CN103466546B - 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 clean energy technology field, be specifically related to a kind of method utilizing bifunctional adsorbent to carry out sorption enhance 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.For methane vapor reforming, in traditional industry route, unstripped gas finally need could obtain high-purity hydrogen by reforming reactor, water gas shift reactor and purifying plant three processing steps.First methane and water vapour react (1) obtained H in reformer
2and CO, then enter in water gas shift reactor react (2) and improve H further
2productive rate, removes the CO in gas product finally 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
4be difficult to realize transforming completely with CO.In addition, reforming reaction is a strong thermo-negative reaction, in order to improve transformation efficiency, need to use external heat source heat supply, usually need to keep service temperature at 800-900 DEG C, pressure is at 1.5-2MPa, and the gas product temperature obtained by water gas shift reaction is usually between 200-450 DEG C.But, the CO of ripe application
2/ H
2separating technology route mainly comprises normal temperature or low temperature wet method decarburization technique (as Selexol/NHD technology, active MDEA technology, low-temperature rectisol technology), first need carry out cooling process to synthetic gas after hydrosphere transformation, waste gas sensible heat.
Absorb (absorption) enhanced steam reforming (or synthetic gas hydrosphere transformation) and add CO in traditional reformation (or synthetic gas hydrosphere transformation) reactor
2absorb (absorption) agent.According to Le Chatelier's principle, as the CO that reforming reaction and water gas shift reaction generate
2absorbed, reaction can towards H
2the direction increased is carried out, thus significantly improves feed stock conversion.Due to CO
2absorb the enhancement of (absorption), 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 take Ca-base adsorbent as representative, and its principle is: Ca-base adsorbent reformation (or hydrosphere transformation) reactor in and CO
2after there is chemical reaction, CO in gas
2be removed, adsorb saturated sorbent material and enter regeneration reactor calcining and decomposing and go out CO
2, absorption and regeneration hockets, thus 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 absorbent particles to sinter, the stability of impact circulation.
Namely 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, by separation or the purification of periodic pressure alteration process implementation gas.The product be separated as required is in absorption or non-adsorbed state in adsorption bed, can be divided into Adsorption Phase product and fluid phase product.Such as, 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, usual H
2o, CO
2, H
2s is strong absorbed component, C
xh
y, CO adsorptive power is placed in the middle, O
2, N
2weakly stable component, and H
2adsorb hardly.Usually, in PSA system, use multiple adsorption tower being filled with sorbent material.In each adsorption tower, importing unstripped gas, by repeatedly carrying out sorption enhance hydrogen manufacturing operation, decompression operation, desorption operation and boosting operation, obtaining the product gas as object.The principle obtaining object gas is described below: if the pressure of the gas in adsorption tower uprises, the dividing potential drop of the eliminating gas that unstripped gas reaction generates also uprises, its result, eliminating gaseous constituent is filled in the adsorbent (namely removing some gaseous constituent from gas in tower) in adsorption tower, improve unstripped gas transformation efficiency, discharge gas in tower in this condition, namely obtain getting rid of the few goods gas of gaseous constituent, after this, reduce with adsorption tower internal pressure, or with non-adsorbed gas purging, get rid of gaseous constituent from sorbent material desorption (adsorbent reactivation), composition and other of desorption become to be divided into non-adsorbent object gas, the sorbent material of regeneration then can be further used for removing from the new unstripped gas reaction imported getting rid of gaseous constituent, the sorbent material used in each adsorption tower maybe need should be removed gaseous species according to object gaseous species and select, such as, if in order to remove CO from unstripped gas
2, obtain H
2goods gas, then select gac, adsorbent of molecular sieve usually.
At present, PSA gas separating method has been widely used in the CO in Sweet natural gas, coal firing boiler stack gas, synthetic-ammonia transformation gas, alumina producing in baking tail gases, lime-kiln gas
2remove and the field such as recovery, the method overcome complicated operation in wet method decarburization, desulfurization, energy consumption high, costly, the shortcoming such as equipment corrosion is large.But traditional PSA adsorption separation process sorbent suspension and the restriction of equipment work condition, often can only select normal temperature to run (as 20-45 DEG C).Meanwhile, common PSA sorbent material (as molecular sieve) is for H
2the existence of O is also very responsive, at H
2when O and other gas coexistences, the absorption H of meeting preference
2o, therefore pressure-swing adsorption process and reforming reaction or water gas shift reaction still can not carry out in same reactor simultaneously, and the gas product of reforming reaction or water gas shift reaction needs after cooling and dehydration again by independently PSA system could purifying hydrogen of hydrogen.If directly catalyzer is mixed or compound use with sorbent material, on the one hand catalyzed reaction with absorption reaction and ex situ be coupled, efficiency is lower; Required catalyzer and adsorbent amount are all by increase on the other hand, can amass by augmenting response body, thus add equipment cost.In addition, some unstripped gas also may 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 and a kind ofly bifunctional adsorbent is applied to warm pressure swing absorption process in sorption enhance steam reforming reaction and water gas shift reaction.
A kind ofly bifunctional adsorbent is applied to warm pressure swing absorption process in sorption enhance steam reforming and water gas shift reaction, bifunctional adsorbent is seated in adsorption tower, steam reforming reaction, water gas shift reaction and middle temperature Pressure Swing Adsorption hydrogen can be made to complete in same reactor, and temperature of reaction is 200-500 DEG C; Described bifunctional adsorbent has the dual-use function that catalyzed aqueous vapour is reformed with water gas shift reaction and decarbonization, desulfuration, described bifunctional adsorbent is the mixture of middle temperature sorbent material or middle temperature sorbent material and low temperature adsorbent, and the middle temperature sorbent material in this mixture accounts for more than 2% of sorbent material total mass and is less than 100%; Detailed process for by unstripped gas successively by obtaining gas product after two or more adsorption tower, in each adsorption tower, complete pressurising, sorption enhance hydrogen production reaction, gas product recoverys, drop pressure, forward bleed off pressure, reversely to bleed off pressure, steam desorb, flushing, boost pressure and fill step end.
Above-mentioned bifunctional adsorbent not only has the function of decarburization and desulfurization, and to H
2o absorption is more weak, therefore can be applied directly to the purification of steam reforming and hydrosphere transformation gas product.And this bifunctional adsorbent also possesses the function of catalyzed aqueous vapour reforming reaction and water gas shift reaction simultaneously, and active good at 200-500 DEG C.Therefore this bifunctional adsorbent is utilized, steam reforming reaction and water gas shift reaction and middle temperature pressure-swing adsorption process can be carried out in same reactor, solve and PSA system cannot be incorporated into the shortcoming of defect and the composite catalyst carried out in same reactor with above-mentioned two-step reaction in the past.
Above-mentioned each adsorption tower comprises following concrete steps in one cycle:
(1) pressurising
Being that the unstripped gas of 200-500 DEG C or gas product boost to adsorption tower by temperature, is 0.01-30MPa to adsorptive pressure;
(2) sorption enhance hydrogen production reaction
Unstripped gas is sent into adsorption tower bottom adsorption tower, issues unboiled water steam reforming and water gas shift reaction in the katalysis of sorbent material.Meanwhile, the component CO of the easy absorption of reaction generation
2and H
2s by sorbent material selective adsorption, the gas H not easily adsorbed
2, H
2o and N
2then by whole adsorption tower bed, discharge from outlet; When absorb leading-edge moves to the certain position of bed, stop adsorption operations;
(3) gas product reclaims
Discharge gas product from gas product end, along with the continuous discharge of gas product, tower internal pressure constantly declines, and when adsorbed gas delaunay triangle is 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 for the adsorption tower boosting for another completes desorption process, and this step can change according to adsorption tower number change, can be 1-6 time;
(5) forward bleed off pressure
After drop pressure, continue to release gas along absorption direction, return unstripped gas system.If when gas product recycling step yield is comparatively large, after the end of processing of drop pressure, tower internal pressure has been down to the low pressure of pressure swing adsorption system, then cancel this step;
(6) reversely to bleed off pressure
Along gas in absorption in the other direction release adsorption tower, reduce pressure, this part gas can return unstripped gas system, or directly enters another and completed in the adsorption tower of adsorbent reactivation;
(7) vacuum pump-down
When adsorption bed pressure is when close to normal atmosphere, step-down is vacuumized to adsorption tower;
(8) steam desorb
In adsorption tower, pass into steam, reduce the dividing potential drop of adsorbed gas further, realize the regeneration of sorbent material;
(9) rinse
Bleed off pressure by the Pressure Drop of adsorption tower to normal pressure by reverse, for reducing impurity composition dividing potential drop further, adopting the mode of rinsing sorbent material along venting, impurities partial pressure in adsorption tower being reduced further, completes the regeneration of sorbent material;
(10) boost pressure
By completing the mode adopting pressure between two average between the adsorption tower of adsorption process, the pressure of the adsorption tower of regeneration is improved;
(11) fill eventually
Can only be that adsorption column pressure is necessarily raised by boost pressure, also there is certain difference in the pressure of itself and whole system, this partial difference final utilization gas product carries out pressurising, and the pressure of adsorption tower is risen to system pressure.
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 is 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 is integer, 1≤x≤12,4≤y≤26.
Above-mentioned middle temperature sorbent material is hydrotalcite, houghite, the hydrotalcite of modification, the houghite of modification, Na
2the Al that O modifies
2o
3, modification or unmodified double salt sorbent material or other can realize CO under 200-500 DEG C 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 preferred hydrotalcite sorbing material modified is the hydrotalcite of potassium modification or the hydrotalcite-like materials of potassium modification further.
Above-mentioned modification or unmodified double salt sorbent material are two or more positively charged ion and the salt of a kind of negatively charged ion composition.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.Preferred double salt sorbent material is MgO-K further
2o double salt.
Beneficial effect of the present invention: add bifunctional adsorbent in the reactor, this sorbent material possesses catalyzed reaction and decarbonization, desulfuration dual-use function, multistep hydrogen production reaction can carry out under medium temperature condition in same reactor, cancel hydrogen purification equipment can reduce costs, simplification of flowsheet, and catalytic efficiency and unstripped gas transformation efficiency high; Unstripped gas sensible heat can be reclaimed, improve entire system thermo-efficiency, and decrease heat-exchange equipment, reduce costs further; Without the need to heating and cooling, the absorption/regenerative process of sorbent material can be realized, and adsorbent reactivation speed is fast, can improve the gas processing capability of PSA system; CO in gas can be realized
2with H
2jointly removing of S component, can reduce sweetener, reduces system complexity.When only having CO in unstripped gas
2time, also can realize removing CO separately
2.
Accompanying drawing explanation
Fig. 1 is the middle temperature pressure swing adsorption system schematic diagram of the sorption enhance hydrogen manufacturing of four tower configurations;
Fig. 2 is the middle temperature pressure swing adsorption system schematic diagram of the sorption enhance hydrogen manufacturing of 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 have employed 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 unstripped gas surge tank; Device is made up of 4 adsorption towers, and each adsorption tower needs experience absorption, 2 equal pressure drops, forward bleeds off pressure, reversely to bleed 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 DEG C
The pressure adjustable of four adsorption towers, is equipped with sorbent material in adsorption tower, and sorbent material is by K
2cO
3the Mg-Al hydrotalcite modified and molecular sieve, gac are composited, K
2cO
3the Mg-Al hydrotalcite modified accounts for 50% of sorbent material total mass.
After unstripped gas enters adsorption tower, under the katalysis of bifunctional adsorbent, carry out steam reforming and water gas shift reaction, the CO that reaction produces
2, H
2easily adsorbed gas is by the adsorbent loaded in adsorber for S etc., and hydrogen then flows out adsorption tower; When the loading capacity of sorbent material reaches 60% of its saturated extent of adsorption, automatically switch between adsorption tower, the adsorption tower step-down of Previous work enters step-down reproduced state, and the adsorption tower regenerated enters adsorbed state again after pre-loading to operating pressure.
The regeneration of adsorption tower is mainly different according to pressure, the principle that the adsorptive capacity of adsorbate on mixed fillers is different, and when reducing the pressure of adsorption tower, be attracted to the impurity automatic unbuckling absorption on mixed fillers, be excluded from adsorption tower, mixed fillers realizes regeneration.The regeneration of adsorption tower comprises drop pressure, reverse step-down and steam flush three states.Drop pressure refers to the adsorption tower that is in step-down reproduced state by the gas in adsorption tower all to being in pre-loading state and the lower adsorption tower of pressure, effectively can utilize the residual air in adsorption tower like this, avoid, by its discharge system, causing waste, improve the rate of recovery; Reverse step-down refers to the adsorption tower being in step-down reproduced state, when its pressure is minimal pressure in all adsorption towers, a part for 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. sorption enhance hydrogen production reaction
Unstripped gas enters bottom adsorption tower, and steam reforming and water gas shift reaction occur, and the impurity composition in gas is optionally adsorbed by multiple sorbent material.Not by the hydrogen that adsorbs as gas product.Namely qualified gas product is obtained by this step.
B. desorption
1. all pressure drops
The sorbent material completing adsorption process contains a large amount of impurity compositions, utilize sorbent material loading capacity under high pressure, low temperature large, low pressure, the feature that high temperature adsorption capacity is little, by all pressures between adsorption tower, the working pressure reducing sorbent material makes to be obtained part desorb by the impurity adsorbed.
2. forward bleed off pressure
After completing a pressure equalizing, release the very high gas of a part of density of hydrogen along the direction of absorption, be in the source of the gas of rinse step adsorption tower as another one, reduce the impurities partial pressure in this purge column, purge column is regenerated.And by forward bleeding off pressure, the spontaneous pressure of adsorption tower decreases, and impurity obtains part desorb.
3. reversely to bleed 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 releases adsorption tower against the direction of absorption, makes the pressure of adsorption tower close to normal pressure by reverse process against pressure.
4. vacuum pump-down
Make adsorption column pressure be down to close to after normal pressure by reverse bleeding off pressure, proceed to vacuumize step-down to adsorption tower.
5. steam flush
For reducing impurity composition dividing potential drop further, adopt the mode of steam flush sorbent material, impurities partial pressure in adsorption tower is reduced, and adsorbent reactivation is to the requirement of regulation.
By the acting in conjunction of three kinds of modes above, namely the regeneration of sorbent material complete.
C. preparation is adsorbed
Adsorption column pressure is mainly returned back to system pressure by absorption set-up procedure, and its Recovery Process is generally divided into:
1. all voltage rises
By completing the mode adopting pressure between two average between the adsorption tower of adsorption process, the pressure of the adsorption tower of regeneration is improved.This process is a boost process, is also a process reclaiming dead space active principle in other adsorption towers simultaneously.
2. fill eventually
Adsorption column pressure can only be made necessarily to be raised by equal voltage rise, also there is certain difference in the pressure of itself and whole system, this partial difference final utilization gas product carries out pressurising, and the pressure of adsorption tower is risen to system pressure.
So far, namely single adsorption tower completes a complete adsorption-desorption cycle 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 the cycle of once circulating is 30 minutes.Whole process temperature controls between 400-450 DEG C, and corrosion-resistant withstand voltage material selected by complete assembly, and all devices has Insulation.
Efficiency of carbon conversion >90%, H in unstripped gas
2after S decreasing ratio >95%, product hydrogen purity >90%(drying), the products C O of recovery
2after purity >90%(drying).
Embodiment 2:
This example have employed four tower configurations, as shown in Figure 1.Unstripped gas by utilidor, through high temperature resistant sequencing valve, is delivered to adsorption tower by unstripped gas surge tank.
Feed gas composition is as follows:
Raw gas pressure: 3MPa
Unstripped gas temperature: 200-300 DEG C
The pressure adjustable of four adsorption towers, is equipped with sorbent material in adsorption tower, and the Zn-Al hydrotalcite that sorbent material is modified by Na and molecular sieve, gac are composited, NaNO
3the Zn-Al hydrotalcite modified 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% time, automatically switch between adsorption tower, the adsorption tower step-down of Previous work enters step-down reproduced state, and the adsorption tower regenerated enters adsorbed state again after pre-loading to operating pressure; Whole process temperature controls between 200-300 DEG C.Corrosion-resistant withstand voltage material selected by complete assembly, and all devices has Insulation.
Efficiency of carbon conversion >90%, H in unstripped gas
2after S decreasing ratio >95%, product hydrogen purity >90%(drying), the products C O of recovery
2after purity >90%(drying).
Embodiment 3:
This example have employed 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 unstripped gas surge tank.The step of each adsorption tower experience comprises pressurising, adsorbs, bleeds off pressure, purge four steps.
Feed gas composition is as follows:
Raw gas pressure: 3MPa
Unstripped gas temperature: 200-300 DEG C
The pressure adjustable of two adsorption towers, is equipped with sorbent material in adsorption tower, and sorbent material is by Na
2cO
3the Mg-Al hydrotalcite modified and gac 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% time, automatically switch between adsorption tower, the adsorption tower step-down of Previous work enters step-down reproduced state, and the adsorption tower regenerated enters adsorbed state again after pre-loading to operating pressure; Whole process temperature controls between 200-300 DEG C.Corrosion-resistant withstand voltage material selected by complete assembly, and all devices has Insulation.
Efficiency of carbon conversion >90%, H in unstripped gas
2after S decreasing ratio >95%, product hydrogen purity >90%(drying), the products C O of recovery
2after purity >90%(drying).
Claims (3)
1. bifunctional adsorbent is applied to the method for sorption enhance steam reforming and water gas shift reaction and middle temperature pressure-variable adsorption by one kind, it is characterized in that, bifunctional adsorbent 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 DEG C; Described bifunctional adsorbent has the dual-use function that catalyzed aqueous vapour is reformed with water gas shift reaction and decarbonization, desulfuration, described bifunctional adsorbent is the mixture of middle temperature sorbent material or middle temperature sorbent material and low temperature adsorbent, and the middle temperature sorbent material in this mixture accounts for more than 2% of sorbent material total mass and is less than 100%; Detailed process for by unstripped gas successively by obtaining gas product after two or more adsorption tower, in each adsorption tower, complete pressurising, sorption enhance hydrogen production reaction, gas product recoverys, drop pressure, forward bleed off pressure, reversely to bleed off pressure, steam desorb, flushing, boost pressure and fill step end;
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 is integer, 1 < x≤20,4 < y≤42; Described gas product is mainly H
2;
Described middle temperature sorbent material is hydrotalcite, houghite, the hydrotalcite of modification, the houghite of modification; Described low temperature adsorbent is molecular sieve or gac;
Described 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
+; M
2for Mg
2+, Ca
2+, Mn
2+, Zn
2+divalent cation or its mixture; M
3for Cr
3+, Mn
3+, La
3+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.
2. a kind of method bifunctional adsorbent being applied to sorption enhance steam reforming and water gas shift reaction and middle temperature pressure-variable adsorption according to claim 1, is characterized in that, described C
xh
yin x and y be integer, 1 < x≤12,4 < y≤26.
3. a kind of method bifunctional adsorbent being applied to sorption enhance steam reforming and water gas shift reaction and middle temperature pressure-variable adsorption 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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