CN1025110C - Process for extracting concentrated hydrogen by pressure swing adsorption - Google Patents
Process for extracting concentrated hydrogen by pressure swing adsorption Download PDFInfo
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- CN1025110C CN1025110C CN 92110918 CN92110918A CN1025110C CN 1025110 C CN1025110 C CN 1025110C CN 92110918 CN92110918 CN 92110918 CN 92110918 A CN92110918 A CN 92110918A CN 1025110 C CN1025110 C CN 1025110C
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 30
- 230000008929 regeneration Effects 0.000 claims abstract description 15
- 238000011069 regeneration method Methods 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims description 18
- 230000000274 adsorptive effect Effects 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- 238000003825 pressing Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000001914 calming effect Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 206010016825 Flushing Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Separation Of Gases By Adsorption (AREA)
Abstract
The invention provides a ten-tower process, namely an L10-4-4 process, which is suitable for extracting hydrogen from hydrogen-containing feed gas by pressure swing adsorption. It is composed of adsorption, regeneration and pressure boosting steps, and features that four towers are in adsorption step at the same time, and four pressure equalizing, four pressure boosting and product hydrogen pressurizing are adopted. The processing capacity of the device is improved, and the yield of the product hydrogen is increased by 1-2% (volume).
Description
The invention belongs to the gas delivery field, relate in particular to transformation absorption (PSA) process of separating hydrogen gas from hydrogen-containing gas.Its international Patent classificating number is B01D53/04.
As everyone knows, in many oil refining and chemical plant installations dispensing gas, all contain hydrogen, for example: devices such as hydrofining, hydrocracking, catalytic cracking, synthetic ammonia, hydrocarbon cracking system alkene, synthesizing methanol, catalytic reforming.That is discharged out contains hydrogen mixed gas, also contains N usually
2, CO, CO
2, H
2O, Ar and C
1-C
4Hydrocarbon etc.
About the separation of gas, as far back as U.S.P3 in 1969,430,418 disclosed the PSA technology of once all pressing; U.S.P.3 in 1971,564,816 disclose the PSA technology that four tower secondaries are all pressed, and this technology is widely used in separates hydrogeneous gas mixture, and its hydrogen purity reaches 99.999%.Be expansion instrument throughput, improve hydrogen recovery rate, U.S.P.3,986,849 (1) disclose multitower PSA technology.(1) be 10 adsorption tower technical process, all pressures are arranged in a loop cycle three times, each constantly always has three adsorption towers to be in adsorption step, and other seven towers are in the different regeneration stages respectively.This technology is called for short 10-3-3 flow process (referring to accompanying drawing 1), and the working routine of adsorption tower is seen accompanying drawing 2.Found out that by figure this technology is promptly carried out all pressing for three times, forward put pressures, reversely puts pressure, washes after certain tower adsorption step finishes, a loop cycle is finished in three pressurisings, the pressurising of product hydrogen.USP4402712 (2) discloses new 10 tower PSA technologies (seeing accompanying drawing 3,4).It is three all pressure, the absorption of four towers, abbreviates the 10-3-4 technical process as.Its goal of the invention is to solve the method that can handle two kinds of unstripped gass simultaneously.After certain tower adsorption step finishes, begin to carry out all to press for three times, forward put pressure, reversely then put pressures, wash.Regeneration step finishes.Then, enter the step of boosting, i.e. three pressurisings, the pressurising of product hydrogen has entered adsorption step again.Document (2) is compared with (1), and its difference is that (2) can adopt two kinds of unstripped gass, and two feeding lines are arranged, two waste lines, and four towers are in adsorbed state simultaneously.When processing power was identical, (2) wanted littler than the adsorption tower size of (1).The weak point of document (2) is: when the hydrogen richness of two kinds of unstripped gass differs bigger, if by hydrogeneous high unstripped gas design adsorption time, the absorb leading-edge of then handling in the low adsorption tower of hydrogen richness will penetrate, and can not guarantee the purity of product hydrogen; If by low hydrogeneous unstripped gas design adsorption time, the sorbent material of then handling in the high hydrogenous adsorption tower can not make full use of, and will reduce the yield of product hydrogen.Moreover, when one of unstripped gas flow changes, then can not adjust adsorption cycle automatically, thereby make it can not be in optimal operational condition with fluctuations in discharge.
The present invention proposes a kind of improved being used for from containing ten tower pressure swing adsorption techniques of hydrogen mixed gas separating and concentrating hydrogen.The yield of the hydrogen product of this technology is than prior art height, and under the same treatment ability, its sorbent material lacks than the consumption of 10-3-3 flow process, and the adsorption tower size is littler than 10-3-3.
Ten tower flow processs of the present invention are four all pressures, and four towers adsorb simultaneously, abbreviate the L10-4-4 technical process as.This technology at any time in, always have four towers to be in adsorption step, other six towers then are in the different regeneration and the step of boosting respectively.This technology by absorption, regenerate and three steps of boosting constitute a loop cycle.Separated unstripped gas enters adsorption tower through feed line, and through adsorbents adsorb, product hydrogen is delivered to the hydrogen basin by the product pipeline.After adsorption step is finished, enter regeneration step.Regeneration step comprises all presses, forward puts pressure four times, reversely puts pressures, washes.After regeneration step finishes, enter (also claiming pressurising, the down together) step of boosting.The step of boosting comprises: four pressurisings and the pressurising of product hydrogen.So just finished a loop cycle.L10-4-4 technology of the present invention always has four towers to be in adsorption step in arbitrary moment of operation, and all the other each towers are in the regeneration and the step of boosting respectively.
Adopt the present invention can bring into play the effect of sorbent material to greatest extent, can improve hydrogen yield 1-2%(body).
Accompanying drawing 1-8 and nomenclature thereof;
Accompanying drawing 1 is the PSA10-3-3 schema;
Accompanying drawing 2 is each tower working routine of PSA10-3-3 flow process;
Accompanying drawing 3 is PSA10-3-4 schemas;
Accompanying drawing 4 is each tower working routine of PSA10-3-4 flow process;
Accompanying drawing 5 is PSA10-4-4 schemas;
Accompanying drawing 6 is each tower working routine of PSA10-4-4 flow process;
Accompanying drawing 7 is each tower working routine of PSAL8-2-3 flow process;
Accompanying drawing 8 is each tower working routine of PSAL5-2-2 flow process.
Symbol in the accompanying drawing:
A-absorption, E1D-once all presses,
The E2D-secondary is all pressed, and E3D-all presses for three times,
E4D-all presses for four times, and PP-is forward put pressure,
The reverse pressure of putting of D-, the P-flushing,
A pressurising of E1R-(promptly boosting, down together), the pressurising of E2R-secondary,
Three pressurisings of E3R-, four pressurisings of E4R-,
The pressurising of R-product gas, the Ff-unstripped gas,
Wg-waste gas, P
M-product hydrogen;
The numbering of adsorption tower is respectively with Arabic numerals 1,2,3,4,5,6,7,8,9,10 expressions; Dated digital valve among the figure (
) be stopping valve.
PSA L10-4-4 technology of the present invention be 10 adsorption towers be divided into respectively odd number (be tower 1,3,5,7,9) series and even number (be tower 2,4,6,8,10) two series of series, they share a feed line, an exhaust pipe and a product pipeline.
Below by accompanying drawing 5-8 PSAL10-4-4 technology of the present invention is carried out concrete description.
Now take tower 1 as example, unstripped gas enters adsorption tower 1 by valve 11, and product hydrogen is delivered to product storage tank by valve 12 by shared product line, and impurity is adsorbed by the adsorbent in the tower. The adsorption step of tower 1 enters regeneration step after finishing, and the adsorbent of tower 1 is regenerated. Tower 1 is once all pressed (E1D) by valve 16,66 pairs of towers 6, (this moment tower 6 be the 4th time boost), by valve 16,76 pairs of towers 7 carry out secondary and all press (E2D) (tower 7 is to boost for the third time), undertaken three times and all press (E3D) by valve 13,83 pairs of towers 8, (tower 8 is to boost for the second time), the 4th time is all pressed (E4D) is by valve 13,93, and tower 9 is once boosted. All press the hydrogen that to store in the tower 1 to be recovered in tower 6,7,8,9 four towers by above-mentioned four times, improved simultaneously their pressure, impurity on tower 1 adsorbent obtains the part desorb, tower 1 after all pressing for four times forward bleeds off pressure (PP) by valve 15,105,104, to tower 10 flushings, the impurity on desorber 10 adsorbents. Afterwards, tower 1 carries out reverse bleeding off pressure (D) by valve 14, makes the further desorb of impurity on tower 1 adsorbent, and the exhaust pipe discharger by sharing. Then, forward bleed off pressure gas with tower 2 and wash (P) by valve 25,15,14 pairs of towers 1. Tower 1 regeneration step finishes. The gas of then, all pressing for the 4th time with tower 3 carries out pressurising (E one time by valve 33,13 pairs of towers 11R); The body of all calming the anger for the third time with tower 4 passes through valve 43,13 couples of tower 1 for the second time pressurising (E2R), with the body of all calming the anger the second time of tower 5 by valve 56, the 16 pairs of towers 1 pressurising (E for the third time3R); All calm the anger for the first time body by valve 66, the 4th pressurising of 16 pairs of towers 1 with tower 6, use at last product hydrogen that adsorptive pressure is arrived in tower 1 pressurising (R). Finished a cycle period of adsorption seperation of gas.
When tower 1 had been finished absorption (A) step, tower 5 had entered adsorption step.The tower 1 that enters regeneration step is when having finished when all pressing for the second time, and tower 2 has been finished adsorption step, and tower 6 has entered adsorption step.This shows that (for example tower 1,2,3 for two adjacent adsorption towers ...) between differed for two steps (seeing accompanying drawing 6), whenever carrying out two step regeneration then has a tower to finish adsorption step, has another adsorption tower to finish simultaneously to boost step and enters adsorption step.
PSA L10-4-4 of the present invention, in operational process, parts under certain tower break down, when causing this tower not run well, then can (automatically or manually) switch to the operation of eight towers by the operation of ten towers, promptly become secondary and all press, eight tower flow processs of three towers absorption abbreviate the PSAL8-2-3 flow process as.
Switch the operation of 8 towers by the operation of 10 towers, respectively cut away a tower in Ying Congqi, two series of idol, and should from a series, not cut away two adsorption towers.10 towers become 8 towers, and five kinds of handover schemes can be arranged, and each tower working routine of these five kinds of schemes is seen accompanying drawing 7.Suppose that now tower 9 breaks down, then cut away tower 9, tower 10, become tower 1,2,3,4,5,6,7,8 and be in running status.Be that example illustrates the L8-2-3 technical process now with tower 1.That is:
Unstripped gas enters tower 1 by valve 11, and product hydrogen is delivered to the hydrogen basin by valve 12 by shared pipeline, and impurity is attracted on tower 1 sorbent material.Tower 1 adsorption step is once all pressed (E by 16,56 pairs of towers 5 of valve after finishing
1D), tower 5 is secondary booster (E
2R), tower 1 once all presses the back forward to put pressure (PP) by valve 15,75, and tower 7 is washed (P), makes the impurity desorb on tower 7 sorbent materials.Afterwards, carry out secondary by valve 15,75 and all press (E
2D), to the tower 7 (E that once boosts
1R).Secondary carries out the reverse pressure (D) of putting by valve 14 after all pressing, and makes impurity desorb further on the sorbent material in the tower 1, and by shared waste line discharger.Then, pressure (PP) gas of forward putting by valve 35,15 usefulness towers 3 washes (P) to the reverse tower of putting after the pressure 1, makes the impurity on its sorbent material obtain desorb, then all presses (E with the secondary of tower 3
2D) gas advances once (the E that boosts by 35,15 pairs of towers 1 of valve
1R), once all press (E with tower 5
1D) gas carries out secondary booster (E by 56,16 pairs of towers 1 of valve
2R).Afterwards, arrive adsorptive pressure with product hydrogen by 12 pairs of tower 1 pressurisings of valve.Finish a fractionation by adsorption loop cycle.
When being switched to 8 towers (L8-2-3) flow process by 10 towers, its processing power remains unchanged substantially, and just yield slightly reduces, and the 10-3-3 of document (1) is when switching to 8-2-2, and its processing power descends about 20%, and yield slightly descends.
L10-4-4 flow process of the present invention is in operation, if the synergic system parts in odd number series or the even number series, perhaps break down simultaneously with two or more adsorption towers in a series of, then can (automatic or manual) switching fall out of order adsorption tower series, make trouble free series continue operation.At this moment operational scheme is the L5-2-2 flow process, and promptly secondary is all pressed (E
1D, E
2D), two towers adsorb simultaneously.The working routine of this each tower of flow process is shown in accompanying drawing 8, supposes that here even number series is cut off, and becomes tower 1,3,5,7,9 these five tower operations, and existing is that example illustrates the L5-2-2 flow process with tower 1 still.As follows:
Unstripped gas enters adsorption tower 1 by valve 11, and product hydrogen is delivered to the hydrogen basin by valve 12 by shared pipeline, and impurity is attracted on the sorbent material in the tower 1.After tower 1 adsorption step (A) finished, tower 1 was once all pressed (E by 16,76 pairs of towers 7 of valve
1D), (this moment, tower 7 was to boost for the second time).After once all pressing, tower 1 is forward put pressure (PP) by valve 15,95, and tower 9 is washed (P), makes the impurity desorb on tower 9 sorbent materials.Then, tower 1 carries out secondary and all presses (E
2D) gas once boosts by 15,95 pairs of towers 9 of valve.Tower 1 after secondary is all pressed carries out the reverse pressure (D) of putting through valve 14, makes the impurity desorb further on tower 1 sorbent material, and by shared waste line discharger.The gas of forward putting pressure (PP) with tower 3 washes (P) to tower 1 then, with the impurity on its sorbent material of desorb.Afterwards, all press (E with tower 3 secondaries
2D) gas carries out pressurising (E one time by 35,15 pairs of towers 1 of valve
1R), once all press (E with tower 5
1D) gas carries out secondary pressurising (E by 56,16 pairs of towers 1 of valve
2R), use product hydrogen to arrive adsorptive pressure then, finish a fractionation by adsorption loop cycle through 12 pairs of tower 1 pressurisings of valve (R).
The 10-3-3 flow process ratio of the same document of L10-4-4 flow process (1), when all switching to the operation of five towers, L5-2-2 flow process of the present invention is bigger than the treatment capacity of the 5-2-1 flow process of document (1).
Embodiment
Example 1, unstripped gas composed as follows, its pressure is 2.45MPa.Requiring the purity of product hydrogen is 99.99%.
Form H
2CO CH
4CO
2
The %(body) 70.91 2.96 6.5 19.56
(V), CO content is not higher than 10ppm, CO
2Content is not higher than 10ppm.Examination is the long-pending and hydrogen yield of tower body of 10-3-3, L10-4-4 flow process relatively.
It the results are shown in table 1:
Table 1
Flow process 10-3-3 L10-4-4
Index
Loop cycle, second 800 800
Adsorption time, second 240 320
Tower height, rice 6.77 6.77
Tower diameter, rice 1.65 1.43
Tower body is long-pending, rice
314.4 10.87
Hydrogen yield, %(V) 88.3 89.3
Be not difficult to find out that from table 1 the present invention exceeds at the hydrogen yield under 1% the situation, the cumulative volume of its 10 towers is littler 35.3 meters than 10-3-3
3, be equivalent to save sorbent material 25%.This is very favourable to the cost, the saving sorbent material that reduce adsorption tower.
The composition of example 2, unstripped gas and its pressure are with example 1.Purity and foreign matter content to product hydrogen require identical with example 1.Examination relatively switches to the 8-2-2 of 8 towers operation, the difference of L8-2-3 flow process by the operation of 10 towers, the results are shown in Table 2.
Table 2
Flow process 8-2-2 L8-2-3
Index
Loop cycle, second 779 640
Adsorption time, second 180 240
Processing power (comparing with 10 towers) decline 20% does not descend substantially
The result shows that the processing power of L8-2-3 flow process is originally identical with original 10 column foots, can not influence the hydrogen supply amount of downstream unit.
Equally, technical process of the present invention, when switching to the operation of five towers, promptly still the 5-2-1 flow process than document (1) is superior for the L5-2-2 flow process, and its processing power is big more a lot of than the latter.
Claims (4)
1, a kind of ten tower process that are applicable to from hydrogeneous unstripped gas with pressure-changed adsorption concentrating hydrogen, form a loop cycle by adsorption step, regeneration step and the step of boosting, the time there are four towers to be in adsorption step simultaneously in operation, it is characterized in that the L10-4-4 process using all presses (E four times
1D, E
2D, E
3D, E
4D), forward put pressure (PP), the reverse pressure (D) of putting, flushing (P); Adopt four times the (E that boosts
1R, E
2R, E
3R, E
4R) and product hydrogen pressurising (R), improve the yield of product hydrogen.
2, L10-4-4 technology according to claim 1, it is characterized in that when a certain adsorption tower of having finished adsorption step enters regeneration step, whenever carry out two step regeneration and enter adsorption step, just have a tower to finish adsorption step with regard to having a tower to finish to boost step.
3, L10-4-4 technology according to claim 1, when this technology can not normally be moved because the parts of a certain adsorption tower break down in operational process, changeable one-tenth eight tower flow processs turn round, it is characterized in that this eight tower process flow process is L3-2-3, promptly always have three towers to be in adsorption step at any one time; Adopt secondary all to press (E
1D, E
2D), secondary booster (E
1R, E
2R) and the pressurising of product hydrogen to adsorptive pressure.
4, L10-4-4 technology according to claim 1, synergic system parts in odd number series or even number series, when perhaps breaking down with the two or more adsorption towers in a series of, changeablely fall out of order series, becoming five tower flow processs moves, it is characterized in that this five tower process flow process is L5-2-2, promptly always have two towers to be in adsorption step at any one time; Adopt secondary all to press (E
1D, E
2D), secondary booster (E
1R, E
2R) and product hydrogen pressurising (R) to adsorptive pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110918 CN1025110C (en) | 1992-09-24 | 1992-09-24 | Process for extracting concentrated hydrogen by pressure swing adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110918 CN1025110C (en) | 1992-09-24 | 1992-09-24 | Process for extracting concentrated hydrogen by pressure swing adsorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070840A CN1070840A (en) | 1993-04-14 |
| CN1025110C true CN1025110C (en) | 1994-06-22 |
Family
ID=4945039
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92110918 Expired - Fee Related CN1025110C (en) | 1992-09-24 | 1992-09-24 | Process for extracting concentrated hydrogen by pressure swing adsorption |
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| Country | Link |
|---|---|
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088443C (en) * | 1997-01-09 | 2002-07-31 | 中国科学院大连化学物理研究所 | Method for producing high-purity hydrogen |
| CN101314098B (en) * | 2008-02-05 | 2010-08-18 | 四川亚连科技有限责任公司 | Purification method for polysilicon tail gas and purifier employing the method |
| CN102344119A (en) * | 2011-06-23 | 2012-02-08 | 莱芜钢铁集团电子有限公司 | Method for automatically switching a plurality of towers in pressure swing adsorption (PSA) hydrogen production system |
| CN103523749B (en) * | 2013-10-16 | 2015-10-28 | 西南化工研究设计院有限公司 | A kind of technique utilizing carbon black tail gas hydrogen manufacturing |
| CN106517092A (en) * | 2015-09-09 | 2017-03-22 | 苏州恒大净化设备有限公司 | Ammonia decomposition hydrogen-production purification equipment |
| CN105268282A (en) * | 2015-09-18 | 2016-01-27 | 北京环宇京辉京城气体科技有限公司 | Method for preparing ultra pure hydrogen by low-temperature pressure-swing adsorption |
| CN105664667A (en) * | 2016-03-11 | 2016-06-15 | 西安华江环保科技股份有限公司 | Hydrogen recycling device and technology for LNG cryogenic separation hydrogen-rich exhaust |
| CN107434242A (en) * | 2017-07-13 | 2017-12-05 | 大连中鼎化学有限公司 | Purifying hydrogen of hydrogen prepares high-purity and superelevation pure hydrogen process from coal gas |
| CN111375288B (en) * | 2018-12-27 | 2022-04-05 | 中国石油化工股份有限公司 | Memory, optimization method, device and equipment of pressure swing adsorption device |
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1992
- 1992-09-24 CN CN 92110918 patent/CN1025110C/en not_active Expired - Fee Related
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