CN100354025C - Reciprocating variable-pressure adsorption process - Google Patents
Reciprocating variable-pressure adsorption process Download PDFInfo
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- CN100354025C CN100354025C CNB001130358A CN00113035A CN100354025C CN 100354025 C CN100354025 C CN 100354025C CN B001130358 A CNB001130358 A CN B001130358A CN 00113035 A CN00113035 A CN 00113035A CN 100354025 C CN100354025 C CN 100354025C
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Abstract
The present invention relates to improved variable-pressure adsorption technology in the field of gas separation. An adsorption dosage flowed across by raw material gas is unchanged through the serial adsorption operation of a plurality of adsorption towers, the total amount of adsorbents is decreased, equipment sizes are correspondingly decreased, and operating energy consumption is also reduced. Adsorption steps are divided into more than two phases, and the direction of adsorption outflow gas is changed backwards and forwards according to a certain rule. In addition, distribution positions of components easily adsorbed can be more reasonable in the adsorption towers when the decompression outflow gas of the adsorption towers flows back into the adsorption towers.
Description
Usually said transformation absorption (comprising the absorption of flushing transformation, Vacuum Pressure Swing Adsorption, the absorption of alternating temperature transformation or the regeneration of multiple compound mode) technology, the flow direction of unstripped gas in adsorption tower that absorption phase contains the adsorbate component all is a fixing direction.
For the pressure swing adsorption technique of non-absorbed component as product, contain less or micro-easy absorbed component in the equal pressure drop stage adsorption tower eluting gas for making, have to before adsorbents adsorb is saturated, just end absorption phase, like this, it is maximum that the each work adsorption capacity of adsorbent does not reach, thereby limited the utilization ratio of adsorbent.
For the pressure swing adsorption technique of easy absorbed component, must make easy absorbed component fully penetrate adsorption tower, to reach the purpose that reduces the used product gas of displacement adsorption tower as product.Yet, in order to guarantee separating effect, or guarantee the available gas rate of recovery, must make in the absorption effluent gases easily the absorbed component amount of penetrating few or do not penetrate again, thus, also have to adsorbent work adsorption capacity is reduced.Generally speaking, adopt equal pressure drop effluent gases from the method that other adsorption tower raw material gas inlet end all is pressed into, can improve adsorbent work adsorption capacity like this, still, the adsorbent utilization rate is still not high enough.
Trace commonly used easily absorbed component adopts adsorption method to remove, and can adopt adsorption tower tandem working (referring to accompanying drawing 1) usually, and this working method can make that easily absorbed component content is lower in the final effluent gases of adsorption tower.But with regard to single system multitower pressure swing adsorption technique, how to adopt adsorption tower, and effectively reclaim the step-down effluent gases, in the past, do not have other people to propose reasonable method in the absorption phase tandem working.
" (the chemical fertilizer industry collected translation " introduction of 92 (2) 6-12 pages or leaves, (the AIRP AIR PRODUCT﹠amp of U.S.'s air products and chemical company; CHEM INC) invented a kind of pressure swing adsorption technique, this technology is with the pressure-swing absorption apparatus tandem working of the different purposes of two covers, and the adsorbent equipment of back adopts the absorption effluent gases of front as unstripped gas, obtains the product gas of two kinds of different components thus stage by stage; Simultaneously, the waste gas of employing back one covering device washes last covering device and all presses, and effectively reclaims valuable gases.This technology does not adopt adsorption tower series connection absorption on the same group, and the adsorption tower of front and back device adsorbate component separately is inequality, and the purpose that gas separates is also inequality.And during each adsorption tower absorption, adsorbate flows to and fixes.
The open CN1071851A of Chinese patent has announced a kind of at same pressure-swing absorption apparatus, obtains the method for two kinds of gas with various component product gas simultaneously.Two kinds of gas products are from the different operating stage of same adsorption tower, and the flow direction of unstripped gas in adsorption tower fixed.It is by using on the same group adsorption tower series connection absorption, absorption phase unstripped gas and the effluent gases direction that flows to change this method back and forth and reach and improve the adsorbent service efficiency, and then improves separating effect, the final purpose that reduces investment.
The pressure-swing absorption apparatus of purification for gas, separation has the adsorption tower more than three to work together usually, wherein at least always has an adsorption tower to be in adsorption step, and other adsorption tower then is in other steps.Generally, each adsorption tower adsorbs successively, step-down, desorb, step such as replace, boost, finally boost, all step cycle operations; Also can adjust in the order of steps arrangement, step also can increase and decrease.
The present invention designs the purpose of adsorption step like this, is in order to allow adsorbent work adsorption capacity reach maximum.Adopt the present invention, be in the adsorption tower in first stage of adsorption step that adsorbent can reach or saturated near absorption, the utilization rate that helps adsorbent improves.Simultaneously, the easy adsorbed gas component that is in the final effluent gases of adsorption tower of adsorption step the last stage still can concentration reach designing requirement.
Reciprocating variable-pressure adsorption process of the present invention has following tangible advantage and significant effect.
For typical process, four towers, the two equal transformations that obtain product from non-absorption are mutually adsorbed process for making hydrogen, and flow of feed gas is when adsorption tower, and easily the absorption forward position of absorbed component is to advance to Way out gradually.When the absorption forward position is advanced to approximately 1/2 the time, just adsorbent fully adsorbed 1/2 o'clock, and absorption finishes.In ensuing adsorption tower dead space gas step-down removal process, easily the adsorbent in the absorbed component second half section adsorption tower seldom only is used as the easy absorbed component of accepting desorb in the step-down process, to prevent that easy absorbed component from entering equal baric flow and giving vent to anger.If divide work two isopyknic little adsorption towers this adsorption tower, according to the present invention two adsorption tower series connection are adsorbed, only make the saturated little adsorption tower step-down of absorption, step-down effluent gases yield reduces half (only doing half time all presses), and gas reclaiming rate just can be consistent with big tower with the product separation requirement.But so, only just can be equivalent to 4 original big adsorption towers with 5 little adsorption towers, adsorbent saves 3/8, the corresponding simultaneously purge gas of saving, or the like.
Pressure-swing absorption apparatus for obtain product mutually from absorption adopts the present invention, is in the adsorption tower of adsorption step phase I, and the absorption forward position can fully be broken through, and can reduce the product tolerance that is used to replace, wash adsorption tower.The corresponding minimizing because the minimizing of displacement, flushing tolerance, displacement, flushing flow are given vent to anger, circulating flow rate also just reduces, and has reduced circulation compression energy consumption.And the easy adsorbed gas concentration of component that is in the final effluent gases of adsorption tower of adsorption step phase I is but very low, helps improving the available gas rate of recovery like this, thus, can use the small device size, and then reduces plant investment.
For typical process, obtain three towers, the one equal conversion gas transformation adsorbing and removing of product mutually and make carbon dioxide process from absorption.Flow of feed gas is when adsorption tower, and easily the absorption forward position of absorbed component carbon dioxide is to advance to Way out gradually.When the absorption forward position is advanced to approximately 1/2 the time, just adsorbent fully adsorbed 1/2 o'clock, and absorption finishes.In ensuing adsorption tower dead space gas step-down removal process, easily the adsorbent in the absorbed component second half section adsorption tower seldom only is used as the easy absorbed component of accepting desorb in the step-down process, to prevent that easy absorbed component from entering equal baric flow and giving vent to anger.If divide work two isopyknic little adsorption towers this adsorption tower, according to the present invention two adsorption tower series connection are adsorbed, only make the saturated little adsorption tower step-down of absorption, step-down effluent gases yield reduces half (only doing half time all presses), and gas reclaiming rate just can be consistent with big tower with the product separation requirement.But so, only just can be equivalent to 3 original big adsorption towers with 4 little adsorption towers, adsorbent saves 1/3, the corresponding simultaneously carbon dioxide replacement gas of saving, or the like.
The present invention divides two or more stages of work to carry out adsorption process back and forth adsorption step.
One, adsorption step divides the adsorption process of doing two stages: the phase I, unstripped gas forward flows into adsorption tower from adsorption tower bottom 1, absorption effluent gases I 1 outflow from the top.Simultaneously, absorption effluent gases I is from the top 1 reverse inflow of the adsorption tower that is in second stage in addition.Second stage, the absorption effluent gases I adsorption tower that 1 inflow is in second stage from the adsorption tower top adsorbs final effluent gases and flows out adsorption towers from raw material gas inlet end 2.In whole pressure swing adsorption system, for each adsorption tower, in whole adsorption step, the flow direction of adsorbate in tower changes back and forth.Like this, because flow of feed gas is through two adsorption towers, just can make the adsorbent that is in phase I absorption when absorption finishes, adsorb saturated or near saturated, easy absorbed component in the abundant unstripped gas of adsorbent utilization, absorbed component content conforms with designing requirement and be in the final effluent gases of absorption of the second absorption phase adsorption tower easily.Design like this, total quantity of sorbent is little more a lot of than original typical process with the ratio of unstripped gas tolerance, has saved adsorbent and corresponding apparatus.
Two, the adsorption step branch is made the adsorption process of three phases: the phase I, unstripped gas forward enters adsorption tower from adsorption tower bottom 1, absorption effluent gases I 1 flows out from the top, and simultaneously, absorption effluent gases I is from the top 1 reverse inflow of the adsorption tower that is in second stage in addition; During second stage, the adsorption tower absorption effluent gases I that is in the phase I 1 flows into the adsorption tower that is in second stage from the adsorption tower top, and the absorption effluent gases II that is in second stage then flows into the adsorption tower that is in the phase III from the adsorption tower bottom; During the phase III, the absorption effluent gases II that is in second stage flows into the adsorption tower that is in the phase III from the adsorption tower bottom, thus, adsorb final effluent gases and flow out from the adsorption tower top.In whole pressure swing adsorption system, for each adsorption tower, in whole adsorption step, the flow direction of adsorbate in tower changes back and forth.Like this, because flow of feed gas is through three adsorption towers, the adsorbent that is in phase I absorption adsorb saturated or approaching saturated when absorption finishes, the adsorbent utilization is abundant, and absorbed component content reaches designing requirement and be in the final effluent gases of absorption of the 3rd absorption phase adsorption tower easily.Design like this, total quantity of sorbent is but little a lot of than original typical process with the ratio of unstripped gas tolerance, has saved adsorbent and corresponding apparatus.
Technology according to the present invention proposes also can be divided into adsorption step three above stages, analogizes according to said method.
Direction changes back and forth because the unstripped gas of different absorption phase flows, and therefore, the present invention claims this working method to be absorption back and forth.
Design gas flow like this can also make when all pressing step, during all baric flow is given vent to anger easily absorbed component can flow into the position of expectation, and make in the adsorption tower easily that absorbed component distributes rationally.
Design N slack tank that is used to store adsorption tower step-down process effluent gases on stream, can make the step-down effluent gases be able to reclaim like this according to designing requirement.Slack tank gas can be used for adsorption tower and boost and wash, replace.
For pressure swing adsorption technique, method regeneration such as adsorbent can adopt flushing, vacuumizes, intensification.Flushing gas can use step-down effluent gases, absorption effluent gases or other gas.The three kinds of methods of washing, vacuumize, heat up are that easily the absorbed component desorb is more abundant in the adsorbent in order to make, and adsorbent adsorption capacity again is bigger when adopting the depressurization desorption method than simple.
Usually, pressure swing adsorption technique adopts unstripped gas or adsorbs final effluent gases adsorption tower is done final pressurising, and the present invention advises adopting the final effluent gases of absorption as final pressurized gas.
Three, the embodiment of the invention
Embodiment 1: the conversion qi exhaustion removes and produces all compression technologies of carbon dioxide four towers 5 (slack tank), pressure 0.6MPa, 40 ℃ of temperature.With the A adsorption tower is that example is illustrated, and other adsorption tower operation methods are identical, just staggers mutually on the time.(as accompanying drawing 2, subordinate list 1)
(1) 1A step (second absorption phase): unstripped gas flows into the D tower by the D1 valve, flow into the A tower through D2, A2 valve from the D tower, flow out the A tower through the A5 valve, carbon dioxide content is less than 0.1% in the A tower effluent gases, when carbon dioxide content in the D tower effluent gases when a certain concentration, connect next step.
(2) 2A step (first absorption phase): unstripped gas flows into the A tower by the A1 valve, flows into the B tower through A2, B2 valve from the A tower, flows out the B tower through the B5 valve, and carbon dioxide content is less than 0.1% in the B tower effluent gases.When A tower effluent gases carbon dioxide content reaches a certain concentration, connect next step.Adsorption tower A stops adsorption operations.
(3) 1～5L steps: adsorption tower A step-down, the step-down effluent gases flows into 5 slack tank E～I stage by stage by A4, E4～I4 valve, and adsorption tower A pressure is reduced to 0.08Mpa, connects next step.
(4) L step: by A4, J4 valve and step-down gas circulation recovery line, reclaim lowpressure stream and give vent to anger (this gas is used as unstripped gas after compression), adsorption tower A pressure further reduces, and connects next step.
(5) 6L step: adsorption tower A is communicated with by A4, D4 with adsorption tower D, all presses, pressure reaches-0.01Mpa, connects next step.
(6) PP step: by A6 valve displacement adsorption tower A, effluent gases flows into the D tower by A4, D4, when gas concentration lwevel reaches requirement among the adsorption tower A, connects next step with the product carbon dioxide.
(7) V step: obtain the product carbon dioxide by the A3 valve adsorption tower A that finds time, adsorption column pressure drops to-0.093Mpa, connects next step.
(8) 6R step: adsorption tower A is communicated with by A4, B4 with adsorption tower B, all presses, adsorption column pressure is increased to-0.01Mpa, connects next step.
(9) R step: by B6 valve displacement adsorption tower B, effluent gases flows into the A tower by B4, A4 with the product carbon dioxide, and adsorption tower A pressure continues to be elevated to predicted value; If it is too many that the B tower flows out tolerance, the redundance effluent gases can enter recirculation system by the J4 valve, connects next step.
(10) 5～1R steps: to adsorption tower A pressurising, connect next step successively with slack tank I～E gas.
(11) step of finally boosting: by the A5 valve adsorption tower A is done final pressurising with final effluent gases.Circulation (1)～(11).
Embodiment 2: water-gas hydrogen eight towers 7 (slack tank) are compression technology all, pressure 1.2MPa, and 40 ℃ of temperature are that example is illustrated with the A tower.(as accompanying drawing 3, subordinate list 2)
(1) 1A1 step (the 4th absorption phase): unstripped gas flows into F, G tower by F1, G1 valve, flows out F, G tower through F2, G2 valve; Flow into A, H tower by A2, H2 valve, flow out A, H tower through A5, H5 valve, density of hydrogen is higher than 99.9% in A, the H tower effluent gases, when the H tower flows out hydrogen impurity concentration near 0.1% the time, connects next step.
(2) 1A2 step (the 3rd absorption phase): unstripped gas flows into G, H tower by G1, H1 valve, flows out G, H tower through G2, H2 valve; Flow into A, B tower by A2, B2 valve, flow out A, B tower through A5, B5 valve, density of hydrogen is higher than 99.% in A, the B tower effluent gases, when the A tower flows out hydrogen impurity concentration near 1% the time, connects next step.
(3) 2A1 step (second absorption phase): unstripped gas flows into A, H tower by A1, H1 valve, flows out A, H tower through A2, H2 valve, flows into B, C tower by B2, C2 valve, flows out B, C tower through B5, C5 valve, and density of hydrogen is higher than 90% in B, the C tower effluent gases.When G tower effluent gases impurity concentration near 10% the time, connect next step.
(4) 2A2 step (first absorption phase): unstripped gas flows into A, B tower by A1, B1 valve, flows out A, B tower through A2, B2 valve; Flow into C, D tower by C2, D2 valve, flow out C, D tower through C5, D5 valve, density of hydrogen is higher than 60% in C, the D tower effluent gases, when the C tower flows out hydrogen impurity concentration near 40% the time, connects next step.Adsorption tower A stops adsorption operations.
(5) 1～7L steps: adsorption tower A step-down, the step-down effluent gases flows into 5 slack tank I～0 stage by stage by A4, I4～04 valve, and adsorption tower A pressure is reduced to 0.15Mpa, connects next step.
(6) L step: by A7, P7 valve and step-down gas circulation recovery line, reclaim lowpressure stream and give vent to anger (this gas can be done him and use), adsorption tower A pressure further reduces, and connects next step.
(7) flushing (displacement) step: wash adsorption tower H by the H6 valve with product hydrogen, effluent gases flows into adsorption tower A as the purge gas in early stage by A7, H7, flows out adsorption tower A by A3, after the end, use product hydrogen instead and directly wash by the A6 valve, effluent gases is as adsorption tower B purge gas in early stage.When impurity concentration reaches requirement among the adsorption tower A, connect next step.
(8) 7～1R steps: to adsorption tower A pressurising, connect next step with slack tank 0～I gas.
(9) step of finally boosting: by the A5 valve adsorption tower A is done final pressurising with product hydrogen.Circulation (1)～(9).
Subordinate list 1 (embodiment 1)
| 1A | 2A | 1-5L | L | 6L | PP | V | 6R | R | 5-1R | FR | |||||||||||||
| V | 6R | R | 5-1R | ?FR | 1A | 2A | 1-5L | L | 6L | PP | V | ||||||||||||
| 1-5L | L | 6L | PP | V | 6R | R | 5-1R | FR | 1A | 2A | |||||||||||||
| 2A | 1-5L | L | 6L | PP | V | 6R | R | 5-1R | FR | 1A | |||||||||||||
Subordinate list 2 (embodiment 2)
| 1A1 | 2A1 | 1A2 | 2A2 | 1-7L | L | PP1 | PP2 | 7-1R | FR | |||||||||||||||
| FR | 1A1 | 2A1 | 2A2 | 2A2 | 1-7L | L | PP1 | PP2 | 7-1R | |||||||||||||||
| PP2 | 7-1R | FR | 1A1 | 2A1 | 1A2 | 2A2 | 1-7L | L | PP1 | PP2 | ||||||||||||||
| PP1 | PP2 | 7-1R | FR | 1A1 | 2A1 | 1A2 | 2A2 | 1-7L | L | PP1 | ||||||||||||||
| 1-7L | L | PP1 | PP2 | 7-1R | FR | 1A1 | 2A1 | 1A2 | 2A2 | |||||||||||||||
| 2A2 | 1-7L | L | PP1 | PP2 | 7-1R | FR | 1A1 | 2A1 | 1A2 | |||||||||||||||
| 1A2 | 2A2 | 1-7L | L | PP1 | PP2 | 7-1R | FR | 1A1 | 2A1 | |||||||||||||||
| 2A1 | 1A2 | 2A2 | 1-7L | L | PP1 | PP2 | 7-1R | FR | 1A1 | |||||||||||||||
Claims (1)
1, a kind of improved pressure swing adsorption technique flow process, it is characterized in that for each adsorption tower, adsorption step divides two or more stages of work: in the phase I, unstripped gas flows into from adsorption tower entrance point 1, wherein most of easily absorbed component gas is adsorbed agent absorption, and the difficult absorbed component that is not adsorbed and a part of easily absorbed component gas are called absorption effluent gases I, flow out from the port of export 1, adsorb effluent gases I simultaneously and flow into from the port of export 1 that other are in the adsorption tower of second absorption phase; In second stage, absorption effluent gases I flows into from the adsorption tower port of export 1, and wherein most of easily absorbed component gas is adsorbed agent absorption, and simultaneously, absorption effluent gases II flows into from the entrance point 2 that other are in the adsorption tower of the 3rd absorption phase; Or optional phase III, absorption effluent gases II flows into from adsorption tower entrance point 2, wherein most of easily absorbed component gas is adsorbed agent absorption, difficult absorbed component that is not adsorbed and the easy absorbed component gas of a part, be called absorption effluent gases III, flow out from the adsorption tower port of export 3, adsorb effluent gases III simultaneously and flow into from the port of export 3 that other are in the adsorption tower of the 4th absorption phase; Several 2 the time when absorption phase, absorption effluent gases II be final absorption effluent gases, and several 3 the time when absorption phase, absorption effluent gases III finally adsorbs effluent gases; Several 4 the time when absorption phase, absorption effluent gases IV finally adsorbs effluent gases; According to above-mentioned method, for each adsorption tower, the carrying out of each absorption phase order is inverted, promptly carries out the absorption phase of back earlier, carries out the absorption phase of front again.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001130358A CN100354025C (en) | 2000-06-19 | 2000-06-19 | Reciprocating variable-pressure adsorption process |
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| CNB001130358A CN100354025C (en) | 2000-06-19 | 2000-06-19 | Reciprocating variable-pressure adsorption process |
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| CN1328863A CN1328863A (en) | 2002-01-02 |
| CN100354025C true CN100354025C (en) | 2007-12-12 |
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| CN105126538A (en) * | 2015-09-10 | 2015-12-09 | 北京氢璞创能科技有限公司 | Efficient multi-tank intake type pressure swing adsorption purifier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122257A (en) * | 1994-09-01 | 1996-05-15 | 普拉塞尔技术有限公司 | Simulataneous step pressure swing adsorption process |
| WO1998018538A2 (en) * | 1996-10-31 | 1998-05-07 | Ultrafilter Gmbh | Adsorption drying unit, and process and device for checking the operating state of same |
| CN1040292C (en) * | 1992-12-03 | 1998-10-21 | 黄家鹄 | Gas separation method by pressure swing adsorption for simultaneously preparing two gas products with high-purity and high-yield |
| WO1999001202A1 (en) * | 1997-06-30 | 1999-01-14 | Questor Industries Inc. | High frequency rotary pressure swing adsorption apparatus |
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2000
- 2000-06-19 CN CNB001130358A patent/CN100354025C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040292C (en) * | 1992-12-03 | 1998-10-21 | 黄家鹄 | Gas separation method by pressure swing adsorption for simultaneously preparing two gas products with high-purity and high-yield |
| CN1122257A (en) * | 1994-09-01 | 1996-05-15 | 普拉塞尔技术有限公司 | Simulataneous step pressure swing adsorption process |
| WO1998018538A2 (en) * | 1996-10-31 | 1998-05-07 | Ultrafilter Gmbh | Adsorption drying unit, and process and device for checking the operating state of same |
| WO1999001202A1 (en) * | 1997-06-30 | 1999-01-14 | Questor Industries Inc. | High frequency rotary pressure swing adsorption apparatus |
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