CN103466546A - Intermediate temperate pressure swing adsorption method for using bifunctional adsorbent in adsorption enhanced type vapor reforming and water-vapor transformation reactions - Google Patents
Intermediate temperate pressure swing adsorption method for using bifunctional adsorbent in adsorption enhanced type vapor reforming and water-vapor transformation reactions Download PDFInfo
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Abstract
The invention discloses an intermediate temperature pressure swing adsorption method for using a bifunctional adsorbent in adsorption enhanced type vapor reforming and water-vapor transformation reactions, belonging to the technical field of clean energy. According to the method, the bifunctional adsorbent which has dual functions of catalytic reaction and decarburization desulphurization is added into a reactor. The process ensures that multiple hydrogen production reactions are performed in the same reactor under an intermediate temperature condition, so that the investment in system equipment is reduced and the process flow is simplified; the temperature of a reforming reactor is low, the requirement for steel products is lowered, and the equipment cost is reduced; the sensitive heat of raw material gas can be directly recovered, the overall thermal efficiency of a system is improved, heat exchange equipment of the system is reduced, and the system cost is reduced; the adsorption/regeneration of the adsorbent can be realized without temperature rise and drop, the energy consumption is reduced, the regeneration speed of the adsorbent is high, and the gas treating capacity of a pressure swing adsorption system can be improved.
Description
Technical field
The invention belongs to the clean energy technology field, be specifically related to a kind of method of utilizing difunctional sorbent material to be adsorbed enhanced steam reforming and water gas shift reaction and middle temperature pressure-variable adsorption.
Background technology
Along with energy environment issues highlights day by day, H
2fuel as a kind of clean and effective receives much concern, and hydrogen is also starting material important in chemical industry simultaneously.Methane vapor reforming is the major way of traditional large-scale industry hydrogen manufacturing, and other hydrocarbon fuel also can prepare hydrogen through steam reforming and synthesis gas from coal gasification through water gas shift reaction in addition.Take methane vapor reforming as example, and in the traditional industry route, unstripped gas need could finally make high-purity hydrogen by reforming reactor, water gas shift reactor and three processing steps of purifying plant.Methane and water vapour at first in reformer, react (1) make H
2and CO, then enter in water gas shift reactor react (2) and further improve H
2productive rate, finally remove the CO in gas product by purifying plant
2deng acquisition high purity H
2.
Reforming reaction:
Water gas shift reaction:
Reforming reaction and water gas shift reaction are reversible reaction, CH
4with CO, be difficult to realize transforming fully.In addition, reforming reaction is a strong thermo-negative reaction, in order to improve transformation efficiency, need to use outer heat supply, usually need to keep service temperature at 800-900 ℃, pressure is at 1.5-2MPa, and the gas product temperature made by water gas shift reaction is usually between 200-450 ℃.But, the CO of ripe application
2/ H
2the separating technology route mainly comprises normal temperature or low temperature wet method decarburization technique (as Selexol/NHD technology, active MDEA technology, low-temperature rectisol technology), need be at first to the processing of lowering the temperature of synthetic gas after hydrosphere transformation, waste gas sensible heat.
Absorb (absorption) enhanced steam reforming (or synthetic gas hydrosphere transformation) and added CO in traditional reformation (or synthetic gas hydrosphere transformation) reactor
2absorb (absorption) agent.According to Le Chatelier's principle, as the CO of reforming reaction and water gas shift reaction generation
2be absorbed, reaction can be towards H
2the direction increased is carried out, thereby significantly improves feed stock conversion.Due to CO
2absorb the enhancement of (absorption), the hydrocarbon fuel vapor reforming hydrogen production can complete reforming reaction, water gas shift reaction and H in a reactor
2purify; Synthesis gas from coal gasification water gas shift reaction and H
2purify and also can complete in a reactor.
CO in reformation (or hydrosphere transformation) reactor
2removing process comprises chemical absorption method and pressure swing adsorption process (Pressure Swing Adsorption, PSA).Chemical absorption method be take Ca-base adsorbent as representative, and its principle is: Ca-base adsorbent is in (or hydrosphere transformation) reactor of reforming and CO
2after chemical reaction occurs, CO in gas
2be removed, adsorb saturated sorbent material and enter the regeneration reactor calcining and decomposing and go out CO
2, absorption and regeneration hockets, thereby realizes the Separation and Recovery of carbonic acid gas.But the regeneration temperature of Ca-base adsorbent is higher, energy consumption is very large, and easily causes the absorbent particles sintering, the stability of impact circulation.
The ultimate principle of PSA technology utilizes the difference of gaseous fraction characterization of adsorption on solid porous sorbent material and adsorptive capacity with the characteristic of change in pressure, realizes separation or the purification of gas by periodic pressure conversion process.The product separated as required in absorption or non-adsorbed state, can be divided into Adsorption Phase product and fluid phase product in adsorption bed.For example, the composition of the synthetic gas of the industries such as hydrocarbon fuel and gasification, gasifying biomass, petrochemical industry, Sweet natural gas there are differences because raw material is different, and its essentially consist mainly comprises: C
xh
y, CO
2, CO, O
2, N
2, H
2, H
2s, H
2o etc.In said components, common H
2o, CO
2, H
2s is strong absorbed component, C
xh
y, the CO adsorptive power is placed in the middle, O
2, N
2weak absorbed component, and H
2absorption hardly.Usually, in the PSA system, use a plurality of adsorption towers that are filled with sorbent material.Import unstripped gas in each adsorption tower, by repeatedly being adsorbed enhanced hydrogen manufacturing operation, decompression operation, desorption operation and the operation of boosting, obtain the product gas as object.The principle that obtains purpose gas is described below: if the pressure of the gas in adsorption tower uprises, the dividing potential drop of the eliminating gas that the unstripped gas reaction generates also uprises, its result, get rid of gaseous constituent and be filled in the sorbent material absorption (in tower, gas, removing some gaseous constituent) in adsorption tower, improve the unstripped gas transformation efficiency, discharge gas in tower under this state, obtain getting rid of the goods gas that gaseous constituent is few, after this, with the adsorption tower internal pressure, reduce, or purge with non-adsorbed gas, get rid of gaseous constituent from sorbent material desorption (adsorbent reactivation), the composition of desorption becomes to be divided into non-adsorptivity purpose gas with other, the sorbent material of regeneration can be further used for removing and getting rid of gaseous constituent from the unstripped gas reaction of new importing, the sorbent material used in each adsorption tower need maybe should be removed gaseous species according to the purpose gaseous species and select, for example, if in order to remove CO from unstripped gas
2, obtain H
2goods gas, select gac, adsorbent of molecular sieve usually.
At present, the PSA gas separating method has been widely used in the CO in baking tail gases, lime-kiln gas in Sweet natural gas, coal firing boiler stack gas, synthetic-ammonia transformation gas, alumina producing
2remove and the field such as recovery, the shortcoming such as the method has overcome complicated operation in wet method decarburization, desulfurization, energy consumption is high, expense is high, equipment corrosion is large.But traditional PSA adsorption separation process sorbent suspension and equipment work condition restriction, often can only select normal temperature operation (as 20-45 ℃).Simultaneously, common PSA sorbent material (as molecular sieve) is for H
2the existence of O is also very responsive, at H
2in the situation of O and other gas coexistences, can preferentially optionally absorb H
2o, so pressure-swing adsorption process and reforming reaction or water gas shift reaction still can not carry out in same reactor simultaneously, the gas product of reforming reaction or water gas shift reaction need to be again by independently the PSA system could purifying hydrogen of hydrogen after cooling and dehydration.If directly catalyzer is mixed or compound use with sorbent material, catalyzed reaction and absorption reaction ex situ coupling on the one hand, efficiency is lower; Required catalyzer and sorbent material consumption all will increase on the other hand, can amass by the augmenting response body, thereby increase equipment cost.In addition, some unstripped gas may also contain H
2s, need arrange desulfurizer, and system complexity and cost of investment increase.
Summary of the invention
The object of the present invention is to provide a kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming reaction and water gas shift reaction.
A kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction, difunctional sorbent material is seated in adsorption tower, can make steam reforming reaction, water gas shift reaction and middle temperature Pressure Swing Adsorption hydrogen complete in same reactor, temperature of reaction is 200-500 ℃; Described difunctional sorbent material has the dual-use function of catalyzed aqueous vapour reformation and water gas shift reaction and decarbonization, desulfuration, the mixture that described difunctional sorbent material is middle temperature sorbent material or middle temperature sorbent material and low temperature adsorbent, the middle temperature sorbent material in this mixture account for the sorbent material total mass more than 2% and be less than 100%; Detailed process for by unstripped gas successively by obtaining gas product after two or more adsorption towers, complete pressurising, absorption enhanced hydrogen production reaction, gas product recovery, drop pressure in each adsorption tower, forward bleed off pressure, reversely bleed off pressure, steam desorb, flushing, boost pressure and fill eventually step.
Above-mentioned difunctional sorbent material not only has the function of decarburization and desulfurization, and to H
2a little less than O absorption, therefore can be applied directly to the purification of steam reforming and hydrosphere transformation gas product.And this difunctional sorbent material also possesses the function of catalyzed aqueous vapour reforming reaction and water gas shift reaction simultaneously, and active good under 200-500 ℃.Therefore utilize this difunctional sorbent material, steam reforming reaction and water gas shift reaction and middle temperature pressure-swing adsorption process can be carried out in same reactor, solve in the past the PSA system can't be incorporated into to the defect of carrying out in same reactor and the shortcoming of composite catalyst with above-mentioned two-step reaction.
Above-mentioned each adsorption tower comprises following concrete steps in one-period:
(1) pressurising
The unstripped gas or the gas product that by temperature, are 200-500 ℃ are boosted to adsorption tower, to adsorptive pressure be 0.01-30MPa;
(2) absorption enhanced hydrogen production reaction
Unstripped gas is sent into to adsorption tower from adsorption tower bottom, in the katalysis of sorbent material, issued unboiled water steam reforming and water gas shift reaction.The component CO of the easy absorption that simultaneously, reaction generates
2and H
2s is adsorbed the agent selective adsorption, is difficult for the gas H of absorption
2, H
2o and N
2, by whole adsorption tower bed, from outlet, discharge; When absorb leading-edge moves to the certain position of bed, stop adsorption operations;
(3) gas product reclaims
Discharge gas product from the gas product end, along with the continuous discharge of gas product, the tower internal pressure constantly descends, and when the adsorbed gas forward position is advanced to certain position, stops reclaiming product;
(4) drop pressure
After stopping reclaiming gas product, the product end of adsorption tower continues Exhaust Gas, but this part gas is used to another adsorption tower that completes desorption process to boost, and this step can change according to the adsorption tower number change, can be 1-6 time;
(5) forward bleed off pressure
After drop pressure, along the absorption direction, continue to emit gas, return to the unstripped gas system.If, when gas product recycling step yield is larger, after the end of processing of drop pressure, the tower internal pressure has been down to the low pressure of pressure swing adsorption system, cancels this step;
(6) reverse bleeding off pressure
Discharge gas in adsorption tower in the other direction along absorption, reduce pressure, this part gas can return to the unstripped gas system, or directly enters in another adsorption tower that has completed adsorbent reactivation;
(7) vacuum pump-down
When approaching normal atmosphere, adsorption tower is vacuumized to step-down when adsorption bed pressure;
(8) steam desorb
Pass into steam in adsorption tower, further reduce the dividing potential drop of adsorbed gas, realize the regeneration of sorbent material;
(9) rinse
By reverse, bleeding off pressure the Pressure Drop of adsorption tower to normal pressure, is further to reduce the impurity composition dividing potential drop, adopts the mode of rinsing sorbent material along venting, and impurities partial pressure in adsorption tower is further reduced, and completes the regeneration of sorbent material;
(10) boost pressure
By and complete between the adsorption tower of adsorption process the mode that adopts pressure in twos average, the pressure of the adsorption tower of regeneration is improved;
(11) fill eventually
By boost pressure, can only be that adsorption column pressure is necessarily raise, also there be certain difference in the pressure of itself and whole system, and this part difference is finally used gas product to carry out pressurising, and the pressure of adsorption tower is risen to system pressure.
The above-mentioned raw materials gas bag is containing C
xh
y, CO
2, CO, O
2, N
2, H
2, H
2s and H
2o, wherein x and y are integer, 1≤x≤20,4≤y≤42; The said products gas is mainly H
2.
Above-mentioned preferred C
xh
y, wherein x and y are integer, 1≤x≤12,4≤y≤26.
Hydrotalcite, the houghite of modification, Na that above-mentioned middle temperature sorbent material is hydrotalcite, houghite, modification
2the Al that O modifies
2o
3, modification or unmodified double salt sorbent material or other can realize CO under 200-500 ℃ of condition
2, H
2the material of the adsorption and desorption of S; Described low temperature adsorbent is molecular sieve or gac.
Above-mentioned modification or unmodified hydrotalcite or houghite sorbing material are following general formula compound:
[M
2 1-xM
3 x(OH)
2][A]
2-x·yH
2O·zM
1 2(1-w)M
3 wB
Wherein, M
1for Li
+, Na
+, K
+, Cr
+, Rb
+in monovalent cation or its mixture; M
2for Mg
2+, Ca
2+, Mn
2+, Fe
2+, Co
2+, Ni
2+, Zn
2+in divalent cation or its mixture; M
3for Al
3+, Cr
3+, Mn
3+, Co
3+, Ni
3+, La
3+in Tricationic or its mixture.[A] is NO
3 -, SO
4 2-, CO
3 2-, Cl
-, Br
-, F
-, I
-, C
xh
yo
z n-; B is O
2-or CO
3 2-; N=1 or 2; X=0-1; Y=0-4; Z=0-7, w=0-1.The houghite material that the hydrotalcite that further the preferred hydrotalcite sorbing material of modifying is the potassium modification or potassium are modified.
The salt that the positively charged ion that above-mentioned modification or unmodified double salt sorbent material are two or more and a kind of negatively charged ion form.Wherein, positively charged ion is from above-mentioned M
1, M
2or M
3middle selection, negatively charged ion is from above-mentioned [A], O
2-or CO
3 2-middle selection.Further preferred double salt sorbent material is MgO-K
2o double salt.
Beneficial effect of the present invention: add difunctional sorbent material in reactor, this sorbent material possesses catalyzed reaction and decarbonization, desulfuration dual-use function, the multistep hydrogen production reaction can carry out under medium temperature condition in same reactor, cancelling hydrogen purification equipment can reduce costs, simplification of flowsheet, and catalytic efficiency and the unstripped gas transformation efficiency high; Can reclaim the unstripped gas sensible heat, improve entire system thermo-efficiency, and reduce heat-exchange equipment, further reduce costs; Without heating and cooling, can realize the absorption/regenerative process of sorbent material, and adsorbent reactivation speed is fast, can improve the gas processing capability of PSA system; Can realize CO in gas
2with H
2jointly removing of S component, can reduce sweetener, reduces system complexity.CO is only arranged in unstripped gas
2the time, also can realize removing separately CO
2.
The accompanying drawing explanation
The middle temperature pressure swing adsorption system schematic diagram of the absorption enhanced hydrogen manufacturing that Fig. 1 is four tower configurations;
The middle temperature pressure swing adsorption system schematic diagram of the absorption enhanced hydrogen manufacturing that Fig. 2 is two tower configurations;
In figure, A, B, C, D, 1 and 2 respectively represent an adsorption tower.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described in detail.
Embodiment 1:
This example has adopted four adsorption tower configurations, as shown in Figure 1.Unstripped gas by utilidor, through high temperature resistant sequencing valve, is delivered to adsorption tower by the unstripped gas surge tank; Device consists of 4 adsorption towers, and each adsorption tower needs experience absorption, 2 equal pressure drops, forward bleeds off pressure, reversely bleeds off pressure, rinses in a loop cycle, 2 equal voltage rises and fill step end.
Feed gas composition is as follows:
Raw gas pressure: 5MPa
Unstripped gas temperature: 400-450 ℃
The pressure of four adsorption towers is adjustable, and sorbent material is housed in adsorption tower, and sorbent material is by K
2cO
3mg-Al hydrotalcite and molecular sieve, the gac modified are composited, K
2cO
3the Mg-Al hydrotalcite of modifying accounts for 50% of sorbent material total mass.
After unstripped gas enters adsorption tower, carry out steam reforming and water gas shift reaction under the katalysis of difunctional sorbent material, the CO that reaction produces
2, H
2s etc. easily adsorbed gas are adsorbed the sorbent material absorption of loading in device, and hydrogen flows out adsorption tower; When the loading capacity of sorbent material reach its saturated extent of adsorption 60% the time, between adsorption tower, automatically switch, the adsorption tower step-down of previous work enters the step-down reproduced state, the adsorption tower of having regenerated enters adsorbed state through pre-loading to operating pressure again.
The regeneration of adsorption tower is mainly according to the pressure difference, and the principle that the adsorptive capacity of adsorbate on mixed fillers is different, when reducing the pressure of adsorption tower, is attracted to the impurity automatic unbuckling absorption on mixed fillers, is excluded from adsorption tower, and mixed fillers is realized regeneration.The regeneration of adsorption tower comprises drop pressure, reverse step-down and three states of steam flush.Drop pressure refer to adsorption tower in the step-down reproduced state by the gas in adsorption tower all in pre-loading state and the lower adsorption tower of pressure, can effectively utilize like this residual air in adsorption tower, avoid, by its discharge system, causing waste, improve the rate of recovery; Reverse step-down refers to the adsorption tower in the step-down reproduced state, when its pressure is in all adsorption towers during minimal pressure, the part of this part residual gas is collected through backflow gas.
Be below the concrete operation step of the above pressure-variable adsorption enhanced hydrogen production process:
A. adsorb the enhanced hydrogen production reaction
Unstripped gas enters from the adsorption tower bottom, and steam reforming and water gas shift reaction occur, and the impurity composition in gas is optionally adsorbed by multiple sorbent material.The hydrogen be not adsorbed is as gas product.Obtained qualified gas product by this step.
B. desorption
1. all pressure drops
The sorbent material that completes adsorption process contains a large amount of impurity compositions, utilize sorbent material loading capacity under high pressure, low temperature large, low pressure, the characteristics that the high temperature adsorption capacity is little, by all pressures between adsorption tower, the working pressure that reduces sorbent material makes the impurity be adsorbed obtain the part desorb.
2. forward bleed off pressure
After completing pressure equalizing, along the direction of absorption, emit the gas that a part of density of hydrogen is very high, the source of the gas as another one in the rinse step adsorption tower, reduce the impurities partial pressure in this purge column, and purge column is regenerated.And by forward bleeding off pressure, the spontaneous pressure of adsorption tower decreases, and impurity obtains the part desorb.
3. reverse bleeding off pressure
After completing equal pressure drop process, certain pressure that adsorption tower generally still exists.At this moment, the impurity composition that adsorption tower is desorbed out is full of, and this partial impurities is emitted adsorption tower against the direction of absorption, by reverse process against pressure, makes the pressure of adsorption tower approach normal pressure.
4. vacuum pump-down
By reverse bleed off pressure adsorption column pressure is down to approach normal pressure after, adsorption tower is proceeded to vacuumize step-down.
5. steam flush
For further reducing the impurity composition dividing potential drop, adopt the mode of steam flush sorbent material, impurities partial pressure in adsorption tower is reduced, adsorbent reactivation is to the requirement of regulation.
By the acting in conjunction of top three kinds of modes, the regeneration of sorbent material complete.
C. absorption is prepared
The absorption set-up procedure is mainly that adsorption column pressure is returned back to system pressure, and its Recovery Process generally is divided into:
1. all voltage rises
By and complete between the adsorption tower of adsorption process the mode that adopts pressure in twos average, the pressure of the adsorption tower of regeneration is improved.This process is the process of boosting, and is also a process that reclaims dead space active principle in other adsorption towers simultaneously.
2. fill eventually
By equal voltage rise, can only make adsorption column pressure necessarily be raise, also there is certain difference in the pressure of itself and whole system, and this part difference is finally used gas product to carry out pressurising, and the pressure of adsorption tower is risen to system pressure.
So far, single adsorption tower has completed a complete absorption-desorption circulation after experiencing above process, can start the adsorption process of new one-period, and other three adsorption towers are like this too, just each time step staggers mutually, and once the cycle of circulation is 30 minutes.Whole process temperature is controlled between 400-450 ℃, and complete assembly is selected corrosion-resistant withstand voltage material, and all devices has Insulation.
Efficiency of carbon conversion in unstripped gas>90%, H
2the S decreasing ratio>95%, the product hydrogen purity>after the 90%(drying), the products C O of recovery
2purity>after the 90%(drying).
Embodiment 2:
This example has adopted four tower configurations, as shown in Figure 1.Unstripped gas by utilidor, through high temperature resistant sequencing valve, is delivered to adsorption tower by the unstripped gas surge tank.
Feed gas composition is as follows:
Raw gas pressure: 3MPa
Unstripped gas temperature: 200-300 ℃
The pressure of four adsorption towers is adjustable, and sorbent material is housed in adsorption tower, and Zn-Al hydrotalcite and molecular sieve, gac that sorbent material is modified by Na are composited, NaNO
3the Zn-Al hydrotalcite of modifying accounts for 70% of sorbent material total mass.
Concrete operation step is with embodiment 1, the place changed is as follows: when the loading capacity of sorbent material reach capacity adsorptive capacity 60% the time, between adsorption tower, automatically switch, the adsorption tower step-down of previous work enters the step-down reproduced state, and the adsorption tower of having regenerated enters adsorbed state through pre-loading to operating pressure again; Whole process temperature is controlled between 200-300 ℃.Complete assembly is selected corrosion-resistant withstand voltage material, and all devices has Insulation.
Efficiency of carbon conversion in unstripped gas>90%, H
2the S decreasing ratio>95%, the product hydrogen purity>after the 90%(drying), the products C O of recovery
2purity>after the 90%(drying).
Embodiment 3:
This example has adopted 2 adsorption tower configurations, as shown in Figure 2.Unstripped gas by utilidor, through high temperature resistant sequencing valve, is delivered to adsorption tower by the unstripped gas surge tank.The step of each adsorption tower experience comprises pressurising, adsorbs, bleeds off pressure, four steps of purge.
Feed gas composition is as follows:
Raw gas pressure: 3MPa
Unstripped gas temperature: 200-300 ℃
The pressure of two adsorption towers is adjustable, and sorbent material is housed in adsorption tower, and sorbent material is by Na
2cO
3mg-Al hydrotalcite and the gac modified are composited, and the Mg-Al hydrotalcite that Na modifies accounts for 20% of sorbent material total mass.
Concrete operation step is with embodiment 1, the place changed is as follows: when the loading capacity of sorbent material reach capacity adsorptive capacity 40% the time, between adsorption tower, automatically switch, the adsorption tower step-down of previous work enters the step-down reproduced state, and the adsorption tower of having regenerated enters adsorbed state through pre-loading to operating pressure again; Whole process temperature is controlled between 200-300 ℃.Complete assembly is selected corrosion-resistant withstand voltage material, and all devices has Insulation.
Efficiency of carbon conversion in unstripped gas>90%, H
2the S decreasing ratio>95%, the product hydrogen purity>after the 90%(drying), the products C O of recovery
2purity>after the 90%(drying).
Claims (5)
1. a middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction, it is characterized in that, difunctional sorbent material is seated in adsorption tower, steam reforming reaction, water gas shift reaction and middle temperature Pressure Swing Adsorption hydrogen are completed in same reactor, and temperature of reaction is 200-500 ℃; Described difunctional sorbent material has the dual-use function of catalyzed aqueous vapour reformation and water gas shift reaction and decarbonization, desulfuration, the mixture that described difunctional sorbent material is middle temperature sorbent material or middle temperature sorbent material and low temperature adsorbent, the middle temperature sorbent material in this mixture account for the sorbent material total mass more than 2% and be less than 100%; Detailed process for by unstripped gas successively by obtaining gas product after two or more adsorption towers, complete pressurising, absorption enhanced hydrogen production reaction, gas product recovery, drop pressure in each adsorption tower, forward bleed off pressure, reversely bleed off pressure, steam desorb, flushing, boost pressure and fill eventually step.
2. a kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction according to claim 1, is characterized in that, described unstripped gas comprises C
xh
y, CO
2, CO, O
2, N
2, H
2, H
2s and H
2o, wherein x and y are integer, 1≤x≤20,4≤y≤42; Described gas product is mainly H
2.
3. a kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction according to claim 2, is characterized in that described C
xh
yin x and y be integer, 1≤x≤12,4≤y≤26.
4. a kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction according to claim 1, it is characterized in that hydrotalcite, the houghite of modification, Na that described middle temperature sorbent material is hydrotalcite, houghite, modification
2the Al that O modifies
2o
3, modification or unmodified double salt sorbent material or other can realize CO under 200-500 ℃ of condition
2, H
2the material of the adsorption and desorption of S; Described low temperature adsorbent is molecular sieve or gac.
5. a kind of middle temperature pressure swing absorption process that difunctional sorbent material is applied to adsorb enhanced steam reforming and water gas shift reaction according to claim 1, is characterized in that, described middle temperature sorbent material is the houghite that the hydrotalcite modified of potassium or potassium are modified.
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| CN104030241A (en) * | 2014-06-27 | 2014-09-10 | 清华大学 | Adsorbing strengthening steam conversion technology with pre-transform reactor for processing CO gas |
| CN105688870A (en) * | 2016-03-31 | 2016-06-22 | 烟台智本知识产权运营管理有限公司 | Preparation method of X-type molecular sieve/LDHs composite adsorbent for separating methane and nitrogen through pressure swing adsorption |
| CN109748242A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of adsorbent efficiently purified for hydrogen |
| CN115475602A (en) * | 2022-08-29 | 2022-12-16 | 浙江金海高科股份有限公司 | Activated carbon-based adsorption material for carbon-sandwiched cloth and preparation method thereof |
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| CN109748242A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of adsorbent efficiently purified for hydrogen |
| CN109748242B (en) * | 2017-11-03 | 2022-09-16 | 中国科学院大连化学物理研究所 | Adsorbent for efficient purification of hydrogen |
| CN115475602A (en) * | 2022-08-29 | 2022-12-16 | 浙江金海高科股份有限公司 | Activated carbon-based adsorption material for carbon-sandwiched cloth and preparation method thereof |
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