CN100423811C - Pressure-variation absorption method for separating and recovering adsorbed phase products from mixed gas - Google Patents

Pressure-variation absorption method for separating and recovering adsorbed phase products from mixed gas Download PDF

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CN100423811C
CN100423811C CNB2005101182417A CN200510118241A CN100423811C CN 100423811 C CN100423811 C CN 100423811C CN B2005101182417 A CNB2005101182417 A CN B2005101182417A CN 200510118241 A CN200510118241 A CN 200510118241A CN 100423811 C CN100423811 C CN 100423811C
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adsorption
adsorption tower
gas
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CN1861245A (en
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杨云
赵洪法
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Southwest Research and Desigin Institute of Chemical Industry
Haohua Chemical Science and Technology Corp Ltd
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Sichuan Tianyi Science and Technology Co Ltd
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Abstract

The present invention discloses a pressure swing adsorption method which can be used for separating and recovering adsorbed phase products from mixed gas. The pressure swing adsorption system of the method comprises a first pressure swing adsorption section and a second pressure swing adsorption section, which are respectively composed of at least two adsorption towers filled with adsorption agents, in each adsorption tower, the steps of adsorption, replacement, reverse release, evacuation and final pressure boosting are orderly and cyclically carried out, and replacement exhaust gas of the first pressure swing adsorption section is used as raw gas which enters the second pressure swing adsorption section. The pressure swing adsorption method of the present invention is suitable for the pressure swing adsorption system which contains a replacement step and obtains products from adsorbed phases, and is especially suitable for separating and recovering carbon dioxide, carbon monoxide, or mixed gas whose main component comprises C2 and hydrocarbons above C2. The method can increase a recovery rate of adsorbed phase products; when the raw gas contents are identical, the recovery rate of the adsorbed phase products can be increased from 5% to 50%.

Description

From gaseous mixture, separate the pressure swing absorption process that reclaims absorption phase product
Technical field
The present invention relates to a kind of transformation absorption (PSA) method of from gaseous mixture, separating recovery absorption phase product, particularly relate to a kind of the recovery and adsorb the pressure swing absorption process that includes displacement step in the phase product process in separation.
Background technology
Pressure swing absorption process is to utilize the porosu solid adsorbent under certain pressure, and different component in the mist is had the characteristic of selective absorption, realizes the separation of mist.The absorption or the non-adsorbed state that are in adsorbent bed of the product of Fen Liing as required can be divided into absorption phase product and non-absorption product mutually.Existing separation is reclaimed carbon dioxide in the synthetic-ammonia transformation gas, is separated water-gas, the semiwater gas after removing carbon dioxide and reclaim carbon monoxide and separate the hydrocarbon component that reclaims in the mist, reclaims with C as separating from the oil plant catalytic cracked dry gas 2And C 2Above hydrocarbon component is in the pressure swing adsorption of main absorption phase products such as gaseous mixture, in order to improve the content of absorption phase product, has adopted the technology of returning part product gas displacement adsorbent bed.Inevitably can from displacement waste gas, give off some product gas in this replacement process, when especially requiring purity of product gas higher, product gas component by the displacement toxic emission is more, has caused product gas component recovery to reduce, and has influenced the economic benefit of pressure-swing absorption apparatus.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the technical problem to be solved in the present invention provides a kind of pressure swing absorption process that separates absorption phase product from gaseous mixture, and this method can improve the rate of recovery of product in including the pressure-swing absorption process of displacement step.
For solving the problems of the technologies described above, pressure swing adsorption system of the present invention comprises 2 sections of 1 section of transformation absorption and transformation absorption, they are made of at least two adsorption towers that are filled with adsorbent respectively, each adsorption tower circulate at least successively experience absorption, displacement, contraryly put, find time, the step of finally boosting, and the displacement waste gas of 1 section of transformation absorption enters 2 sections of transformation absorption as unstripped gas.
The present invention adopts two sections interconnective pressure-swing absorption apparatus, and each adsorption tower circulates at least successively and experiences absorption, displacement, contrary five steps of putting, find time, finally boost.According to parameters such as the pressure of concrete technology, purity, also can comprise the equal voltage drop step of one or many at least in absorption and contrary strideing between rapid, and after evacuation step, be right after the equal voltage rise of one or many at least; All voltage drop step can be right after after the adsorption step, also can carry out after displacement step.In pressure-swing absorption process, the 1st stage pressure swing adsorption apparatus is handled the absorption phase product in the unstripped gas that enters pressure swing adsorption system.Obtain the product gas of absorption phase component by contrary venting and exhaust, directly returning part product gas or returning part are through the product gas of pressurization, to finishing the adsorption tower of adsorption step, enter from the displacement import of adsorption tower unstripped gas arrival end and to replace, or the adsorption tower through equal pressure drop behind adsorption step replaced, in the displacement adsorption tower space and a small amount of non-absorption of adsorbing on the adsorbent impurity of product mutually, to improve the content that adsorbs the phase product component in the adsorption tower.The gas of emitting from the adsorption tower port of export in the displacement step of transformation absorption is called displacement waste gas.The displacement waste gas that transformation absorption is 1 section enters 2 sections of transformation absorption as unstripped gas, by adsorbing the further product gas of easily absorption that reclaims once more to reach the purpose of the raising product gas content and the rate of recovery.With the existing pressure swing adsorption method that obtains product mutually from absorption that comprises displacement step relatively, under identical condition, when promptly unstripped gas content was identical, the rate of recovery of product can improve 5%~50%.
Be further to improve the rate of recovery of product, enter transformation absorption after the displacement waste gas that also transformation can be adsorbed 1 section of 2 sections displacement waste gas and transformation absorption mixes and adsorb again for 2 sections.
The adsorbent of selecting for use in the adsorption step of the present invention is at least a in active carbon, activated alumina, silica gel and the molecular sieve.The selection of adsorbent and be used in combination can be according to the composition of processed mist or content and decide.
The adsorption step gauge pressure of 1 section of transformation absorption is greater than 0.05MPa in the above-mentioned pressure swing absorption process, the adsorption step pressure that transformation absorption is 2 sections is the displacement exhaust gas pressure of 1 section of transformation absorption, the displacement step gauge pressure of two sections transformations absorption greater than 0MPa, contrary stride rapid gauge pressure greater than 0MPa, evacuation step gauge pressure be-0.03~-0.09MPa, the unstripped gas temperature is 5-60 ℃.
Pressure swing absorption process of the present invention is applicable to what include displacement step and obtains the pressure swing adsorption system of product mutually from absorption, for example from synthetic-ammonia transformation gas, separate to reclaim to separate carbon dioxide, the water-gas after removing carbon dioxide, the semiwater gas and reclaim carbon monoxide and separate the hydrocarbon component that reclaims in the mist, as from the oil plant catalytic cracked dry gas, reclaiming with C 2And C 2Above hydrocarbon component is main gaseous mixture.
In the above-mentioned pressure swing adsorption technique of the present invention, in the once circulation of each adsorption tower, all to experience absorption, displacement, contraryly put, find time, the step of finally boosting, and require, separate process conditions such as reclaiming the requirement of absorption phase product purity according to adsorptive pressure, absorption exhaust gas concentration, can to equal pressure drop, all the voltage rise step reasonably accept or reject, arrangement and number of times setting.Each adsorption tower all will experience identical step, and each tower just staggers in time mutually, so that device is continuous, stable operation.
Can be as follows during the above-mentioned transformation adsorbing separation of the present invention reclaims for each the step detailed process that adopts:
Absorption A
The mist that contains easy absorption and be difficult for absorbed component enters adsorbent bed from the adsorption tower raw material gas inlet, and the easy absorbed component in the mist is adsorbed the adsorbents adsorb of loading in the tower, is difficult for adsorbed components and discharges from the adsorption tower outlet and be called as absorption waste gas.This step realizes easy absorbed component and is difficult for separating of absorbed component.
Equal pressure drop ED
All voltage drop step is adsorption step to be finished or adsorption tower that displacement step is finished, be communicated with adsorption tower that enters equal voltage rise step or equalizer tank by pipeline and sequencing valve, reclaim useful constituent and pressure in the equal voltage drop step adsorption tower, improve the content of absorption phase component in the adsorption tower.All voltage drop step can be arranged to 1 time according to adsorptive pressure, or repeatedly, all falls E1D, two as one and all fall E2D.Each time all pressure drop can be carried out or separately carry out continuously.
Displacement RP
Returning part is contrary to be put and the absorption of finding time to obtain product gas mutually, to finishing the adsorption tower of adsorption step, enter adsorbent bed from the displacement import of adsorption tower unstripped gas arrival end, utilize absorption phase component content high product gas to the impurity in the adsorbent bed space, replace with the small amount of impurities of adsorbing in the adsorbent, improve the content of absorption phase component in the adsorption tower.In displacement step of the present invention, the displacement waste gas from adsorption tower displacement waste gas outlet is discharged enters the unstripped gas that 2 sections of transformation absorption are used as 2 sections of transformation absorption.
The contrary D of putting
Displacement step is finished or displacement step has been carried out the adsorption tower of equal voltage drop step after finishing again, open the contrary valve of putting of adsorption tower unstripped gas arrival end, discharge the gas in the adsorption tower, reduce the pressure of adsorption tower, make the absorption phase component that is adsorbed in the adsorption tower partly separate the sucking-off adsorbent, obtain absorption phase product.
V finds time
Adsorption tower after utilizing vavuum pump to contrary putting is found time, and further reduces the pressure of adsorption tower, makes the absorption phase product that is adsorbed in the adsorbent further separate the sucking-off adsorbent, obtains absorption phase product.
Equal voltage rise ER
Adsorption tower after evacuation step finished, be connected with adsorption tower that is in equal voltage drop step or equalizer tank with sequencing valve by pipeline, make higher equal voltage drop step adsorption tower of pressure or the gas in the equalizer tank enter the adsorption tower of equal voltage rise, with the pressure of the equal voltage rise adsorption tower that raises, and the absorption phase product in the equal pressure drop gas of recovery section.All the voltage rise step can be arranged to 1 time according to adsorptive pressure, or repeatedly, all rises E2R, as two and all rise E1R.All the number of times of voltage rise is corresponding with the number of times of all pressure drops.
FR finally boosts
Utilize absorption waste gas that adsorption tower is boosted, make it to reach adsorptive pressure, prepare to enter next adsorption step.
Below the present invention is further detailed explanation for the embodiment by the specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 is extracted the carbon dioxide process schematic flow sheet;
Fig. 2 is that the embodiment of the invention 2 is extracted the carbon monoxide process flow diagram;
Fig. 3 is that the embodiment of the invention 3 is extracted with C 2And C 2Above hydrocarbon component is main gaseous mixture process flow diagram.
The specific embodiment
Embodiment 1
Present embodiment is to separate the pressure swing adsorption method that reclaims carbon dioxide, raw gas flow 15000Nm from synthetic-ammonia transformation gas 3/ h, adsorptive pressure 0.75MPa, 10 ℃ of temperature, processed unstripped gas becomes to be grouped into as shown in table 1:
Table 1 unstripped gas is formed
As shown in Figure 1, the present embodiment pressure swing adsorption system is made of 1 section PSA-1 of transformation absorption and 2 sections PSA-2 of transformation absorption.The volume of each adsorption tower of PSA-1 is 29 cubic metres, and the volume of each adsorption tower of PSA-2 is 19 cubic metres.The adsorbent that loads in two sections each adsorption towers is respectively active carbon, silica gel, activated alumina from top to bottom, and the height ratio of its filling is 1: 5: 1.PSA-1 by 8 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 3 vavuum pumps, 1 displacement off-gas buffer tank, 1 product blending tank, 1 displacement gas surge tank, 2 displacement gas compressors, 2 product air compressors and corresponding pipeline and sequencing valve be formed by connecting, wherein the back is that PSA-1 and PSA-2 are shared.Each adsorption tower circulates each time all that experience absorption A, falls all that E1D, two all falls E2D, displacement RP, contraryly puts D among the PSA-1, the V that finds time, two all rises E2R, and all rise E1R, final nine steps of FR of boosting, and its program operation sequential, each step gauge pressure value see Table 2:
Table 2PSA-1 work schedule table
Figure C20051011824100062
During the pressure swing adsorption system operation, by the switch of computer by certain each sequencing valve of programme-control.Be example now with adsorption tower A among the PSA-1 shown in Figure 1, each processing step of narration PSA-1 operation:
Absorption A: open sequencing valve KV1A and KV2A, unstripped gas is that conversion gas enters adsorption tower A, and adsorbent is to CO in bed 2Adsorb, and H 2, O 2, N 2, CH 4Discharge from adsorption tower A top by sequencing valve KV2A as absorption waste gas Deng being difficult for absorbed component.After adsorption time arrived, shut off valve KV1A and KV2A stopped absorption, and another adsorption tower that this moment, unstripped gas entered after finally boosting adsorbs.
One all falls E1D: open sequencing valve KV5A and KV5E, the adsorption tower A that finishes after the absorption all presses with finishing two adsorption tower E after all rising, and after two adsorption column pressures were in a basic balance, shut off valve KV5A finished one of adsorption tower A and all falls.
Two all fall E2D: open sequencing valve KV7A and KV7F, the gas in the adsorption tower A enters adsorption tower F, and finishes the adsorption tower F that finds time and carries out isostasy, and after two adsorption column pressures were in a basic balance, shut off valve KV7A and KV7F finished two of adsorption tower A and all fall.
Displacement RP: open sequencing valve KV3A and KV4A, come self-converse put with the absorption of finding time to obtain mutually product gas enter adsorption tower A through product blending tank 5, displacement gas compressor bank 10, displacement gas surge tank 6, the adsorbent bed of finishing equal voltage drop step is replaced, to improve the content of absorption phase component.Impurity that is displaced and portion C O 2Discharge from adsorption tower A top by valve KV4A as displacement waste gas, enter displacement off-gas buffer tank 7, as the unstripped gas of PSA-2.After time swap arrived, shut off valve KV3A and KV4A stopped displacement.
The contrary D of putting: open sequencing valve KV8A and KV7, the adsorbent bed that displacement step is finished is discharged the absorption phase component, reduces adsorption tower A pressure.The contrary venting enters the contrary jar 1 of putting through valve KV8A, KV7, enters product blending tank 5 through manual modulation valve HV1, the contrary jar 2 of putting again.After adsorption tower A pressure is reduced to normal pressure, shut off valve KV8A, KV7, contrary putting finished.
V finds time: open sequencing valve KV6A, find time by the adsorbent bed after 8 pairs of contrary putting of vavuum pump group, the gas that vavuum pump group 8 is extracted out is mixed into product blending tank 5 mutually with contrary venting, a part is as the output after 11 pressurizations of product air compressor group of product gas, and another part is as displacement gas retrieval system after 10 pressurizations of displacement gas compressor bank.Find time further the to reduce pressure of adsorption tower A makes the abundant desorb of absorption phase product that is adsorbed in the adsorbent, obtains absorption phase product, finishes adsorbent reactivation.After finding time to finish, shut off valve KV6A.
Two all rise E2R: open sequencing valve KV7D and KV7A, gas enters adsorption tower A in the adsorption tower D, finishes an adsorption tower D who all falls and finishes the adsorption tower A that finds time and carry out isostasy, when two pressure towers equate substantially, shut off valve KV7D and KV7A finish two of adsorption tower A and all rise.
One all rises E1R: open valve KV5A and KV5E, and finish two and all rise adsorption tower A and all press with the adsorption tower E that finishes after the absorption, after two adsorption column pressures were in a basic balance, shut off valve KV5E finished one of adsorption tower A and all rises.
FR finally boosts: continue open valve KV5A, by manual modulation valve HV3, utilize absorption waste gas that the adsorption tower A that finishes equal voltage rise step is boosted, make it to reach adsorptive pressure, prepare to enter adsorption step.
So far, the institute of adsorption tower A in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other 7 adsorption towers is identical with adsorption tower A, just staggers mutually in time, carries out continuously with the assurance separation process.
Each adsorption column pressure is cyclically-varying with the variation of processing step, and according to the practical operation situation, adsorptive pressure can suitably be adjusted, then other step pressure is corresponding changes.
In the present embodiment PSA-2 by 4 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 1 vavuum pump and corresponding pipeline and sequencing valve be formed by connecting.Each adsorption tower circulate each time all experience absorption A, all pressure drop ED, displacement RP, contraryly put D, the V that finds time, all voltage rise ER, final seven steps of FR of boosting, the circulation step of each tower experience and gauge pressure value such as table 3 are listed:
Table 3PSA-2 work schedule table
Figure C20051011824100081
Be example now with adsorption tower I, each processing step of narration PSA-2 operation:
Absorption A: open sequencing valve KV1I and KV2I, enter adsorption tower I through valve KV1I, adsorbing separation CO in bed by displacement off-gas buffer tank 7 from the displacement waste gas of PSA-1 2, and H 2, O 2, N 2, CH 4Discharge from adsorption tower I top by valve KV2I as absorption waste gas Deng being difficult for absorbed component.When the forward position of adsorption zone was moved upwards up to the certain position of bed, after adsorption time arrived, shut off valve KV1I and KV2I stopped absorption, and another adsorption tower that this moment, unstripped gas entered after finally boosting adsorbs.
Equal pressure drop ED: open sequencing valve KV5I and KV5K, the adsorption tower I that finishes after the absorption all presses with the adsorption tower K that finishes after finding time, and after two adsorption column pressures were in a basic balance, shut off valve KV5I finished the equal pressure drop of adsorption tower I.
Displacement RP: open sequencing valve KV3I and KV4I, come self-converse put with the absorption of finding time to obtain mutually product gas enter adsorption tower I through product blending tank 5, displacement gas compressor bank 10, displacement gas surge tank 6, the adsorbent bed of finishing equal voltage drop step is replaced, to improve the content of absorption phase component.Impurity that is displaced and portion C O 2Discharge from adsorption tower I top by valve KV4I as displacement waste gas, after time swap arrived, shut off valve KV3I and KV4I stopped displacement.
The contrary D of putting: open sequencing valve KV6I and KV10, KV11, the adsorbent bed that displacement step is finished is discharged the absorption phase component, reduces adsorption tower I pressure.Contrary venting enters the contrary jar 1 of putting through valve KV6I, KV10, enters product blending tank 5 through manual modulation valve HV2, vacuum tank 4, KV11, vavuum pump 9 again.After adsorption tower I pressure is reduced to normal pressure, shut off valve KV10 and KV11, contrary putting finished.
V finds time: continue open valve KV6I, open sequencing valve KV12 simultaneously, find time by the adsorbent bed after 9 pairs of contrary putting of vavuum pump, the gas that vavuum pump 9 is extracted out mixes mutually with contrary venting, a part is as the output after 11 pressurizations of product air compressor group of product gas, and another part is as displacement gas retrieval system after 10 pressurizations of displacement gas compressor bank.Find time further the to reduce pressure of adsorption tower I makes the abundant desorb of absorption phase product that is adsorbed in the adsorbent, obtains absorption phase product, finishes adsorbent reactivation.After finding time to finish, shut off valve KV6I and KV10.
Equal voltage rise ER: open valve KV5I and KV5K, the adsorption tower K after finishing the adsorption tower I after finding time and finishing absorption all presses, and after two adsorption column pressures were in a basic balance, shut off valve KV5K finished the equal voltage rise of adsorption tower I.
FR finally boosts: continue open valve KV5I, by manual modulation valve HV4, utilize absorption waste gas that the adsorption tower I that finishes equal voltage rise step is boosted, make it to reach adsorptive pressure, prepare to enter adsorption step.
So far, the institute of adsorption tower I in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other 3 adsorption towers is identical with adsorption tower I, just staggers mutually in time, carries out continuously with the assurance separation process.
Each adsorption column pressure is cyclically-varying with the variation of processing step, and according to the practical operation situation, adsorptive pressure can suitably be adjusted, then other step pressure is corresponding changes.
Present embodiment separates the absorption phase product that reclaims and forms as shown in table 4:
Table 4 product gas is formed
Figure C20051011824100091
The rate of recovery is meant that being recovered the component absolute magnitude from the product that pressure-swing absorption apparatus obtains accounts for and be recovered component absolute magnitude percentage in the unstripped gas that enters pressure-swing absorption apparatus.When unstripped gas content is identical, only experience that PSA-1 carries out CO among this embodiment 2Separation reclaim its CO 2The rate of recovery be 58%, CO in present embodiment product gas 2The rate of recovery rise to 87%.
Embodiment 2
Present embodiment is to separate the pressure swing absorption process that reclaims carbon monoxide, raw gas flow 500Nm from water-gas 3/ h, adsorptive pressure 0.25MPa, 50 ℃ of temperature, unstripped gas is formed as shown in table 5:
Table 5 unstripped gas is formed
Figure C20051011824100092
The volume of each adsorption tower of PSA-1 is 5 cubic metres in the present embodiment, and the volume of each adsorption tower of PSA-2 is 1 cubic metre.The adsorbent that loads in two sections each adsorption towers is respectively molecular sieve, active carbon, activated alumina from top to bottom, and its loading height ratio is 4: 1: 1.As shown in Figure 2, PSA-1 by 4 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 3 vavuum pumps, 1 displacement off-gas buffer tank, 1 product blending tank, 1 displacement gas surge tank, 1 displacement gas compressor, 1 product air compressor and corresponding pipeline and sequencing valve be formed by connecting, wherein the back is that PSA-1 and PSA-2 are shared.Each tower circulate each time all experience absorption A, all pressure drop ED, displacement RP, contraryly put D, the V that finds time, all voltage rise ER, final seven steps of FR of boosting, its program operation sequential, each step gauge pressure value see Table 6:
Table 6PSA-1 work schedule table
In the present embodiment, unstripped gas is compared at the processing step of its PSA-1 adsorption tower A process with the unstripped gas of embodiment 1 at PSA-1 adsorption tower A, difference is, the equal pressure drop of present embodiment, all the voltage rise step each only for once, the sequencing valve of its unlatching is KV5A and KV5C.All all press with the adsorption tower C that finishes after finding time by the adsorption tower A that finishes after the absorption during pressure drop, all press with the adsorption tower C that finishes after the absorption by the adsorption tower A that finishes after finding time during voltage rise.All the other processing step contents of two embodiment are all identical, so no longer repeat to state it.
The institute of adsorption tower A in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other 3 adsorption towers is identical with adsorption tower A, just staggers mutually in time, carries out continuously with the assurance separation process.
Each adsorption column pressure is cyclically-varying with the variation of processing step, and according to the practical operation situation, adsorptive pressure can suitably be adjusted, then other step pressure is corresponding changes.
As shown in Figure 2, the PSA-2 of present embodiment by 3 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 1 vavuum pump and corresponding pipeline and sequencing valve be formed by connecting.Each cyclic process experience absorption A, displacement RP, contraryly put D, the V that finds time, final five steps of FR of boosting, its each tower operation sequential, gauge pressure value see Table 7.
Table 7PSA-2 work schedule table
Figure C20051011824100102
Displacement waste gas is compared in the step of adsorption tower I experience among the processing step of the displacement waste gas of present embodiment adsorption tower E experience in PSA-2 and the embodiment 1, has lacked equal pressure drop, equal voltage rise steps, and all the other step contents are all identical, so no longer repetition.
So far, the institute of adsorption tower E in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other 2 adsorption towers is identical with adsorption tower E, just staggers mutually in time.Present embodiment separates the absorption phase product that reclaims and forms as shown in table 8:
Table 8 product gas is formed
Figure C20051011824100111
When unstripped gas content is identical, compare with the method for separating and recovering that merely carries out CO by PSA-1 in the present embodiment, the rate of recovery of CO can rise to 76% from 65% in the present embodiment product gas.
Embodiment 3
Present embodiment is to reclaim with C from the oil plant catalytic cracked dry gas 2And C 2Above hydrocarbon component is the pressure swing adsorption method of master's gaseous mixture, dry gas flow 25000Nm 3/ h, adsorptive pressure 0.60MPa, 30 ℃ of temperature, its gas componant is formed as shown in table 9:
Table 9 dry gas becomes to be grouped into
Figure C20051011824100112
C in the table 4Expression contains the hydrocarbon gas of 4 carbon atoms, as normal butane, iso-butane, isobutene, n-butene, anti-butylene; C 5 +Expression contains the hydrocarbon gas of 5 and 5 above carbon atoms.
The volume of each adsorption tower of PSA-1 is 56 cubic metres in the present embodiment, and the volume of each adsorption tower of PSA-2 is 10 cubic metres.The adsorbent that loads in two sections each towers is respectively molecular sieve, silica gel, active carbon, activated alumina from top to bottom, and the loading height ratio is 1: 4: 2: 1.As shown in Figure 3, PSA-1 by 10 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 10 vavuum pumps, 1 displacement off-gas buffer tank, 1 product blending tank, 1 displacement gas surge tank, 3 displacement gas compressors, 3 product air compressors and corresponding pipeline and sequencing valve be formed by connecting, wherein the back is that PSA-1 and PSA-2 are shared.Every tower circulates each time all that experience absorption A, displacement RP, fall all that E1D, two all falls E2D, contraryly puts D, the V that finds time, two all rises E2R, and all rises E1R, final nine steps of FR of boosting, and its program operation sequential sees Table 10:
Table 10PSA-1 work schedule table
Figure C20051011824100113
Be subjected to the restriction of margin, the E in the table in the expression symbol of equal pressure drop and all voltage rises is omitted; The gauge pressure of the third line value is unlisted in the table, and this value is respectively: 0.60,0.55,0.30,0.05,0.02 ,-0.08,0.05,0.30,0.59, and units MPa.
Be example now with adsorption tower A among the PSA-1 shown in Figure 3, each processing step of narration PSA-1 operation:
Absorption A: open sequencing valve KV1A and KV2A, enter adsorption tower A from the catalytic cracked dry gas outside the battery limit (BL) as unstripped gas, adsorbent is to C in bed 2H 4, C 2H 6And C 2Above hydrocarbon components etc. easily absorbed component adsorb, and H 2, O 2, N 2, CH 4Discharge from adsorption tower A top by valve KV2A as absorption waste gas Deng being difficult for absorbed component.After adsorption time arrived, shut off valve KV1A and KV2A stopped absorption, and another adsorption tower that this moment, unstripped gas entered after finally boosting adsorbs.
Displacement RP: open sequencing valve KV3A and KV4A, come self-converse put with the absorption of finding time to obtain mutually product gas enter adsorption tower A through product blending tank 5, displacement gas compressor 10, displacement gas surge tank 6, the adsorbent bed of finishing adsorption step is replaced, to improve the content of absorption phase component.Impurity that is displaced and portion C 2H 4, C 2H 6And C 2Above hydrocarbon component is discharged from adsorption tower A top by valve KV4A as displacement waste gas, enters displacement off-gas buffer tank 7, as the unstripped gas of PSA-2.After time swap arrived, shut off valve KV3A and KV4A stopped displacement.
One all falls E1D: open sequencing valve KV5A and KV5G, the adsorption tower A that finishes after the displacement all presses with finishing two adsorption tower G after all rising, and after two adsorption column pressures were in a basic balance, shut off valve KV5A finished one of adsorption tower A and all falls.
Two all fall E2D: open sequencing valve KV7A and KV7H, the gas in the adsorption tower A enters adsorption tower H, and finishes the adsorption tower H that finds time and carries out isostasy, and after two adsorption column pressures were in a basic balance, shut off valve KV7A and KV7H finished two of adsorption tower A and all fall.
The contrary D of putting: open sequencing valve KV8A, the adsorbent bed that equal voltage drop step is finished is discharged the absorption phase component, reduces adsorption tower A pressure.Contrary venting enters the contrary jar 1 of putting through valve KV8A, enters product blending tank 5 through manual modulation valve HV1, vacuum tank 2, sequencing valve KV9, KV10, vavuum pump group 8 again.After adsorption tower A pressure is reduced to normal pressure, shut off valve KV8A, contrary putting finished.
V finds time: open sequencing valve KV6A, while open valve KV9, find time by the adsorbent bed after 8 pairs of contrary putting of vavuum pump group, the gas that vavuum pump group 8 is extracted out mixes mutually with contrary venting, a part is as the output after 11 pressurizations of product air compressor group of product gas, and another part is as displacement gas retrieval system after 10 pressurizations of displacement gas compressor bank.Open valve KV10 when finding time to proceed to 150 seconds, the pressure of the adsorption tower A that finds time further to reduce makes the abundant desorb of absorption phase product that is adsorbed in the adsorbent, obtains absorption phase product, finishes adsorbent reactivation.Find time to finish shut off valve KV6A, KV9 and KV10.
Two all rise E2R: open valve KV7D and KV7A, gas enters adsorption tower A in the adsorption tower D, finishes an adsorption tower D who all falls and finishes the adsorption tower A that finds time and carry out isostasy, when two pressure towers equate substantially, close KV7D and KV7A valve, finish two of adsorption tower A and all rise.
One all rises E1R: open valve KV5A and KV5E, and finish two adsorption tower A after all rising and all press with the adsorption tower E that finishes after the absorption, after two adsorption column pressures were in a basic balance, shut off valve KV5E finished one of adsorption tower A and all rises.
FR finally boosts: continue open valve KV5A, by manual modulation valve HV3, utilize absorption waste gas that the adsorption tower A that finishes equal voltage rise step is boosted, make it to reach adsorptive pressure, prepare to enter adsorption step.
So far, the institute of adsorption tower A in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other nine adsorption towers is identical with adsorption tower A, just staggers mutually in time, carries out continuously with the assurance separation process.
Each adsorption column pressure is cyclically-varying with the variation of processing step, and according to the practical operation situation, adsorptive pressure can suitably be adjusted, then other step pressure is corresponding changes.
Present embodiment PSA-2 by 6 adsorption towers, 1 contraryly put jar, 1 vacuum tank, 3 vavuum pumps and corresponding pipeline and sequencing valve be formed by connecting.Each cyclic process of each tower experience absorption A, displacement RP, all pressure drop ED, contraryly put D, the V that finds time, all voltage rise ER, final seven steps of FR of boosting, each tower operation sequential, gauge pressure see Table 11:
Table 11PSA-2 work schedule table
Figure C20051011824100131
Be example now with adsorption tower K, each processing step of narration PSA-2 operation:
Absorption A: open sequencing valve KV1K and KV2K, enter adsorption tower K through valve KV1K, adsorbing separation C in bed by displacement off-gas buffer tank 7 from the displacement waste gas of PSA-1 2H 4, C 2H 6And C 2Above hydrocarbon components etc. are absorbed component easily, and H 2, O 2, N 2, CH 4Discharge from adsorption tower K top by valve KV2K as absorption waste gas Deng being difficult for absorbed component.After adsorption time arrived, shut off valve KV1K and KV2K stopped absorption, and another adsorption tower that this moment, unstripped gas entered after finally boosting adsorbs.
Displacement RP: open sequencing valve KV3K and KV4K, come self-converse put with the absorption of finding time to obtain mutually product gas enter adsorption tower K through product blending tank 5, displacement gas compressor bank 10, displacement gas surge tank 6, the adsorbent bed of finishing adsorption step is replaced, to improve the content of absorption phase component.Impurity that is displaced and portion C 2H 4, C 2H 6And C 2Above hydrocarbon component is discharged from adsorption tower K top by valve KV4K as displacement waste gas, enters displacement off-gas buffer tank 7 and further reclaims.After time swap arrived, shut off valve KV3K and KV4K stopped displacement.
Equal pressure drop ED: open sequencing valve KV5K and KV5N, the adsorption tower K that finishes after the absorption all presses with the adsorption tower N that finishes after finding time, and after two adsorption column pressures were in a basic balance, shut off valve KV5K finished the equal pressure drop of adsorption tower K.
The contrary D of putting: open sequencing valve KV8K, the adsorbent bed that equal voltage drop step is finished is discharged the absorption phase component, reduces adsorption tower K pressure.Contrary venting enters the contrary jar 3 of putting through valve KV8K, enters product blending tank 5 through manual modulation valve HV2, vacuum tank 4, sequencing valve KV11, KV12, vavuum pump group 9 again.After adsorption tower K pressure is reduced to normal pressure, shut off valve KV8K, contrary putting finished.
V finds time: open sequencing valve KV6K, while open valve KV11, find time by the adsorbent bed after 9 pairs of contrary putting of vavuum pump group, the gas that vavuum pump group 9 is extracted out mixes mutually with contrary venting, a part is as the output after 11 pressurizations of product air compressor group of product gas, and another part is as displacement gas retrieval system after 10 pressurizations of displacement gas compressor bank.Open valve KV12 when finding time to proceed to 360 seconds, the pressure of the adsorption tower K that finds time further to reduce makes the abundant desorb of absorption phase product that is adsorbed in the adsorbent, obtains absorption phase product, finishes adsorbent reactivation.Find time to finish shut off valve KV6K, KV11 and KV12.
Equal voltage rise ER: open valve KV5N and KV5K, the adsorption tower N after finishing the adsorption tower K after finding time and finishing absorption all presses, and after two adsorption column pressures were in a basic balance, shut off valve KV5N finished the equal voltage rise of adsorption tower K.
FR finally boosts: continue open valve KV5K, by manual modulation valve HV4, utilize absorption waste gas that the adsorption tower K that finishes equal voltage rise step is boosted, make it to reach adsorptive pressure, prepare to enter adsorption step.
So far, the institute of adsorption tower K in one-period all is finished in steps, and begins to enter next time circulation, and the performed step of other 5 adsorption towers is identical with adsorption tower K, just staggers mutually in time.
Present embodiment separates the absorption phase product that reclaims and forms as shown in table 12:
Table 12 product gas is formed
When unstripped gas content is identical, identical with the comparative approach of the foregoing description, C in the present embodiment product gas 2And C 2The rate of recovery of above hydrocarbon component rises to 85% from 80%.

Claims (6)

1. from gaseous mixture, separate the pressure swing absorption process that reclaims absorption phase product, it is characterized in that, this pressure swing adsorption system comprises 2 sections of 1 section of transformation absorption and transformation absorption, they are made of at least two adsorption towers that are filled with adsorbent respectively, each adsorption tower circulate at least successively experience absorption, displacement, contraryly put, find time, the step of finally boosting, and the displacement waste gas of 1 section of transformation absorption enters 2 sections of transformation absorption as unstripped gas.
2. the pressure swing absorption process that separate to reclaim absorption phase product from gaseous mixture according to claim 1 is characterized in that, the displacement waste gas that described transformation absorption is 2 sections with enter transformation after the displacement waste gas of 1 section of transformation absorption mixes and adsorb 2 sections.
3. the pressure swing absorption process that reclaims absorption phase product that from gaseous mixture, separates according to claim 1 and 2, it is characterized in that, described absorption and contrary strideing also comprise at least once all voltage drop step between rapid, and are right after at least once all voltage rise steps after the evacuation step.
4. the pressure swing absorption process that separate to reclaim absorption phase product from gaseous mixture according to claim 1 and 2 is characterized in that, described adsorbent is at least a in active carbon, activated alumina, silica gel and the molecular sieve.
5. the pressure swing absorption process that reclaims absorption phase product that from gaseous mixture, separates according to claim 1 and 2, it is characterized in that, the adsorption step gauge pressure that described transformation absorption is 1 section is greater than 0.05MPa, the adsorption step pressure that transformation absorption is 2 sections is the displacement exhaust gas pressure of 1 section of transformation absorption, the displacement step gauge pressure of two sections transformations absorption greater than 0MPa, contrary stride rapid gauge pressure greater than 0MPa, evacuation step gauge pressure be-0.03~-0.09MPa, the unstripped gas temperature is 5-60 ℃.
6. the pressure swing absorption process that separate to reclaim absorption phase product from gaseous mixture according to claim 1 and 2 is characterized in that, the absorption phase product that described separation is reclaimed comprises carbon dioxide, carbon monoxide or with C 2And C 2Above hydrocarbon component is main gaseous mixture.
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CN102935324B (en) * 2012-10-17 2014-07-16 四川天一科技股份有限公司 Variable pressure absorption method for increasing absorption phase product yield
CN104338412B (en) * 2013-08-07 2016-09-28 中国石油化工股份有限公司 A kind of packing method of pressure-swing absorber
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CN106256409B (en) * 2016-08-21 2019-09-03 杭州东安科技有限公司 A kind of pressure swing adsorption system
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CN108545697A (en) * 2018-04-27 2018-09-18 杨皓 A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique
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