synthesis purity for use in ammonia and methanol syntheses in hydrocracking processes. The first scrubbing step 12 is preferably subdivided so that in a primary hvdrogen sulfide (~12S) scrubbing a sulfur free gas is produced, which may be directly used in a methanol synthesis step 20 followed by a methanol distillation step 22 for the production of pure methanol. The removed hydrogen sulfide rich gas is transported, for example, to a Claus installation for further processing. A conventional carbon monoxide pressure conversion step 14 is in~erted after the first scrubbing step 12 for the production of input gas for ammonia synthesis and for the production of purified hydrogen gas. The carbon dioxide of the converted crude gas is either removed as lye by hot potash scrubbing or by ethanolamine scrubbing with monoethanolamine in a second scrubbing step 16, or the converted crude gas is directly adjusted in an additional step (not illustrated) with cold methanol to the synthesis purity required for methanol synthesis. The pre-purified hydrogen obtained is cleaned of remaining carbon monoxide and methane (CH4) with high pressure liquid nitrogen (HP-N2) at -180C by cryogen scrubbing in a third scrubbing step 18.
Simultaneously, the nitrogen and hydrogen contents required for the ammonia synthesis are ad~usted to 26% nitrogen and 74~/0 hydrogen. The hydrogen/nitrogen mixture resulting from the cryogenic scrubbing is used in an ammonia synthesis step 50 after compression to 200 bar by a turbo compressor/turbine combination 30, for example. In the alternative, the hydrogen/nitrogen mixture is selectively fed at the :
2~5~2~
same input preSs~lre to the ammonia synthesis step 50 and to a high pressure PSA system 70. Turning now to Figure 2, a PSA system is preferably used in a process in accordance with the invention inlcudes 5 parallel operating adsorbers 72 which include appropriate high pressure molecular sieves 74 (type 4 A grade from ~nlon Carbide).
Molecular sleves 74 are poured solid bed sieves. Synthesis gas is supplied through conduit 74 to all absorbers 72 and highly pure high pressure hydrogen is removed from the PSA system through line 76.
Depending on the degree of purity, highly pure hydrogen is produced by the PSA system 70 at a discharge pressure of about 150 bar. The feed of synthesis gas to adsorbers 72 is controlled by valves 78 which permit the selective feeding of an excess supply of synthesis gas to a nitrogen liquifaction installation 60 (see Fig. l). Thus, a hydrogen/nitrogen mixture is supplied at a ratio of 70:30 volume ~O and at a pres3ure of for example 50 bar to the nitrogen liquifaction installation 60. Finally, a waste gas is produced at about 2 bar which contains only little hydrogen and may be used, for example for the heating of the steam superheater 40.
Returning to Figure 1, the turbo compressor/turbine combination 30 which is used to compress the hydrogen/nitrogen gas mixture to the reaction pressure required ln the ammonia synthesis step 50, is driven by superheated steam generated in steam superheater ~0. The throughput of the nitrogen scrubbing step 18 must be controlled, in this embodiment, to remain within the throughput limits of step 18 and turbo compressor 30 when the input of the ammonia synthesis changes.
The throughput must be especially controlled to remain above the lower throughput limit of scrubbing step 18 and to avoid a lowering of the turbo compressor output below the minimum output limit or below the minimum pump limit. If the throughput in the nitrogen scrwbbing step 18 fell below the lower throughput limit, the beds would dry up, which would lead to a breakthrough of carbon monoxide to the ammonia synthesis resulting in irreversible catalyst damage. Thus, in order to avoid these difficulties, the throughput of nitrogen scrubbing step 18 is maintained above a lower limit, which may lead to the production of excess compressed ammonia synthesis gas, when the throughput of the ammonia synthesis step 50 is reduced. This excess gas, however, is advantageously fed at pressures of 100 to 220 bar to the PSA system 70 . .
20~2~
which includes high pressure molecular sleves (not shown) for the production of highly pure high pressure hydrogen tHP-H2).
The highly pure high pressure hydrogen may be used without additional compression costs for example, in hydrocracking processes commonly used in refineries. However, ~he highly pure high pressure hydrogen may also be directly used in high pressure hydrocracking processes at, for example, 170 bar without additiona]. compression in contrast to hydrogen obtained from reformer installations which is produced at about 15 bar and must be compressed.
As discussed above, a nitrogen/hydrogen mixture may be supplied to nitrogen liquifaction step 60 whereby this mixture is advantageously passed through a depressurization turbine (not shown) for the recovery of compression energy.
Also, the highly pure high pressure hydrogen may be advantageously used for other hydrations such as white oil hydration, or naphtha hydration, or may be directly filled into pressurized tanks for sale.
Thus, it i9 apparent that synthesis gas producing installations may be operated more flexibly and with more efficiency with a process in accordance with the invention in that the synthesis gas may be very energy efficiently provided to an additional production step for the production of high pressure highly pure hydrogen.
Claims (4)
1. Process for the production of highly pure hydrogen at high pressure in a synthesis gas producing operation including integrated high pressure syntheses by using an integrated high pressure swing adsorption (PSA) process, characterized in that molecular sieves are used in the PSA process at input pressures of 100 to 220 bar.
2. A process as defined in claim 1, characterized in that a synthesis gas is produced by thermal cracking of hydrocarbon containing materials with oxygen and/or oxygen enriched air and under presence of steam in an autotherm non-catalytic reaction, by a subsequent first hydrogen sulfide scrubbing with cold methanol, a pressure conversion of the sulfur free gas, a second scrubbing with cold methanol, a third scrubbing with liquid nitrogen, and compression of the purified synthesis gas obtained by way of a turbo compressor to a pressure of 100 to 220 bar, the turbo compressor being driven by high pressure steam, the synthesis gas being fed to the high pressure PSA process for the production of highly pure hydrogen gas at high pressure.
3. A process as defined in claim 2, wherein the hydrocarbon containing materials are selected from the group of crude oil, light or heavy fuel oil, residue oils, tar oils, heavy gasoline, light gasoline, liquid gas, refinery gas and natural gas.
4. A process as defined in claim 1, 2 or 3 wherein the input pressures of the PSA process are 150 to 200 bar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4041147.8 | 1990-12-21 | ||
| DE4041147A DE4041147C2 (en) | 1990-12-21 | 1990-12-21 | Process for the production of high-purity hydrogen (H2) at high discharge pressure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2058246A1 true CA2058246A1 (en) | 1992-06-22 |
Family
ID=6421007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058246A Abandoned CA2058246A1 (en) | 1990-12-21 | 1991-12-20 | Process for the production of highly pure hydrogen (h2) at high output pressures |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2058246A1 (en) |
| DE (1) | DE4041147C2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2199254A1 (en) * | 2008-12-11 | 2010-06-23 | BP p.l.c. | Integrated gas refinery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011589A (en) * | 1960-03-21 | 1961-12-05 | Mark Chemical Company Inc Van | Method for producing exceptionally pure hydrogen |
| EP0115752B1 (en) * | 1981-08-07 | 1986-12-10 | Union Carbide Corporation | Improved process and apparatus for the production of ammonia |
| US4861351A (en) * | 1987-09-16 | 1989-08-29 | Air Products And Chemicals, Inc. | Production of hydrogen and carbon monoxide |
-
1990
- 1990-12-21 DE DE4041147A patent/DE4041147C2/en not_active Expired - Fee Related
-
1991
- 1991-12-20 CA CA002058246A patent/CA2058246A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE4041147C2 (en) | 1994-12-08 |
| DE4041147A1 (en) | 1992-07-02 |
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