CN100469417C - System for recovering hydrogen from air of methanol synthesis processing by membrane method - Google Patents
System for recovering hydrogen from air of methanol synthesis processing by membrane method Download PDFInfo
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- CN100469417C CN100469417C CNB2005100460523A CN200510046052A CN100469417C CN 100469417 C CN100469417 C CN 100469417C CN B2005100460523 A CNB2005100460523 A CN B2005100460523A CN 200510046052 A CN200510046052 A CN 200510046052A CN 100469417 C CN100469417 C CN 100469417C
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Abstract
A membrane separation system for recovering the H2 from the air released in methanol synthesizing process is composed of gas-liquid separator, precise filler, heater and membrane separator. The membrane in the membrane separator is an asymmetrical polyimide one. It has high tolerence to methanol.
Description
Technical field the present invention relates to a kind of from the dropping a hint of industrial synthesizing methanol process the equipment of recover hydrogen.
The process of background technology industry synthesizing methanol is to be raw material with carbon monoxide, carbon dioxide and hydrogen, and reaction generates the first alcohol and water under high temperature and catalyst action.For making full use of unstripped gas, unreacted gas circulation to be used, its result can make inert gas (methane, nitrogen) accumulation, discharge unit circulating air aperiodically for this reason, it is called drops a hint, and its Main Ingredients and Appearance is hydrogen 50～80%, carbon dioxide 0.1～10%, carbon monoxide 3～10% and nitrogen 10～30%.This shows that the emptying process causes the loss of effective ingredient inevitably.For addressing this problem, U.S. Meng Shangdou company takes the lead in adopting the membrane technology airborne hydrogen of folding and unfolding back and forth.The preferential selection permeability (with respect to gases such as nitrogen, methane, carbon monoxide, carbon dioxide) of hydrogen is realized recovery in order to utilize macromolecule member material to hydrogen in the emptying gaseous mixture, simultaneously inert gases such as nitrogen, methane are discharged from circulating air, people design a complete embrane method reclaim the methyl alcohol building-up process drop a hint in the system of hydrogen, be called for short film separation system, it mainly includes eparating methanol tower, gas-liquid separator, heater and membrane separator.
Wherein the film in the membrane separator is again the crucial object of recover hydrogen, for guaranteeing its operate as normal, must set up auxiliary facilities such as eparating methanol tower, gas-liquid separator and heater.Contain a spot of methyl alcohol (general＜1%) in owing to drop a hint, it has corrosiveness to employed common polysulfones and polyimide film material, therefore be provided with eparating methanol tower in order to washing methyl alcohol, methyl alcohol is dropped a hint after eparating methanol tower removes methyl alcohol and to be removed drop in degassing through gas-liquid separator, heater via is heated to 60～80 ℃ and makes it temperature away from dew point again, increases the infiltration rate of gas by film simultaneously.The methyl alcohol membrane separator of being allowed for access after above-mentioned auxiliary facility is handled of dropping a hint can get two bursts of logistics after film separation system separates.One for enrichment the infiltration gas of hydrogen, another strand is the non-infiltration gas of poor hydrogen.Reclaimed the effective ingredient of a large amount of synthetic reactions in the infiltration gas, but Returning reactor continues to participate in reaction.But not in the infiltration gas enrichment mainly be the indifferent gas (as methane, nitrogen etc.) that does not participate in reacting, can discharge.Though do the loss that can avoid effective ingredients such as hydrogen like this, also there is certain defective, promptly eparating methanol tower need be equipped with power-equipments such as high-pressure hydraulic pump usually, causes thus that equipment investment is big, operating cost is high, operation sequence is complicated.
Summary of the invention the objective of the invention is to for reclaim the hydrogen of methyl alcohol building-up process in dropping a hint provide a kind of right≤embrane method that the methyl alcohol of 5% concentration has long-term tolerance and film separation system is simplified reclaim the methyl alcohol building-up process drop a hint in the system of hydrogen.
The material of film of the present invention also is a polyimides, but it is the polymer of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamine monomers,
Its structural formula is
A wherein
rBe aromatic hydrocarbon.
Film of the present invention is to constitute anisotropic membrane by the selective separation layer of one deck densification and loose supporting layer, and it can adopt above-mentioned polyimide material to make top layer densification, unsymmetric structure that bottom is loose; Also can make composite membrane at the top layer of anisotropic membrane coating silicon rubber.This film is to the transmission rates of the hydrogen transmitance much larger than nitrogen, oxygen, methane, carbon monoxide and carbon dioxide etc.When there is certain partial pressure difference the film both sides, hydrogen can be separated with gases such as nitrogen, oxygen, methane, carbon monoxide and carbon dioxide.Film of the present invention can bear the pressure reduction of 12MPa, though and the pressure that methyl alcohol is dropped a hint according to different production procedures and difference to some extent is generally 4～12MPa.Film of the present invention is that 5% gaseous methanol has long-term tolerance to concentration.And methyl alcohol drop a hint under the concentration normal condition of methyl alcohol mostly＜1%.Film of the present invention can be made flat sheet membrane or hollow-fibre membrane, and its kit form also can have multiple, as plate and frame, spiral wound, membrane stack formula, tubular type and doughnut formula etc.Membrane separator can single-stage be arranged, also can adopt two-stage or multistage arrangement (being about to the infiltration gas of one-level or non-infiltration gas), also can adopt way that the per-meate side at film vacuumizes to obtain better separating effect through boosting or keeping original pressure feeding gas as next stage.
Film of the present invention can be used for film separation system of the prior art, but because this film has long-term tolerance to methyl alcohol, therefore existing film separation system can be simplified, remove eparating methanol tower, make film separation system include only gas-liquid separator, heater and membrane separator.Wherein the structure of gas-liquid separator and heater and effect are same as the prior art.Be preferably in the gas-liquid separator back and be provided with accurate filter, can further remove the lime set in the raw material like this.
Because the simplification of film separation system, the technology of hydrogen became simply during feasible recovery methyl alcohol building-up process was dropped a hint, promptly
1. be that the methyl alcohol of 4～12MPa is dropped a hint and directly introduced the gas-liquid separator of film separation system with pressure, remove the drop in the gas;
2. will introduce heater by the gas that gas-liquid separator is told, be heated to 60～80 ℃, make it temperature, increase the infiltration rate of gas simultaneously by film away from dew point;
3. the gas after will heating is introduced membrane separator, separate to form two strands of air-flows through film: one for enrichment the infiltration gas of hydrogen, its pressure is 0.1～2MPa (generally a little more than inlet pressure between compressor section), temperature is 40～80 ℃, hydrogen 85～98%, all the other 2 ~ 15% gases are gases such as nitrogen, methane, carbon monoxide, carbon dioxide, methyl alcohol.This infiltration gas can cause the suction port of compressor of synthesizing methanol, participates in the reaction of synthesizing methanol after compressed the boosting again; Another strand air-flow is the non-infiltration gas of poor hydrogen, and pressure is that (lower by 0.05～0.2MPa) than unstripped gas, temperature is 60～80 ℃ to 5～12MPa, and hydrogeneous is 3～45%, and this non-infiltration gas can directly enter the gas pipe network and reclaim remaining calorific value.
The present invention has following advantage compared to existing technology:
1. film of the present invention has long-term tolerance to methyl alcohol, so long service life, has saved the expense of changing and keeping in repair.
2. adopt film of the present invention can simplify film separation system, both saved equipment investment, saved operating cost again, also reduced floor space, the operation and maintenance of equipment is more prone to.
3. the recovery of hydrogen during film separation system of the present invention is dropped a hint applicable to the methyl alcohol of the exclusive connection alcohol technology of high, medium and low voltage methyl alcohol building-up process and China, it also is applicable to residual oil, acetylene tail gas, natural gas etc. be that raw material is produced the drop a hint recovery of middle hydrogen of methyl alcohol simultaneously.
Description of drawings
Fig. 1 is the schematic flow sheet of example 1 of the present invention.
Fig. 2 is the generalized section of film of the present invention.
Fig. 3 is the schematic flow sheet of example 2 of the present invention.
Fig. 4 is the schematic flow sheet of example 3 of the present invention.
Fig. 5 is the schematic flow sheet of example 4 of the present invention.
The specific embodiment
Example 1
Embrane method shown in Figure 1 reclaim the methyl alcohol building-up process drop a hint in the system schematic of hydrogen, film separation system is made up of gas-liquid separator 1, heater 2 and membrane separator 3, methyl alcohol drop a hint (concrete parameter see Table 1) enter gas-liquid separator, after separating, remove drop wherein, enter heater again, through heat temperature raising to 60 ℃, enter membrane separator then.Doughnut formula assembly is arranged in this membrane separator, and the film 4 that is adopted in the assembly is that monomer is the polyimides asymmetric hollow fiber membrane (production of company of Ube Industries Ltd.) of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamines, and its section as shown in Figure 2.Because there is the effect of partial pressure difference and film itself in the both sides of film, the hydrogen of dropping a hint then sees through film, and gases such as nitrogen, methane, carbon monoxide and carbon dioxide then tunicle " are held back " in an original side.Methyl alcohol is dropped a hint and is separated the back through film and form two strands of exit flows like this, and one is the rich hydrogen infiltration gas of 0.8MPa for hydrogeneous 94.07%, pressure, and it can directly cause the suction port of compressor and participate in again reacting after boosting; Another strand is the non-infiltration gas of poor hydrogen of 9.6MPa for hydrogeneous 3.76%, methane 42.47%, pressure, and it contains more fuel gas, can enter the gas pipe network gas that acts as a fuel and use.
The table 1-1 methyl alcohol film separation system material balance of dropping a hint
Table 1-2 separating methanol flow process and not separating methanol technology contrast (processing tolerance 2500nm
3/ hr)
As seen from the above table, adopt the improvement flow process can save equipment investment 10%, in addition, the annual operating cost (4.4 ten thousand yuan) that accounts for existing equipment investment 6.8% of saving.
Example 2
Embrane method shown in Figure 3 reclaim the methyl alcohol building-up process drop a hint in the system schematic of hydrogen, film separation system is made up of gas-liquid separator 1, heater 2 and membrane separator 3, methyl alcohol drop a hint (concrete parameter see Table 2) enter gas-liquid separator, behind separator, remove drop wherein, enter heater again, through heat temperature raising to 60 ℃, enter membrane separator then.In this membrane separator spiral wound module is arranged, the film 4 that is adopted in the assembly is that monomer is the asymmetric flat sheet membrane of polyimides of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamines, and its top layer coating silicon rubber.Because the hydrogen that the both sides of film exist the effect of partial pressure difference and film itself to drop a hint then sees through film, gases such as nitrogen, methane, carbon monoxide and carbon dioxide then tunicle " are held back " in an original side.Methyl alcohol is dropped a hint and is separated the back through film and form two strands of exit flows like this, and one is the rich hydrogen infiltration gas of 0.8MPa for hydrogeneous 95.11%, pressure, and it can directly cause the suction port of compressor and participate in again reacting after boosting; Another strand is the non-infiltration gas of poor hydrogen of 3.8MPa for hydrogeneous 13.55%, methane 41.45%, pressure, and it contains more fuel gas, can enter the gas pipe network gas that acts as a fuel and use.
The table 2-1 methyl alcohol film separation system material balance of dropping a hint
Table 2-2 separating methanol flow process and not separating methanol technology contrast (processing tolerance 2500nm
3/ hr)
As seen from the above table, adopt the improvement flow process can save equipment investment 7.6%, in addition, the annual operating cost (4.5 ten thousand yuan) that accounts for existing equipment investment 6.9% of saving.
Example 3
Embrane method shown in Figure 4 reclaim the methyl alcohol building-up process drop a hint in the system schematic of hydrogen, film separation system is made up of gas-liquid separator 1, heater 2 and membrane separator 3, methyl alcohol drop a hint (concrete parameter see Table 3) enter gas-liquid separator, after separating, remove drop wherein, enter accurate filter 5 afterwards again, just enter heater then,, enter membrane separator then through heat temperature raising to 80 ℃.The plate and frame assembly is arranged in this membrane separator, and the film 4 that is adopted in the assembly is that monomer is the asymmetric flat sheet membrane of polyimides of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamines.Because the hydrogen that the both sides of film exist the effect of partial pressure difference and film itself to drop a hint then sees through film, gases such as nitrogen, methane, carbon monoxide and carbon dioxide then tunicle " are held back " in an original side.Methyl alcohol is dropped a hint and is separated the back through film and form two strands of exit flows like this, and one is the rich hydrogen infiltration gas of 0.8MPa for hydrogeneous 90.84%, pressure, and it can directly cause the suction port of compressor and participate in again reacting after boosting; Another strand is the non-infiltration gas of poor hydrogen of 11.8MPa for hydrogeneous 7.39%, methane 39.85%, pressure, and it contains more fuel gas, can enter the gas pipe network gas that acts as a fuel and use.
The table 3-1 methyl alcohol film separation system material balance of dropping a hint
Table 3-2 separating methanol flow process and not separating methanol technology contrast (processing tolerance 2500nm
3/ hr)
As seen from the above table, adopt the improvement flow process can save equipment investment 13.8%, in addition, the annual operating cost (4.5 ten thousand yuan) that accounts for existing equipment investment 7.8% of saving.
Example 4
Embrane method shown in Figure 5 reclaim the methyl alcohol building-up process drop a hint in the system schematic of hydrogen, film separation system is made up of gas-liquid separator 1, heater 2 and membrane separator 3, methyl alcohol drop a hint (concrete parameter see Table 4) enter gas-liquid separator, after separating, remove drop wherein, enter heater again, through heat temperature raising to 60 ℃, enter membrane separator then.Doughnut formula assembly is arranged in this membrane separator, and the film 4 that is adopted in the assembly is that monomer is the polyimides asymmetric hollow fiber membrane of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamines.Because there is the effect of partial pressure difference and film itself in the both sides of film, the hydrogen of dropping a hint then sees through film, and gases such as nitrogen, methane, carbon monoxide and carbon dioxide then tunicle " are held back " in an original side.Membrane separator adopts two-stage to arrange, and can obtain the hydrogen production of variable concentrations like this in the per-meate side of first order film and second level film.Methyl alcohol is dropped a hint and is separated the back through film and form three strands of exit flows like this, and one is the one-level infiltration gas of 0.12MPa for hydrogeneous 99.08%, pressure, can be used as pure hydrogen use; Another strand is hydrogeneous 97.4% secondary infiltration gas, and it can directly cause the suction port of compressor and participate in reaction again after boosting; Also having one be the non-infiltration gas of poor hydrogen hydrogeneous 43.26%, methane 24.05%, and it contains more fuel gas, can enter the gas use that acts as a fuel of gas pipe network.
The table 4-1 methyl alcohol film separation system material balance of dropping a hint
Table 4-2 separating methanol flow process and not separating methanol technology contrast (processing tolerance 2500nm
3/ hr)
As seen from the above table, adopt the improvement flow process can save equipment investment 6.3%, in addition, the annual operating cost (4.5 ten thousand yuan) that accounts for existing equipment investment 5.6% of saving.
Annotate: the concentration during the present invention describes is molar concentration, and pressure is absolute pressure.
Claims (2)
1. the system of hydrogen during an embrane method recovery methyl alcohol building-up process is dropped a hint, it is characterized in that: this film separation system is made up of gas-liquid separator, heater and membrane separator, and the film in the membrane separator is that monomer is the polyimides anisotropic membrane of biphenyltetracarboxyacid acid base acid anhydride and aromatic diamines.
2. the system of hydrogen is characterized in that: be provided with accurate filter in the gas-liquid separator back during embrane method recovery methyl alcohol building-up process according to claim 1 was dropped a hint.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101417799B (en) * | 2007-10-26 | 2011-08-17 | 上海焦化有限公司 | Method for recovering high-purity carbon monooxide from synthesis gas |
| CN101372314B (en) * | 2008-07-15 | 2011-04-27 | 华南理工大学 | Method and apparatus for producing hydrogen from hydrogen-containing synthesis gas using palladium membrane |
| CN101648105B (en) * | 2009-08-31 | 2011-08-10 | 武汉钢铁(集团)公司 | Method for extracting hydrogen gas with high purity from coke oven gas by metal palladium membrane separation technique |
| US8168685B2 (en) * | 2011-07-01 | 2012-05-01 | Membrane Technology And Research, Inc | Process for the production of methanol including one or more membrane separation steps |
| CN108547673B (en) * | 2018-02-28 | 2020-12-22 | 上海柯来浦能源科技有限公司 | Kohlepu system for generating electricity by utilizing environmental heat |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103494A (en) * | 1984-03-21 | 1986-11-12 | 宇部兴产株式会社 | Aromatic polyimide composition |
| CN1163255A (en) * | 1996-02-15 | 1997-10-29 | 金属股份有限公司 | Process for producing methanol |
| JP2000313742A (en) * | 1999-04-28 | 2000-11-14 | Nitto Denko Corp | Polyimide, gas separation membrane using the same and method for producing the polyimide and the membrane |
| US6171574B1 (en) * | 1996-09-24 | 2001-01-09 | Walter Juda Associates, Inc. | Method of linking membrane purification of hydrogen to its generation by steam reforming of a methanol-like fuel |
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2005
- 2005-03-15 CN CNB2005100460523A patent/CN100469417C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103494A (en) * | 1984-03-21 | 1986-11-12 | 宇部兴产株式会社 | Aromatic polyimide composition |
| CN1163255A (en) * | 1996-02-15 | 1997-10-29 | 金属股份有限公司 | Process for producing methanol |
| US6171574B1 (en) * | 1996-09-24 | 2001-01-09 | Walter Juda Associates, Inc. | Method of linking membrane purification of hydrogen to its generation by steam reforming of a methanol-like fuel |
| JP2000313742A (en) * | 1999-04-28 | 2000-11-14 | Nitto Denko Corp | Polyimide, gas separation membrane using the same and method for producing the polyimide and the membrane |
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