CN1215627A - Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas - Google Patents
Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas Download PDFInfo
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- CN1215627A CN1215627A CN97107738A CN97107738A CN1215627A CN 1215627 A CN1215627 A CN 1215627A CN 97107738 A CN97107738 A CN 97107738A CN 97107738 A CN97107738 A CN 97107738A CN 1215627 A CN1215627 A CN 1215627A
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Abstract
A pressure-swing adsorption process for separating and purifying CO from mixed gas containing CO features that in the two-stage pressure-swing adsorption system, the adsorbent filled in adsorption beds can selectively adsorb and separate the mixed gas. In the first stage the components with stronger adsorptivity are removed. In the second stage each adsorption bed is subjected to adsorption, displacement, counter-relief, vacuumizing and raising pressure and the displacements for each bed are cascaded to remove the components with weaker adsorptivity. The purity of CO can reach 90-99%. Its advantages are simple process, low consumption of energy and no environmental pollution.
Description
The present invention relates to from gaseous mixture the pressure swing adsorption technique of separation and purified gases, particularly the two-phase method pressure swing adsorption technique of separation purifying carbon oxide from the gas mixture that contains monochlor(in)ate carbon.
Pressure swing adsorption process is a kind of technology of separating and purify purifying gas from gaseous mixture.Be a kind of gas that carries out at normal temperatures, solid phase physical adsorption process.Pressure swing adsorption also is the technology of less energy-consumption, non-environmental-pollution.Pressure swing adsorption has the feature of adsorption selectivity to different gas compositions according to sorbent material, big with loading capacity under high pressure (adsorptive pressure) to gas composition, and in the following little characteristics of loading capacity of low pressure (desorption pressures), alternately switch circulation technology by what absorption and desorb were formed, in order to the separation of realization gas composition.
The table composed as follows (percent by volume) that typically contains carbon mono oxide mixture:
| Component/classification | Converter gas | Water-gas | Blast furnace gas |
| ????H 2 | ????1.5 | ????50 | ????2.4 |
| ????CO | ????51 | ????40 | ????25 |
| ????CO 2 | ????22 | ????7 | ????14.5 |
| ????CH 4 | ????48ppm | ????3 | ????0.3 |
| ????N 2 | ????25 | ????57.5 | |
| ????O 2 | ????0.5 | ????0.2 | ????0.3 |
Because common used youngster plants the adsorptive power difference of sorbent material to each gas composition in the above-mentioned gas mixture in the pressure swing adsorption technique, the power of their adsorptive poweies is arranged by following order:
H
2O＞CO
2＞CH
4＞CO＞N
2＞O
2＞H
2Or
H
2O＞CO
2＞CO＞CH
4＞N
2＞O
2＞H
2
Promptly in mixed gas, the adsorptivity of CO is between CO
2And N
2, O
2, H
2Between component, for based on These characteristics, existing two-phase method transformation absorption purification CO technology is adsorbed successively through first section absorption process, all pressure drops, isolation, the reverse pressure of putting, and flushing, all voltage rises, the final program of boosting are at first removed H
2O, CO
2Be better than the component of CO etc. adsorptive power; Enter second section absorption process then, carry out CO and N
2, O
2, H
2Separation Deng component.In second section operation, CO is the strongest component of adsorptivity, is adsorbed agent absorption and stays in the adsorption bed.N
2, O
2, H
2Pass adsorption bed discharge system Deng component, the CO that is adsorbed obtains the CO product through reducing pressure, vacuumizing.Existing two-phase method transformation adsorbing and extracting CO technology, not high to the purification degree of CO, the adsorption bed utilization ratio is not high.
Given this, the object of the invention is to provide a kind of energy consumption low, free from environmental pollution, can from various be rich in or contain to purify the gas mixture of carbon monoxide of lower concentration produce the pressure swing adsorption technique of high-purity carbon monooxide.
The present invention increases the series connection displacement step in second section operation of existing two-phase method transformation absorption purification CO technology, with portioned product CO as displacement gas remaining in nitrogen in the adsorption bed, oxygen, components such as hydrogen are replaced away, to improve CO concentration in the bed, use the CO that a great deal of is still arranged behind this replacement process to discharge the displacement gas of gas again as another adsorption bed, the series connection displacement that formation is made of several adsorption beds, repeatedly utilize displacement gas, improve the utilization ratio of CO, reduce the displacement consumption of product, obtain the highly purified products C O and the higher CO rate of recovery, and realize its purpose.
Of the present invention from contain carbon mono oxide mixture the pressure swing adsorption process (referring to accompanying drawing) of purifying carbon oxide, in the pressure swing adsorption system that constitutes by the first section operation (PSA-I) that has two adsorption beds separately at least that the filling sorbent material is arranged and second section operation (PSA-II) serial connection, it is characterized in that containing successively and adsorb (A) through first section each adsorption bed of operation, all pressure drops (ED), the reverse pressure (BD) of putting, flushing (P), all voltage rises (ER), the circulation step of (FR) finally boosts, occlusion and removing after adsorptivity is better than the component of carbon monoxide in the gas mixture, contain successively through second section each adsorption bed of operation again and adsorb (A), displacement (RP), the reverse pressure (BD) of putting, vacuumize (VC), the circulation step of (R) boosts, occlusion and extract carbon monoxide, remove the component that adsorptivity is weaker than carbon monoxide, the series connection displacement that above-mentioned second section operation has the displacement step by at least two adsorption beds to be in series and to constitute.
The waste gas of using gas to discharge of first section above-mentioned operation rinse step from second section operation.
Sorbent material in the adsorption bed of first section above-mentioned operation is at least a in silica gel, gac, aluminium glue, the activated alumina, and the sorbent material in the adsorption bed of second section operation is at least a in gac, carbonaceous molecular sieve, the zeolite molecular sieve.
The pressure of the adsorption step of first section above-mentioned operation is 0.3～1.9MPa, and the pressure of the adsorption step of second section operation is 0.2～1.9MPa, and the pressure of displacement step is 0.1～1.9MPa, the pressure that vacuumizes step is-0.07～-0.098MPa.
Of the present invention from carbon mono oxide mixture the pressure swing adsorption process (referring to accompanying drawing) of purifying carbon oxide, constitute pressure swing adsorption system by first section (PSA-I) and second section (PSA-II) serial connection, the purification process of its CO is as follows.
Contain the unstripped gas (gas mixture that promptly contains CO) of CO, under certain pressure, send into the adsorption bed of first section operation through pipeline.This operation is made of at least two adsorption bed and corresponding pipeline, program valves etc. that are filled with sorbent material.The quantity of adsorption bed is determined the processing power of unstripped gas according to composition and pressure, the adsorption bed of raw material.The sorbent material of filling in the adsorption bed is determined according to the composition of unstripped gas, in order to remove the H that adsorptivity in the unstripped gas is better than CO
2O, CO
2, CH partly
4Reach sulfide, can select in silica gel, gac, aluminium glue, the activated alumina etc. one or more for use.
First section operation is purpose with the component that removes adsorptivity and be better than CO, and adsorption bed is finished a cyclical operation will experience absorption, all pressure drops, reverse pressures, flushing, equal voltage rise, the final processing step such as boost put, and a plurality of adsorption beds are alternately finished above-mentioned processing step.Each absorption bed is all being carried out mutually different step at one time, at any time, always there are one or more adsorption beds to be in adsorption step, and under the substantially invariable situation of pressure, work in-process gas is transferred to the adsorption bed of second section operation through pipeline, below the step of this operation is illustrated.
Absorption (A): unstripped gas enters adsorption bed continuously and stably under 0.5～2.0MPa pressure, and the adsorption bed pressure-controlling is at 0.3～1.9MPa, the H in the unstripped gas
2O, CO
2, sulfide, portion C H
4Be adsorbed agent absorption, stay in the adsorption bed, and the CO that is not adsorbed, H
2, N
2, CH
4, Ar etc. is discharged from bed and sends into second section operation, carries out separating of CO and other component.When adsorption bed through after a while absorption after, sorbent material is basically by CO
2, H
2Impurity such as O institute is saturated, need enter next step operation for sorbent material is regenerated.
All pressure drops (ED): all to be this adsorption bed of finishing adsorption step put the process of pressure to the adsorption bed of the equal voltage rise of needs to voltage drop step, and all voltage drop step can reclaim the useful component in the adsorption bed.Equal voltage drop step can be divided into repeatedly to be finished, and is called once all pressure drops (E1D), the equal pressure drop of secondary (E2D) ...In concrete technological process, the equal pressure drop number of times that is adopted is looked the pressure of unstripped gas and is formed and determine.
The reverse pressure (BD) of putting: the reverse pressure of putting is that adsorption bed pressure is reduced, and makes the impurity component that adsorbs in the adsorption bed promptly need the component desorb discharging process that removes.Its air flow direction and flow of feed gas are to opposite.
Flushing (P): flushing is the gas purging adsorption bed with component free from foreign meter, makes the process of the abundant desorb of impurity component.Purge gas comes from second section absorption waste gas.
All voltage rises (ER): all voltage rise is a process of utilizing the gas of the adsorption bed of equal pressure drop that this adsorption bed is boosted.Equal voltage rise step can be divided into repeatedly to be finished, and is called once all voltage rises (E1R), the equal voltage rise of secondary (E2R) ...In concrete technological process, all pressures number of times that is adopted is decided on raw gas pressure and composition.All voltage rise is with all the pressure drop number of times is corresponding.
(FR) finally boosts: this step is to utilize work in-process gas to return some to make this adsorption bed pressure be raised to the process of adsorptive pressure.
After finishing above-mentioned steps, adsorption bed has been finished the cyclical operation of one-period.The processing step of each adsorption bed experience is identical, just staggers mutually in time, at any time all has an adsorption bed carrying out the adsorption step operation with assurance, thus the continuous operation of holding device.
Second section operation is serially connected in after first section operation, is made of at least two adsorption bed and corresponding pipeline, sequence valves that are filled with sorbent material.The quantity of adsorption bed, the composition of the work in-process gas of sending here according to first section operation and pressure, adsorption bed are determined the processing power of work in-process gas.Filling in the adsorption bed is determined according to the composition of work in-process gas, in order to adsorb the CO in the work in-process gas, can select in gac, molecular sieve, the carbonaceous molecular sieve one or more for use.In second section adsorption bed, sorbent material carries out selective adsorption to CO, and CO stays in the adsorption bed, other H
2, N
2, O
2, CH
4Discharge Deng from exit end, return first section operation through pipeline, as the purge gas of first section adsorbent reactivation, flushing back gas exhausting device can be done fuel or other chemical industry utilizations.After absorption finished, except that CO, residual had an a certain amount of H in the adsorption bed
2, N
2, O
2, CH
4Component returns the adsorption bed displacement of replacing and connect with portion C O product gas, again with H
2, N
2, O
2, CH
4Drive adsorption bed out of, after second section operation adsorption bed displacement is qualified, reclaim the interior CO product gas of adsorption bed, obtain the CO product of purifying with step-down and vacuum take-off mode.
Obtain pure CO product second section operation, in the once circulation of each adsorption bed, to experience absorption, all pressure drops, displacement, reversely put pressures, vacuumize, boost or processing step such as equal voltage rise, no matter adopt several adsorption bed combinations, all alternately carry out these processing steps, so that the output of CO product continous-stable.Now each step is respectively described below.
Absorption (A): enter from the adsorption bed inlet end as unstripped gas from work in-process pneumatic transmission to this operation of first section operation output, the adsorption bed pressure-controlling is at 0.2～1.9MPa, CO in the work in-process is selected to be adsorbed on the sorbent material, other component is discharged from the adsorption bed top as absorption waste gas, sends to first section operation.Adsorbent reactivation gas as first section operation.This step has realized that CO is difficult for separating of absorbed component with other.
Displacement (PR): utilize a part of CO product that returns, adsorption bed is carried out replacement operator from bottom to top, its working pressure is controlled at 0.1～1.9MPa, in same adsorption bed, displacement step can be divided into repeatedly to be finished, and is called once displacement (RP1), twice replaced (RP2), three displacements (RP3), four displacements (RP4) ...The displacement vent gas of discharging from the adsorption bed top, deliver to next adsorption bed again, carry out displacement from bottom to top, this displacement vent gas is replaced next adsorption bed more again ... several adsorption bed series connection are communicated with, different adsorption beds is replaced one by one, in many bed process, form the series connection displacement like this.Series connection metathetical adsorption bed has at least two, can equal the adsorption bed quantity of second section operation.Repeatedly metathetical number of times and concrete many bed process couplings.Repeatedly the metathetical purpose is to reduce foreign matter content in the bed, reclaims the CO in the displacement waste gas, obtains the high-purity CO product.The displacement waste gas that displacement is at last discharged mixes with absorption waste gas, recycles and send first section operation to make purge gas.
The reverse pressure (BD) of putting: after the replacement completion, against the direction of travel step-down of absorption, the gas after the step-down promptly is the CO product of making, and is transported to product gas system.Reverse putting presses step to finish several times, is called once reverse pressure (BD1), the reverse pressure (BD2) of putting of secondary of putting ...
Vacuumize (VC): it is right that the adsorption bed internal pressure is reduced near normal pressure, further reduces the pressure of adsorption bed by the power of vacuum pump, and its working pressure is-0.07～-0.0MPa, withdrawing gas is the CO product, carries the product gas system that goes.A part is used for displacement step.After this step was finished, the agent of adsorption bed internal adsorption was also regenerated and is finished, and prepared to carry out cyclical operation next time.Vacuumizing step can finish several times, is called once to vacuumize (VC1), secondary vacuum pumping (VC2) ...
(R) boosts: after finishing evacuation step, utilize absorption waste gas, displacement waste gas or unstripped gas that this bed is boosted.The step of boosting can be divided into repeatedly to be finished, and is called once (the R that boosts
1), secondary booster (R
2), boost for three times ...
Two-phase method of the present invention has following tangible advantage and significant effect.
One, this two-phase method increases displacement step, after the displacement step of particularly connecting, can improve the purification degree of CO, and its CO purity can reach 90～99%, and product can be made good industrial chemicals.
Two, after this two-phase method increases displacement step, can improve purification degree and the purification efficiency of CO, the CO that can from the gas mixture that contains lower concentration CO, purify, and can be from impurity gas such as the CH of adsorptivity near CO arranged
4Contain the CO that purifies in the CO gas mixture.Therefore, the CO that can from multiple industrial gaseous waste, purify, it is applied widely.
Three, this two-phase method, with the displacement waste gas of second section operation and the purge gas of first section operation of absorption waste gas work, exhaust emission system after the flushing, do the burning gas utilization in addition, adopt the series connection displacement in addition, repeatedly utilize displacement waste gas and absorption waste gas, make this technology non-pollution discharge, and has energy consumption advantage low and free from environmental pollution.
Below, use embodiment and accompanying drawing thereof again, the utility model is described in further detail.
Brief description of drawings.
Fig. 1 be of the present invention from contain carbon mono oxide mixture the FB(flow block) of the pressure swing adsorption process of purifying carbon oxide.
Fig. 2 is the schematic flow sheet of a kind of pressure swing adsorption process of Fig. 1, shows four bed process flow processs.
Fig. 3 is the corresponding relation and the gas flow figure of each step in each adsorption bed of first section operation (PSA-I) of Fig. 2.
Fig. 4 is the corresponding relation and the gas flow figure of each step in each adsorption bed of second section operation (PSA-II) of Fig. 2.
Fig. 5 is the pressure trend figure of each step of Fig. 3.
Fig. 6 is the pressure trend figure of each step of Fig. 4.
Fig. 7 is the schematic flow sheet of another kind of the present invention pressure swing adsorption process of purifying carbon oxide from contain the broken gas mixture of an oxidation.Showing first section, to be six, second section be eight technical process.
Fig. 8 is the corresponding relation and the gas flow figure of each step in each adsorption bed of first section operation (PSA-I) of Fig. 7.
Fig. 9 is the corresponding relation and the gas flow figure of each step in each adsorption bed of second section operation (PSA-II) of Fig. 7.
Embodiment 1
Of the present invention a kind of from contain carbon mono oxide mixture the pressure swing adsorption process of purifying carbon oxide, shown in Fig. 2～6.
Unstripped gas is a semi-water gas:
Form: CO CO
2N
2H
2CH
4+ Ar O
2
Volume %:26.5 9.0 19.0 44.0 1.0 0.5
This pressure swing adsorption process is according to composition employing four bed systems as shown in Figure 2 of above-mentioned raw materials, and this system is made of first section operation PSA-I and second section operation PSA-II of serial connection.
First section operation is by adsorption bed I A, I B, I C, the I D of four tower structures, with the compressor 1 of adsorption bed UNICOM and unstripped gas house steward 2, work in-process gas house steward 3 and control valve 4, purge gas house steward 5, waste gas header 6, take over 7 and each pipeline in sequencing valve 8a, the 9a, 10a, 11a, the 12a that match with I A, sequencing valve 8b, the 9b, 10b, 11b, the 12b that match with I B, sequencing valve 8c, the 9c, 10c, 11c, the 12c that match with I C, formations such as sequencing valve 8d, the 9d that matches with I D, 10d, 11d, 12d.The sorbent material of filling is activated alumina and silica gel in this adsorption tower.
Second section operation is by the adsorption bed II A of four tower structures, II B, II C, II D, above-mentioned work in-process gas house steward 3 with adsorption bed UNICOM, above-mentioned purge gas house steward 5 and control valve 15,16,17, displacement gas house steward 18 and on control valve 23, CO finished product gas house steward 19 and on vacuum pump 20, sequencing valve 24, compressor 25, take over 26, each adsorption bed of UNICOM and discharging gas house steward 35, and the sequencing valve 27a that matches with II A in each pipeline, 28a, 29a, 30a, 31a, 32a, the sequencing valve 27b that matches with II B, 28b, 29b, 30b, 31b, 32b, the sequencing valve 27c that matches with II C, 28c, 29c, 39c, 31c, 32c, the sequencing valve 27d that matches with II D, 28d, 29d, 30d, 31d, formations such as 32d.The sorbent material of filling is a zeolite molecular sieve in this section adsorption tower.
The native system operation is right, press each sequencing valve of programming Control and control valve by computer, unstripped gas is that gas mixture is by compressor 1, under about 0.5MPa pressure, through raw material house steward 2, enter each adsorption bed of first section operation respectively on time, each adsorption bed alternately carries out identical successive circulation step as shown in Figure 3 successively, it is the gas flow of example that arrow among Fig. 3 illustrates with adsorption bed I A, the steps include: to adsorb A, once equal pressure drop E1D, isolate I S, the equal pressure drop E2D of secondary, reverse putting pressed BD, flushing P, the equal voltage rise E2R of secondary, once equal voltage rise E1R, FR finally boosts.Above-mentioned between adjacent once equal pressure drop E1D and the isolation I S step between the equal pressure drop E2D of secondary, be that each step ordering takes pause together.The pressure change of this section each step of operation as shown in Figure 4.It is the gas flow of example that arrow among Fig. 4 illustrates with adsorption bed II A, and the control pressure that the steps include: the adsorption step of this operation is gauge pressure 0.5MPa.Through four transformation absorption of first section operation, removed the strong adsorbent component H in the unstripped gas
2O, CO
2, CH partly
4, foreign gas such as trace sulfide, desorb is after waste gas header 6 discharge systems, the work in-process gas of gained is under about 0.5MPa pressure, through work in-process gas house steward 3, by to entering each adsorption bed of second section operation respectively, each adsorption bed alternately carries out identical continuous circulation step as shown in Figure 4 successively: absorption A, once replace RP1, twice replaced RP2, reverse put press BD, vacuumize VC, R1, secondary booster R2 once boost.The pressure change of each step as shown in Figure 5.The control pressure of the adsorption step of this operation is gauge pressure 0.2MPa, and the working pressure of displacement step is controlled at gauge pressure 0.2MPa, and the working pressure that vacuumizes step is the vacuum tightness 0.8MPa at the vacuum pump inlet place.Through four transformation absorption of second section operation, remove the weak adsorbent component N in the work in-process gas
2, H
2, CH partly
4, foreign gas such as Ar, send each adsorption bed of first section operation back to as purge gas through purge gas house steward 5.The displacement step series connection of above-mentioned 4 adsorption beds constitutes the series connection displacement.Through above-mentioned reverse put press and vacuumize step after, obtain the CO product.The some of this CO product is sent this section adsorption bed back to as displacement gas through displacement gas house steward 18.CO product reverse put splenium part, through discharging gas house steward 35, sequencing valve 24, directly send into vacuum pump 20 pipeline afterwards, reverse put press to finish after, by vacuum pump 20,, adsorption bed is vacuumized through discharging gas house steward 35, sequencing valve 33, sequencing valve 34, the product of extracting out converges with contrary venting, by compressor 25 output systems.
This pressure swing adsorption process, obtainable CO product purity 〉=96%, product impurity H
2+ N
2+ CH
4+ Ar≤4.0%, CO
2, O
2+ H
2O all≤10ppm.This products C O can make the good raw material of organic synthesis.
Embodiment 2
The pressure swing adsorption process of another kind of the present invention purifying carbon oxide from contain carbon mono oxide mixture is shown in Fig. 7～9.Its technical process is identical substantially with embodiment 1 with system architecture.Its unstripped gas as gas mixture is the semi-water gas of factory:
Form: H
2 CON
2CH
4CO
2
Volume %:42 35 16 16
The technical process of present embodiment is identical substantially with embodiment 1 with system architecture, and unstripped gas is that gas mixture compresses to 0.7MPa, enters PSA-I operation at normal temperatures, removes CO
2, H
2Impurity such as O, sulfide, work in-process gas advance PSA-II operation, N
2, H
2, CH
4Separate purification CO with CO.CO after the purification is by vacuumizing the step desorb.Part CO returns PSA-II operation as displacement gas, and all the other CO carry to the user as product gas.The displacement of PSA-II and absorption waste gas send PSA-I operation, as the purge gas of PSA-I operation.Exhaust extractor after the flushing is as fuel gas.
The characteristics of present embodiment are:
First section operation is by the adsorption bed I A of six tower structures, I B, I C, I D, I E, I F, compressor 1 and unstripped gas house steward 2 with adsorption bed UNICOM, work in-process gas house steward 3 and control 3 the system valves 4, purge gas house steward 5, the sequencing valve 7a that matches with I A in waste gas header 6 and each pipeline, 8a, 9a, 10a, 11a, 12a, the sequencing valve 7b that matches with I B, 8b, 9b, 10b, 11b, 12b, the sequencing valve 7c that matches with I C, 8c, 9c, 10c, 11c, 12c, the sequencing valve 7d that matches with I D, 8d, 9d, 10d, 11d, 12d, the sequencing valve 7e that matches with I E, 8e, 9e, 10e, 11e, 12e, the sequencing valve 7f that matches with I F, 8f, 9f, 10f, 11f, formations such as 12f.The sorbent material of filling is active aluminum chloride and silica gel in this adsorption tower.
Second section operation is by the adsorption bed II A of eight tower structures, II B, II C, II D, II E, II F, II G, II H, above-mentioned work in-process gas house steward 3 with adsorption bed UNICOM, above-mentioned purge gas house steward 5, with discharging gas house steward 15,16, vacuum pump 19,20 and displacement gas compressor 26 each pipeline in the sequencing valve 27a that matches with II A, 28a, 29a, 30a, 31a, 32a, the sequencing valve 27b that matches with II B, 28b, 29b, 30b, 31b, 32b, the sequencing valve 27c that matches with II C, 28c, 29c, 39c, 31c, 32c, the sequencing valve 27d that matches with II D, 28d, 29d, 30d, 31d, 32d, the sequencing valve 27e that II E matches, 28e, 29e, 30e, 31e, 32e, the sequencing valve 27f that matches with II F, 28f, 29f, 30f, 31f, 32f, the sequencing valve 27g that matches with II C, 28g, 29g, 39g, 31g, 32g, the sequencing valve 27h that matches with II H, 28h, 29h, 30h, 31h, formations such as 32h.The sorbent material of filling is a zeolite molecular sieve in this section adsorption tower.
PSA-I operation is pressed the equal processing steps operation of six two of Fig. 8, each loop cycle of each adsorption bed by absorption A, once all pressure drop E1D, the equal pressure drop E2D of secondary, reverse put press BD, flushing P, the equal voltage rise E2R of secondary, once all voltage rise E1R, finally eight steps of FR of boosting are formed.Fig. 8 is the gas flow that example illustrates each processing step for the corresponding relation of each each processing step of adsorption bed with I A bed, and the gas flow between other each is similar to I A bed, does not mark in addition.Being in operation always has two adsorption beds to be in the adsorption step of charging, output work in-process gas, and all the other four adsorption beds are in the different step of adsorbent reactivation.PSA-I operation can make work in-process gas continous-stable transport to PSA-II operation, as the unstripped gas of PSA-I II operation.The adsorption bed of PSA-I operation is made sorbent material with activated alumina and silica gel, and a circulation time is about 720 seconds.Adsorptive pressure is 0.6MPa, and adsorbent reactivation is pressed and step such as washed and finish under normal pressure by equal pressure drop, reverse putting.
PSA-II operation is undertaken by the processing step of Fig. 9, eight adsorption bed II A, II B, II C, II D, II E, II F, II C, II H are arranged, each loop cycle of each adsorption bed is by absorption A, equal pressure drop ED, once replace RP1, twice replaced RP2, three displacement RP3, four displacement RP4, once reverse putting presses BD1, reverse the putting of secondary to press BD2, once vacuumizes VC1, secondary vacuum pumping VC2,11 steps of ER of boosting form.The equal pressure drop ED effect of this operation is identical with the equal pressure drop of PSA-I operation.Fig. 9 is the gas flow that example illustrates each processing step for the corresponding relation of each each processing step of adsorption bed with II A bed, and the gas flow between other each is similar to II A bed, does not mark in addition.Being in operation always has two adsorption bed chargings to be in adsorption step, and adsorptive pressure is 0.4MPa, to remove the N in the work in-process gas
2, H
2, portion C H
4With weak absorption such as Ar impurity composition.Absorption finishes the back and carries out equal voltage drop step with another adsorption bed that just vacuumizes end, and this equal voltage drop step gas is the equal voltage rise step of another adsorption bed relatively.The about 0.16MPa of end of a period pressure of equal voltage drop step.All and then voltage drop step carries out displacement step after finishing, and the control pressure of displacement step is 0.2MPa.The displacement step series connection of eight adsorption beds is carried out, and further removes the impurity composition in the bed, improves the purity of CO product.After the replacement completion, obtain pure CO product in the reverse step-down mode of pressing step and vacuumizing step of putting.Sorbent material is regenerated simultaneously.Mode with equal voltage rise makes this bed rise to 0.16MPa then, finishes a circulation and enters next circulation, and pressure rises to 0.4MPa from 0.16MPa and adsorbs in charging.In 8 adsorption beds, all load zeolite molecular sieve and make sorbent material.About 900 seconds of circulation time of this operation.
The native system operation is right, press each sequencing valve of programming Control and control valve by computer, unstripped gas is a gas mixture, compressed machine 1, be compressed to 0.7MPa, enter PSA-I operation at normal temperatures, PSA-I operation is made up of 6 adsorption towers, unstripped gas enters wantonly two in being total to, and being in operation always has two adsorption beds to be in adsorption step.Unstripped gas enters adsorption bed I A, I B, I C, I D, I E, I F respectively from sequencing valve 7a, 7b, 7c, 7d, 7e, 7f, and the sorbent material of filling is selected CO absorption in the bed
2, H
2Impurity such as O, sulfide, the CO that is not adsorbed
2, N
2, H
2, CH
4In work in-process gas through program valve 8a, 8b, 8c, 8d, 8e, 8f, work in-process gas house steward 3, control valve 4 enters PSA-II operation.Be adsorbed on the CO in the sorbent material solid phase
2, H
2Impurity such as O, sulfide is just by the reverse pressure of putting, discharge adsorption bed respectively from sequencing valve 9a, 9b, 9c, 9d, 9e, 9f, again by the purge gas of coming from PSA-II operation, by purge gas house steward 5, enter each adsorption bed from sequencing valve 10a, 10b, 10c, 10d, 10e, 10f respectively, bed is washed, and further CO is discharged in desorb
2, H
2Impurity such as O, sulfide.Stripping gas after the flushing is also discharged adsorption bed through sequencing valve 9a, 9b, 9c, 9d, 9e, 9f, outside waste gas header 6 discharge systems.Sequencing valve 11a, 11b in the PSA-I, 11c, 11d, 11e, 11f are equalizing valve, and sequencing valve 12a, 12b, 12c, 12d, 12e, 12f are final back-up valve.
In PSA-II operation, work in-process gas is from work in-process gas house steward 3, sequencing valve 27a, 27b, 27c, 27e, 27f, 27g, 27h, enter any two among eight adsorption bed II A, II B, II C, II D, II E, II F, II G, the II H respectively, being in operation also always has two adsorption beds to be in adsorption step, and adsorption step carries out under 0.4MPa pressure.To remove the weak absorption impurity composition N in the work in-process
2, H
2, portion C H
4With Ar etc., its absorption waste gas is discharged adsorption beds from sequencing valve 29a, 29b, 29c, 29e, 29f, 29g, 29h through purge gas house steward 5 respectively.Absorption finishes back and another adsorption bed that just vacuumizes end, carry out equal pressure drop or all voltage rises by sequencing valve 28a, 28b, 28c, 28e, 28f, 28g, 28h, the equal pressure drop gas that makes this is to the equal voltage rise of another adsorption bed, and and then the about 0.16MPa of end pressure replaces after all pressure finishes.With II A bed is example explanation replacement process, and displacement gas is sent by displacement gas compressor 26, and by control valve 35, sequencing valve 31a enters adsorption bed II A, carries out RP
4Displacement discharges the displacement gas of II A bed from sequencing valve 32a, enters adsorption bed II B adsorption bed II B is carried out RP
3Displacement enters adsorption bed II C from adsorption bed II B outlet through sequencing valve 32b, and C carries out RP to the adsorption bed II
2Displacement enters adsorption bed II D from adsorption bed II C outlet through sequencing valve 32c, and D carries out RP to the adsorption bed II
1Displacement, the displacement waste gas after the adsorption bed II D displacement is discharged from sequencing valve 29d, through flushing tracheae 5, as the purge gas of PSA-I.The displacement pressure-controlling is at 0.2MPa, and several adsorption beds are connected successively and carried out, and further remove the impurity composition in the adsorption bed, improves the CO product purity.After the replacement completion, the CO product is exported from PSA-II system with the form that vacuumizes earlier with reverse form of putting pressure again.Reverse put press to finish after, by the mode that vacuumizes further to the adsorption bed step-down to obtain the CO product.Vacuum pump 19 or the 20 CO product gas of extracting out are supplied with the user through CO product gas house steward 24 outputs; Another part CO product gas enters displacement compressor 26 by pipeline 25, returns the PSA-II through control valve 35, makes displacement gas.
The obtainable CO product purity 98% of this embodiment, impurity H in the product
2Be 0.01%, N
2Be 0.8%, CH
4Be 1.18%, CO
2Be 0.01%, H
2O≤10ppm.
Claims (4)
1, the pressure swing adsorption process of purifying carbon oxide from contain carbon mono oxide mixture, in the pressure swing adsorption system that constitutes by the first section operation (PSA-I) that has two adsorption beds separately at least that the filling sorbent material is arranged and second section operation (PSA-II) serial connection, it is characterized in that containing successively and adsorb (A) through first section each adsorption bed of operation, all pressure drops (ED), the reverse pressure (BD) of putting, flushing (P), all voltage rises (ER), the circulation step of (FR) finally boosts, occlusion and removing after adsorptivity is better than the component of carbon monoxide in the gas mixture, contain successively through second section each adsorption bed of operation again and adsorb (A), displacement (RP), the reverse pressure (BD) of putting, vacuumize (VC), the circulation step of (R) boosts, occlusion and extract carbon monoxide, remove the component that adsorptivity is weaker than carbon monoxide, the series connection displacement that above-mentioned second section operation has the displacement step by at least two adsorption beds to be in series and to constitute.
2, pressure swing adsorption process according to claim 1 is characterized in that the waste gas of the usefulness gas of said first section operation rinse step from second section operation discharge.
3, pressure swing adsorption process according to claim 1 and 2, it is characterized in that sorbent material in the adsorption bed of said first section operation is at least a in silica gel, gac, aluminium glue, the activated alumina, the sorbent material in the adsorption bed of second section operation is at least a in gac, carbonaceous molecular sieve, the zeolite molecular sieve.
4, pressure swing adsorption process according to claim 3, the pressure that it is characterized in that the adsorption step of said first section operation is 0.3～1.9MPa, the pressure of the adsorption step of second section operation is 0.2～1.9MPa, the pressure of said displacement step is 0.1～1.9MPa, the said pressure that vacuumizes step is-0.07～-0.098MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107738A CN1073876C (en) | 1997-10-24 | 1997-10-24 | Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN97107738A CN1073876C (en) | 1997-10-24 | 1997-10-24 | Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas |
Publications (2)
| Publication Number | Publication Date |
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| CN1215627A true CN1215627A (en) | 1999-05-05 |
| CN1073876C CN1073876C (en) | 2001-10-31 |
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| WO2005120681A1 (en) * | 2004-06-11 | 2005-12-22 | Chengdu Tianli Chemical Engineering Technology Co., Ltd. | A two-stage complete recycle pressure-swing adsorption process for gas seperation |
| CN101822929B (en) * | 2010-02-02 | 2012-06-06 | 华东理工大学 | Method for capturing carbon dioxide by utilizing electrical desorption technology |
| CN105203440A (en) * | 2015-09-14 | 2015-12-30 | 大连理工大学 | Method of measuring variable-pressure absorption gas separation performance of carbon molecular sieve on basis of liquid absorption gas flooding principle |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539020A (en) * | 1983-07-10 | 1985-09-03 | Kawasaki Steel Corporation | Methods for obtaining high-purity carbon monoxide |
| JPS62241524A (en) * | 1986-04-14 | 1987-10-22 | Kawasaki Steel Corp | Separation and purification for carbon monoxide excellent in stabilization of purity |
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1997
- 1997-10-24 CN CN97107738A patent/CN1073876C/en not_active Expired - Lifetime
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| WO2005120681A1 (en) * | 2004-06-11 | 2005-12-22 | Chengdu Tianli Chemical Engineering Technology Co., Ltd. | A two-stage complete recycle pressure-swing adsorption process for gas seperation |
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| US8545601B2 (en) | 2004-06-11 | 2013-10-01 | Yuwen Song | Two-stage complete recycle pressure-swing adsorption process for gas separation |
| CN101822929B (en) * | 2010-02-02 | 2012-06-06 | 华东理工大学 | Method for capturing carbon dioxide by utilizing electrical desorption technology |
| CN105203440A (en) * | 2015-09-14 | 2015-12-30 | 大连理工大学 | Method of measuring variable-pressure absorption gas separation performance of carbon molecular sieve on basis of liquid absorption gas flooding principle |
| CN105203440B (en) * | 2015-09-14 | 2017-10-17 | 大连理工大学 | A kind of method that carbon molecular sieve PSA Gas separating property is determined based on imbibition purging principle |
| CN111770892A (en) * | 2018-03-06 | 2020-10-13 | 住友精化株式会社 | Method for removing oxygen from crude carbon monoxide gas and method for purifying carbon monoxide gas |
| CN109364691B (en) * | 2018-10-17 | 2021-06-04 | 四川天采科技有限责任公司 | Asymmetric desorption method for simultaneously recovering adsorption phase and non-adsorption phase components by PSA |
| CN111989149A (en) * | 2020-04-14 | 2020-11-24 | 成都盈辰科技有限公司 | Method of movable pressure swing adsorption oxygen production device |
| CN111871149A (en) * | 2020-08-28 | 2020-11-03 | 成都华西化工科技股份有限公司 | Two-stage pressure swing adsorption system for recovering adsorbed components and use method thereof |
| CN111871149B (en) * | 2020-08-28 | 2024-04-09 | 成都华西化工科技股份有限公司 | Two-stage pressure swing adsorption system for recovering adsorbed components and application method thereof |
| CN116588938A (en) * | 2023-06-21 | 2023-08-15 | 上海汉兴化工科技有限公司 | Process for pretreating coal gas and purifying carbon monoxide |
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