CN102343196B - Method and device for one-stage pressure swing adsorption hydrogen extraction and carbon-rich gas recovery - Google Patents
Method and device for one-stage pressure swing adsorption hydrogen extraction and carbon-rich gas recovery Download PDFInfo
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Abstract
The invention discloses a method and a device for one-stage pressure swing adsorption hydrogen extraction and carbon-rich gas recovery. The method adopts a pressure swing adsorption principle. Through the method and the device, high-purity hydrogen is extracted from methanol synthesis discharge gas and is utilized as product gas; simultaneously, high-purity carbon-rich gas produced in recovery desorption is utilized as feed gas utilized for a methanol device; produced concurrently discharged hydrogen with high concentration is fed back to a methanol system; and produced concurrently discharged replacement gas with low concentration is utilized as fuel gas and is discharged into a fuel pipe net. Each one cycle of the method comprises a adsorption process, a concurrent discharge process, a displacement process, a countercurrent discharge process, a vacuum-pumping process, a even pressure rise process and a final stroke process. Compared with a conventional two-stage method-based hydrogen extraction technology, the method provided by the invention improves a total hydrogen recovery rate and a product hydrogen recovery rate of the device. Through the method and the device, high-purity carbon-rich gas can be extracted from analysis gas. The device has the advantages of low cost, small floor space and good economic benefits.
Description
Technical field
The present invention relates to a kind of pressure swing adsorption hydrogen production device, refer more particularly to a kind of method and device that can greatly improve the one-stage pressure swing adsorption hydrogen extraction of rich carbon gas recovery rate and reclaim rich carbon gas.
Background technology
In similar device for converting coke oven gas methyl alcohol processed or coproducing synthetic ammonia (or needing hydrogen production), in unstripped gas, contain hydrogen, carbon dioxide, carbon monoxide, the gas componants such as nitrogen, the general two-phase method hydrogen production process that adopts, first unstripped gas is obtained to raw hydrogen through pressure swing adsorption decarbonization flow processing, the carbonaceous gas (rich carbon gas) parsing in decarburization flow process returns to methyl alcohol system, again raw hydrogen is put forward to hydrogen flow processing and is obtained the finished hydrogen of higher degree by molecular sieve pressure-variable adsorption, carry the gas parsing in hydrogen flow process and directly send to fuel pipe network or emptying, if China Patent No. is CN200610022102.9, name is called a kind of patent of invention of method for preparing hydrogen by reforming methanol with high recovery rate, comprise that methyl alcohol being mixed to rear supercharging with water sends into vaporization superheater, after reaching reaction temperature, enter converter, under catalyst action, reform and generate reformed gas, again this reformed gas is cooled to normal temperature, by sending into one after this reformed gas purified treatment, be set with in the pressure-changeable adsorption decarbonization device of decarburization adsorbent and slough carbon dioxide, obtain containing H
2, CO, CH
4decarburization raw hydrogen, this decarburization raw hydrogen being sent into a set of pressure-variable adsorption take molecular sieve as main adsorbent carries and in hydrogen production device, sloughs all impurity and obtain product hydrogen again, carry after the tail gas supercharging in hydrogen production device and be incorporated to from the vaporization methyl alcohol of superheater and the mist of water and enter converter, tail gas in decarbonization device directly discharges, though this kind of method can increase substantially the total yield of hydrogen, reduce hydrogen manufacturing cost, but owing to adopting two-phase method, investment to equipment is larger, plant area area is large, and the carbon monoxide rate of recovery is lower, be about 15%, the rate of recovery of High Purity Hydrogen is also lower, be about 91%.
Summary of the invention
The present invention mainly solves that two-phase method carries that hydrogen storage equipment investment is large, hydrogen recovery rate is lower, the technical problem that the rate of recovery is low, hydrogen manufacturing cost is high of carbon monoxide and carbon dioxide; Provide a kind of and can fully reclaim carbon monoxide and carbon dioxide, high, the total hydrogen rate of recovery of hydrogen purity is high, equipment investment is few, floor space is little, the good one-stage pressure swing adsorption hydrogen extraction of device overall economic benefit reclaim method and the device of rich carbon gas.
In order to solve the technical problem of above-mentioned existence, the present invention adopts following technical proposals:
One-stage pressure swing adsorption hydrogen extraction also reclaims the method for rich carbon gas, adopt the highly purified hydrogen of pressure-variable adsorption principle extraction from methanol synthetic discharged gas delayed as gas product, reclaim the unstripped gas of the rich carbon gas of the high-purity producing in desorption process as methanol device simultaneously, and the higher concentration producing be back to methyl alcohol system along putting hydrogen, the suitable placement ventilation of low concentration enters fuel pipe network as fuel gas, each circulation in its technological process includes adsorption process, drop pressure process, along letting slip journey, replacement process, inverse put process, vacuum, boost pressure process and the whole journey of breaking through, concrete technology flow process is as follows:
A) adsorption process: methanol synthetic discharged gas delayed after unstripped gas cell processing enters pressure-variable adsorption by import sequencing valve and carry in the adsorption tower that is in adsorbed state in hydrogen unit, under the selective absorption successively of multiple adsorbent, by the H in methanol synthetic discharged gas delayed
2o, alcohols, CO
2, CO, CH
4, N
2etc. component, absorb, the components such as the hydrogen not being adsorbed flow into product tracheae from tower top by gas product sequencing valve, input in the hydrogen gas buffer in gas product unit;
B) drop pressure process: after adsorption process finishes, by all pressing sequencing valve, along absorption direction, the hydrogen discharge of the elevated pressures in adsorption tower is entered in other lower pressure adsorption tower that has completed regeneration, this process is not only step-down process, reclaim especially the process of hydrogen in adsorption bed dead space, this process can comprise that repeatedly depressurization step is to guarantee the abundant recovery of hydrogen;
C) along letting slip journey: after drop pressure process finishes, to in adsorption tower, also have the hydrogen of certain pressure along running out, by entering along putting hydrogen air accumulator along venting sequencing valve with along putting hydrogen control valve, again be transmitted back to methyl alcohol system, thereby this process can reclaim the total hydrogen rate of recovery that improves device by the lower pressure hydrogen of adsorbent bed dead space;
D) replacement process: along letting slip after journey finishes, rich carbon gas from elevated pressures in displacement gas air accumulator enters adsorption tower bottom by displacement sequencing valve, nitrogen in adsorbent bed and methane are cemented out along putting, the gas cementing out is by exporting fuel pipe network to along venting sequencing valve and fuel gas control valve, this process can cement out the nitrogen in adsorption layer and methane, carbon dioxide in raising adsorption tower and the concentration of carbon monoxide, also improve carbon dioxide in resolution gas and the content of carbon monoxide, effectively reduced the content of nitrogen component in resolution gas;
E) inverse put process: after replacement process finishes, the gas that also has certain pressure is drained into inverse put gas surge tank by displacement sequencing valve is contrary, and send into resolution gas blending tank by pressure-regulating valve in adsorption tower, now the gas pressure in adsorption tower is down to normal pressure;
F) vacuum: after inverse put process finishes, vavuum pump vacuumizes adsorption tower by vacuumizing sequencing valve, pressure in adsorption tower further reduces, make the complete desorption of component that is adsorbed out, desorption gas is directly delivered to resolution gas blending tank, a part of desorption gas in resolution gas blending tank is sucked by compressor and compresses after boosting and enters displacement gas air accumulator, as the rich carbon gas of elevated pressures, be that replacement process is got ready, remaining desorption gas becomes the unstripped gas of methanol device again as rich carbon gas output;
G) boost pressure process: after vacuum finishes, use from the elevated pressures hydrogen in other adsorption towers this adsorption tower is continued to boost, comprise that the step of repeatedly boosting is to guarantee the abundant recovery of hydrogen, this process is corresponding with drop pressure process;
H) break through journey eventually: after boost pressure process finishes, in order to make adsorption tower can steadily switch to next time adsorption process and guarantee that product Hydrogen Vapor Pressure does not fluctuate in this course, by rushing sequencing valve end, gas product slowly and is reposefully sent in adsorption tower, make the pressure in adsorption tower rise to adsorptive pressure, guarantee that product boosts process fully and reduces the impact that adsorptive pressure fluctuates;
I) several adsorption tower alternating sequences carry out above absorption-regenerative operation process, can realize the object to methanol synthetic discharged gas delayed continuous Separation & Purification.
One-stage pressure swing adsorption hydrogen extraction also reclaims the device of rich carbon gas, comprise unstripped gas unit, pressure-variable adsorption is carried hydrogen unit, gas product unit, along venting unit and resolution gas unit, the methanol synthetic discharged gas delayed pressure-variable adsorption that enters after unstripped gas cell processing is carried hydrogen unit, extract high-purity hydrogen and export gas product unit to, the gas that desorption produces is after resolution gas cell processing, part desorption gas reenters pressure-variable adsorption as displacement gas and carries hydrogen unit, another part is recycled to methyl alcohol system as rich carbon gas, for methanol synthetic discharged gas delayed, by the pressure-variable adsorption of this device, put forward hydrogen technique, can extract highly purified hydrogen, the rich carbon gas that simultaneously obtains high-load is recycled to methyl alcohol system.
As preferably, described unstripped gas unit comprises inlet adjusting valve, superpressure control valve, metering valve and gas-liquid separator, methanol synthetic discharged gas delayed by inlet adjusting valve reduction pressure, and after metering valve calculated flow rate, enter gas-liquid separator processing, unstripped gas after treatment enters pressure-variable adsorption and carries hydrogen unit, unstripped gas after step-down and the gas-liquid separating treatment, has reached pressure-variable adsorption and has proposed the requirement of hydrogen technique.
As preferably, described pressure-variable adsorption is carried hydrogen unit and is comprised some adsorption towers and corresponding sequencing valve, pressure-variable adsorption is carried hydrogen unit and is provided with raw material gas inlet pipe, adsorption tower outlet, product tracheae, balance pipe, along bleeder pipe, whole qi of chong channel ascending adversely pipe, adsorption tower inverse put pipe, resolve tracheae and vacuum-pumping tube, between the adsorption tower inverse put pipe of described raw material gas inlet pipe and adsorption tower bottom, be provided with import sequencing valve, methanol synthetic discharged gas delayedly by import sequencing valve, enter adsorption tower, between described product tracheae and the adsorption tower outlet at adsorption tower top, be provided with gas product sequencing valve, the High Purity Hydrogen that pressure-variable adsorption extracts flows into product tracheae by gas product sequencing valve, and output to gas product unit, between described balance pipe and adsorption tower outlet, be provided with and all press sequencing valve, the hydrogen that finishes the interior elevated pressures of adsorption tower of adsorption process can be by all pressing accordingly sequencing valve flow in the adsorption tower of the lower pressure that finishes regeneration, between described suitable bleeder pipe and adsorption tower escape pipe, be provided with along venting sequencing valve, flowing into along bleeder pipe and exporting to along the unit of exitting by suitable venting sequencing valve along venting in pressure-swing absorption process, between described whole qi of chong channel ascending adversely pipe and adsorption tower outlet, be provided with and rush eventually sequencing valve, gas product from gas product unit can complete and boost by rushing end in sequencing valve inflow adsorption tower, between described parsing tracheae and adsorption tower inverse put pipe, be provided with displacement sequencing valve, desorption gas can flow into resolution gas tube side-by-side by displacement sequencing valve and go out to resolution gas unit, simultaneously, displacement gas also can be flowed into adsorption tower inverse put pipe and be entered in adsorption tower by displacement sequencing valve adsorbent is replaced, between described vacuum-pumping tube and adsorption tower inverse put pipe, be provided with and vacuumize sequencing valve, remaining desorption gas in adsorption tower enters vacuum-pumping tube and is expelled to resolution gas unit by vacuumizing sequencing valve, by controlling each sequencing valve, make different adsorption towers be operated in the different stages, the absorption and the regenerative process that guarantee adsorption tower are continuous and steady, in adsorbent bed, the hydrogen of dead space can be delivered in other adsorption tower, the gas of each component is all recycled and utilizes, total hydrogen rate of recovery of device is high, by utilizing the displacement of rich carbon gas to adsorbent bed, can improve the concentration of carbon monoxide and carbon dioxide in resolution gas, reduce the nitrogen content in resolution gas, reach the object that reclaims resolution gas.
As preferably, the quantity of described adsorption tower is 6～12, multitower cycle operation forms repeatedly all pressing in absorption-regenerative process, both reclaimed the high-purity hydrogen in adsorbent bed dead space, greatly improve the rate of recovery of hydrogen, reduced again the pressure oscillation in adsorbent bed, extended the service life of adsorbent, user can be according to actual needs and economic indicator, the quantity of reasonable selection adsorption tower.
As preferably, in described adsorption tower, be provided with one or more adsorbents, described multiple adsorbent is pressed absorption property layering filling composition composite adsorption bed successively, the different gas component of the corresponding absorption of different types of adsorbent, can fully adsorb the each gas component in methanol synthetic discharged gas delayed, gas separation effect well and and then promoted device total hydrogen rate of recovery and rich carbon gas recovery rate, improved economic benefit.
As preferably, described gas product unit comprises hydrogen gas buffer, Hydrogen Vapor Pressure control valve and whole qi of chong channel ascending adversely pressure-regulating valve, described Hydrogen Vapor Pressure control valve one end is connected with product tracheae, the other end is connected with hydrogen gas buffer, described whole qi of chong channel ascending adversely pressure-regulating valve one end is connected with product tracheae, the other end is connected with whole qi of chong channel ascending adversely pipe, the pressure that has guaranteed product hydrogen is steady, meet and use needs, simultaneously, regulate whole qi of chong channel ascending adversely to make the pressure energy that finishes regeneration adsorption tower steadily rise to adsorptive pressure, reduce the impact of pressure oscillation on adsorption process and adsorbent.
As preferably, described comprises along putting hydrogen control valve along venting unit, fuel gas control valve and the suitable hydrogen air accumulator of putting, described along putting hydrogen control valve one end and being connected along bleeder pipe, the other end is connected with along putting hydrogen air accumulator, described fuel gas control valve one end is connected with suitable bleeder pipe, the other end is connected with fuel pipe network, the hydrogen of the elevated pressures in adsorbent bed dead space is reclaimed again, be recycled to methyl alcohol system, improved the total hydrogen rate of recovery of device, and cement out contain nitrogen, the low-pressure gas of methane, can be used as fuel gas and deliver to fuel pipe network, make full use of, good in economic efficiency.
As preferably, described resolution gas unit comprises vavuum pump, compressor, displacement gas air accumulator, inverse put gas air accumulator and resolution gas blending tank, described resolution gas blending tank is respectively equipped with two imports and two outlets, between the outlet of described inverse put gas air accumulator and the import of resolution gas blending tank, be provided with pressure-regulating valve, one end of described pressure-regulating valve is connected with inverse put gas air accumulator, the other end is connected with resolution gas blending tank, the import of inverse put gas air accumulator is connected with parsing tracheae by desorption gas control valve, another import of resolution gas blending tank is connected with vacuum delivery side of pump, the import of vavuum pump is connected with vacuum-pumping tube, described compressor air suction mouth is connected with an outlet of resolution gas blending tank, the exhaust outlet of compressor is connected with displacement gas air accumulator, the other end of displacement gas air accumulator is connected with parsing tracheae by displacement gas control valve, the adsorption process desorption desorption gas that is rich in carbon dioxide and carbon monoxide is out after secondary regulates, a part is compressed by compressor and is sent into displacement gas air accumulator, as nitrogen in displacement sorption bed, the displacement gas of the gases such as methane, can improve carbon monoxide and the carbon dioxide content of desorption gas, reduce the content of nitrogen in desorption gas, can in resolution gas, obtain again highly purified rich carbon gas, be recycled to methyl alcohol system, the favorable regeneration effect of vacuum desorption, can improve the purity of product yield height and resolution gas.
As preferably, between described displacement gas air accumulator and displacement gas control valve, be provided with displacement gas flow valve, can detect in real time the flow of displacement gas.
The invention has the beneficial effects as follows: compared with conventional two sections of pressure swing adsorption methods:
1., adopt this kind of method can reach reduced investment, cost performance is high;
2., to install total hydrogen rate of recovery high, >=98%;
3., product hydrogen recovery rate is high, >=94%(CO+CO2≤10PPM);
4., the carbon monoxide rate of recovery is high, >=80%(nitrogen content≤5%), be conducive to methyl alcohol volume increase;
5., technic index is reliable and stable, handling strong;
6., install rationally distributedly, floor space is little.
Accompanying drawing explanation
Fig. 1 is a kind of process flow diagram of the present invention;
Fig. 2 is a kind of device schematic diagram of the present invention;
Fig. 3 is a kind of technological process time-scale of the present invention;
Fig. 4 is a kind of technological process operating parameter table of the present invention;
1. unstripped gas unit in figure, 11. inlet adjusting valves, 12. superpressure control valves, 13. metering valves, 14. gas-liquid separators, 2. pressure-variable adsorption is carried hydrogen unit, 21. adsorption towers, 22. raw material gas inlet pipes, 23. adsorption tower outlets, 24. product tracheaes, 25. balance pipes, 26. along bleeder pipe, 27. whole qi of chong channel ascending adversely pipes, 28. adsorption tower inverse put pipes, 29. resolve tracheae, 30. vacuum-pumping tubes, 31. import sequencing valves, 32. gas product sequencing valves, 33. all press sequencing valve, 34. along venting sequencing valve, 35. rush sequencing valve eventually, 36. displacement sequencing valves, 37. vacuumize sequencing valve, 4. gas product unit, 41. hydrogen gas buffers, 42. Hydrogen Vapor Pressure control valves, 43. whole qi of chong channel ascending adversely pressure-regulating valves, 5. along venting unit, 51. along putting hydrogen control valve, 52. fuel gas control valves, 53. along putting hydrogen air accumulator, 6. resolution gas unit, 61. vavuum pumps, 62. compressors, 63. displacement gas air accumulators, 64. inverse put gas air accumulators, 65. resolution gas blending tanks, 66. pressure-regulating valves, 67. desorption gas control valves, 68. displacement gas control valves, 69. displacement gas flow valves.
The specific embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment: the one-stage pressure swing adsorption hydrogen extraction of the present embodiment also reclaims the device of rich carbon gas, as shown in Figure 1, adopt the highly purified hydrogen of pressure-variable adsorption principle extraction from methanol synthetic discharged gas delayed as gas product, reclaim the unstripped gas of the rich carbon gas of the high-purity producing in desorption process as methanol device simultaneously, and the higher concentration producing be back to methyl alcohol system along putting hydrogen, the suitable placement ventilation of low concentration enters fuel pipe network as fuel gas, pressure-variable adsorption is carried hydrogen unit and is adopted 10-2-6PR/VPSA, as shown in Figure 2, adsorption tower quantity is 10, wherein there are all the time two adsorption towers in adsorbed state, pressure equalizing is 6 times, each circulation in its technological process includes adsorption process, drop pressure process, along letting slip journey, replacement process, inverse put process, vacuum, boost pressure process and the whole journey of breaking through, technological process time-scale as shown in Figure 3, the operating parameter table of technological process as shown in Figure 4, concrete technology flow process (take the work of A tower as example) is as follows:
A) adsorption process: the pressure coming from the outside is 5.0Mpa, temperature is 30 ℃ of methanol synthetic discharged gas delayed this devices that enter, after unstripped gas cell processing, be decompressed to 2.7 MPa, by import sequencing valve 31A, enter in A tower, under the selective absorption successively of multiple adsorbent, by the H in methanol synthetic discharged gas delayed
2o, alcohols, CO
2, CO, CH
4, N
2etc. component, absorb, the components such as the hydrogen not being adsorbed flow into product tracheae 24 from tower top by gas product sequencing valve 32A, input in the hydrogen gas buffer in gas product unit 4 41, and adsorption time is about 120 seconds;
B) drop pressure process: after adsorption process finishes, close import sequencing valve 31A and gas product sequencing valve 32A, open and all press sequencing valve 33A and 33D, along absorption direction, the hydrogen discharge of 2.7 MPa in A tower is entered to complete the D tower of regeneration, time is 15 seconds, and now A, D two pressure tower balances are 2.302 MPa;
Close and all press sequencing valve 33D, open and all press sequencing valve 33E, in A tower, the hydrogen of 2.302 MPa flows into E tower along absorption direction, and the time is 15 seconds, and now A, E two pressure tower balances are 1.905 MPa;
Close and all press sequencing valve 33E, open and all press sequencing valve 33F, in A tower, the hydrogen of 1.905 MPa flows into F tower along absorption direction, and the time is 15 seconds, and now A, F two pressure tower balances are 1.508MPa;
Close and all press sequencing valve 33F, open and all press sequencing valve 33G, in A tower, the hydrogen of 1.508MPa flows into G tower along absorption direction, and the time is 15 seconds, and now A, G two pressure tower balances are 1.111 MPa;
Close and all press sequencing valve 33G, open and all press sequencing valve 33H, in A tower, the hydrogen of 1.111 MPa flows into H tower along absorption direction, and the time is 15 seconds, and now A, H two pressure tower balances are 0.714 MPa;
Close and all press sequencing valve 33H, open and all press sequencing valve 33I, in A tower, the hydrogen of 0.714 MPa flows into I tower along absorption direction, and the time is 15 seconds, and now A, I two pressure tower balances are 0.317 MPa;
C) along letting slip journey: after drop pressure process finishes, close and all press sequencing valve 33A and 33I, open along venting sequencing valve 34A with along putting hydrogen control valve 51, in A tower, the hydrogen of 0.317 MPa flows into along putting hydrogen air accumulator 53, time is 15 seconds, and now the pressure drop in A tower is 0.15 MPa;
D) replacement process: along letting slip after journey finishes, close along putting hydrogen control valve 51, open fuel gas control valve 52, displacement sequencing valve 36A and displacement gas control valve 68, rich carbon gas from displacement gas air accumulator 63 interior elevated pressures enters A tower by displacement sequencing valve 36A, nitrogen in adsorbent bed and methane are cemented out along putting, the gas cementing out is by exporting fuel pipe network to along venting sequencing valve 34A and fuel gas control valve, time swap is 15 seconds, and now the pressure drop in A tower is 0.1 MPa;
E) inverse put process: after replacement process finishes, close along venting sequencing valve 34A, fuel gas control valve 52 and displacement gas control valve 68, open desorption gas control valve 67, the contrary inverse put gas surge tank 64 that drains into of the gas of 0.1 MPa in A tower, and send into resolution gas blending tank 65 by pressure-regulating valve 66, the inverse put time is 15 seconds, and now the Pressure Drop in A tower is to normal pressure;
F) vacuum: after inverse put process finishes, close desorption gas control valve 67 and displacement sequencing valve 36A, open and vacuumize sequencing valve 37A and vavuum pump 61, A tower is vacuumized, pressure in A tower further reduces, make the complete desorption of component that is adsorbed out, desorption gas is directly delivered to resolution gas blending tank 65, a part of desorption gas in resolution gas blending tank is sucked by compressor 62 and compresses after boosting and enters displacement gas air accumulator 63, as the rich carbon gas of elevated pressures, be that replacement process is got ready, remaining desorption gas is exported the unstripped gas as methanol device again as rich carbon gas, pumpdown time is 60 seconds, now the pressure drop in A tower is-0.08 MPa,
G) boost pressure process: after vacuum finishes, close and vacuumize sequencing valve 37A and vavuum pump 61, open and all press sequencing valve 33A and 33C, along absorption direction, the hydrogen of 0.714 MPa in C tower is introduced to the A tower that has completed regeneration, time is 15 seconds, and now A, C two pressure tower balances are 0.317 MPa;
Close and all press sequencing valve 33C, after time delay in 30 seconds, open and all press sequencing valve 33D, in D tower, the hydrogen of 1.111MPa flows into A tower along absorption direction, and the time is 15 seconds, and now A, D two pressure tower balances are 0.714 MPa;
Close and all press sequencing valve 33D, after time delay in 30 seconds, open and all press sequencing valve 33E, in E tower, the hydrogen of 1.508 MPa flows into A tower along absorption direction, and the time is 15 seconds, and now A, E two pressure tower balances are 1.111MPa;
Close and all press sequencing valve 33E, after time delay in 30 seconds, open and all press sequencing valve 33F, in F tower, the hydrogen of 1.905MPa flows into A tower along absorption direction, and the time is 15 seconds, and now A, F two pressure tower balances are 1.508 MPa;
Close and all press sequencing valve 33F, after time delay in 30 seconds, open and all press sequencing valve 33G, in G tower, the hydrogen of 2.302 MPa flows into G tower along absorption direction, and the time is 15 seconds, and now A, G two pressure tower balances are 1.905 MPa;
Close and all press sequencing valve 33G, after time delay in 30 seconds, open and all press sequencing valve 33H, in H tower, the hydrogen of 2.7MPa flows into A tower along absorption direction, and the time is 15 seconds, and now A, H two pressure tower balances are 2.302 MPa;
Use from the elevated pressures hydrogen in other adsorption towers A tower is continued to boost, comprise that the step of boosting for six times is to guarantee the abundant recovery of hydrogen, this process is corresponding with drop pressure process;
H) break through journey eventually: after boost pressure process finishes, open and rush eventually sequencing valve 35A, the gas product of 2.7 MPa flows in A tower, and the time is 45 seconds, and now the pressure rise in A tower is 2.7 MPa, reaches the pressure requirement of absorption;
I) 10 adsorption tower alternating sequences carry out above absorption-regenerative operation process, can realize the object of the continuous Separation & Purification of unstripped gas.
More than explanation has not been done restriction to the present invention; the present invention is also not limited only to giving an example of above-mentioned explanation; variation that those skilled in the art have done in essential scope of the present invention, retrofit, increase or replace, all should be considered as protection scope of the present invention.
Claims (1)
1. an one-stage pressure swing adsorption hydrogen extraction reclaim the method for rich carbon gas, adopt the highly purified hydrogen of pressure-variable adsorption principle extraction from methanol synthetic discharged gas delayed, reclaim the unstripped gas of the rich carbon gas of the high-purity producing in desorption process as methanol device simultaneously, and the suitable hydrogen of putting of the higher concentration producing reclaims the methyl alcohol system that is returned to, the suitable placement ventilation of low concentration enters fuel pipe network as fuel gas, each circulation in its technological process includes adsorption process, drop pressure process, along letting slip journey, replacement process, inverse put process, vacuum, boost pressure process and the whole journey of breaking through, concrete technology flow process is as follows:
A) adsorption process: methanol synthetic discharged gas delayed after unstripped gas cell processing enters pressure-variable adsorption by import sequencing valve and carry in the adsorption tower that is in adsorbed state in hydrogen unit, under the selective absorption successively of multiple adsorbent, the H in methanol synthetic discharged gas delayed
2o, alcohols, CO
2, CO, CH
4, N
2etc. component, be adsorbed, the components such as the hydrogen not being adsorbed flow into product tracheae from tower top by gas product sequencing valve, input in the hydrogen gas buffer in gas product unit;
B) drop pressure process: after adsorption process finishes, by all pressing sequencing valve, along absorption direction by adsorption tower in the hydrogen discharge of elevated pressures enter in other lower pressure adsorption tower that has completed regeneration, this process is not only step-down process, reclaim especially the process of hydrogen in adsorption bed dead space, this process can comprise that repeatedly depressurization step is to guarantee the abundant recovery of hydrogen;
C) along letting slip journey: after drop pressure process finishes, to in adsorption tower, also have the hydrogen of certain pressure along running out, by entering along putting hydrogen air accumulator along venting sequencing valve with along putting hydrogen control valve, again be transmitted back to methyl alcohol system, thereby this process can reclaim the total hydrogen rate of recovery that improves device by the lower pressure hydrogen of adsorbent bed dead space;
D) replacement process: along letting slip after journey finishes, rich carbon gas from elevated pressures in displacement gas air accumulator enters adsorption tower bottom by displacement sequencing valve, nitrogen in adsorbent bed and methane are cemented out along putting, the gas cementing out is by exporting fuel pipe network to along venting sequencing valve and fuel gas control valve, this process can cement out the nitrogen in adsorption layer and methane, carbon dioxide in raising adsorption tower and the concentration of carbon monoxide, also improve carbon dioxide in resolution gas and the content of carbon monoxide, effectively reduced the content of nitrogen component in resolution gas;
E) inverse put process: after replacement process finishes, the gas that also has certain pressure is drained into inverse put gas surge tank by displacement sequencing valve is contrary, and send into resolution gas blending tank by pressure-regulating valve in adsorption tower, now the gas pressure in adsorption tower is down to normal pressure;
F) vacuum: after inverse put process finishes, vavuum pump vacuumizes adsorption tower by vacuumizing sequencing valve, pressure in adsorption tower further reduces, make the complete desorption of component that is adsorbed out, desorption gas is directly delivered to resolution gas blending tank, a part of desorption gas in resolution gas blending tank is sucked by compressor and compresses after boosting and enters displacement gas air accumulator, as the rich carbon gas of elevated pressures, be that replacement process is got ready, remaining desorption gas becomes the unstripped gas of methanol device again as rich carbon gas output;
G) boost pressure process: after vacuum finishes, use from the elevated pressures hydrogen in other adsorption towers this adsorption tower is continued to boost, comprise that the step of repeatedly boosting is to guarantee the abundant recovery of hydrogen, this process is corresponding with drop pressure process;
H) break through journey eventually: after boost pressure process finishes, in order to make adsorption tower can steadily switch to next time adsorption process and guarantee that product Hydrogen Vapor Pressure does not fluctuate in this course, by rushing sequencing valve end, gas product slowly and is reposefully sent in adsorption tower, make the pressure in adsorption tower rise to adsorptive pressure, guarantee that product boosts process fully and reduces the impact that adsorptive pressure fluctuates;
I) several adsorption tower alternating sequences carry out above absorption-regenerative operation process, can realize the object to methanol synthetic discharged gas delayed continuous Separation & Purification.
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| FR2991192A1 (en) * | 2012-06-04 | 2013-12-06 | Air Liquide | PROCESS FOR THE PRODUCTION OF HYDROGEN AT DIFFERENT LEVELS OF PURITY BY H2 PSA |
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