CN105600752A - Method and system for purifying hydrogen gas in biomass gas - Google Patents
Method and system for purifying hydrogen gas in biomass gas Download PDFInfo
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Abstract
The invention discloses a method and system for purifying hydrogen gas in biomass gas. The method comprises the process units of decarburization, drying, pressure swing adsorption and the like, wherein the process unit of pressure swing adsorption adopts a parallel connection type of a plurality of adsorption towers among which control pipelines are arranged for controlling gas circulation between each two adsorption towers, thus achieving gas pressure exchange between each two adsorption towers; an outlet at top of each adsorption tower is used for outputting product gas, an outlet at bottom is used for outputting desorption gas; and cyclic steps of adsorption, time-averaged pressure drop, concurrent discharge, reverse current discharge, washing, vacuum pumping, time-averaged pressure rise and final rise are sequentially carried out in each adsorption tower. The method and system for purifying hydrogen gas in biomass gas adopt the pressure swing adsorption principle and have reasonable process flow, the hydrogen gas purity after purification can reach 99.99% and the hydrogen gas recovery rate is high.
Description
Technical field
The present invention relates to gas separation technique field, relate in particular to a kind of purification for biological fuel gas hydrogenMethod and system thereof.
Background technology
The combustion product of hydrogen only has water, is described as " green energy resource " and " the most clean fuel ". Current masterWant hydrogen production process to have: fossil fuel hydrogen manufacturing, water electrolysis hydrogen producing, biomass hydrogen preparation and photocatalysis hydrogen production. Fossil combustionMaterial (coal, oil, natural gas etc.) hydrogen production process accounts for the more than 90% of market. But fossil fuel is in hydrogen manufacturingIn journey, give off a large amount of CO2, and hydrogen production process power consumption is excessive, is unsustainable hydrogen manufacturing path. Living beingsHydrogen manufacturing, mainly refers to the hydrogen manufacturing of biomass thermal chemical conversion process, is taking living beings as raw material, turns by heat chemistryChange technology is carried out hydrogen manufacturing, and technology is relatively ripe, comparatively easily realizes industrialization and produces.
Stalk is made up of organic matter, a small amount of mineral matter and moisture, and its organic matter composition is mainly lignin, fiberElement and hemicellulose, be of low nutritive value. After crops maturation, the vitamin in stalk is almost all destroyed.How making full use of agricultural straw resource, avoid environmental pollution simultaneously, is the significant problem that modern agriculture faces.
For example, the biological fuel gas that present inventor company utilizes stalk to carry out obtaining after charing purification mainly becomesBe divided into hydrogen 25%, methane 28%, carbon monoxide 13.5% and carbon dioxide 28.3%, ethane 1.6%, the thirdAlkane 0.57%, ethene 0.95%, propylene 0.37, nitrogen 0.5% etc. But, because the explosion limit of hydrogen is5%-75%, for catering to industrial requirements, need to purify to hydrogen.
The technique of hydrogen purification has pressure swing adsorption method, membrane separation process and separation by deep refrigeration etc. at present, and wherein, film dividesAlso simple from flow process, but that it obtains hydrogen purity is low, and organic film is short service life. And separation by deep refrigerationGenerally in the preliminary purification of reformation hydrogen, apply.
Pressure swing adsorption is the physical absorption in the face of gas molecule with adsorbent (porosu solid material) internal tableFor basis, utilize adsorbent under uniform pressure, easily to adsorb high boiling component, be difficult for absorption low boiling component and heightDepress the characteristic that adsorbance increases, the lower adsorbance of decompression reduces, by unstripped gas under pressure by adsorbent bed,High-boiling-point impurity component with respect to hydrogen is selectively adsorbed, and the hydrogen of low boiling component is difficult for absorption and passes through absorptionAgent bed, reaches separating of hydrogen and impurity composition; Then the impurity composition that under reduced pressure desorb is adsorbed makes absorptionAgent obtains regeneration, is beneficial to again carry out the adsorbing separation of impurity.
Why Pressure Swing Adsorption technical process is achieved is due to adsorbent institute in this physical absorptionTwo character that have: the one, to the adsorption capacity difference of different component, the 2nd, adsorbate is in the absorption of adsorbentCapacity rises and increases with the dividing potential drop of adsorbate. First character of utilizing adsorbent, can realize hydrogeneous source of the gasThe preferential absorption of middle impurity composition and hydrogen is purified: utilize the second individual character matter of adsorbent, can realize suctionAttached dose of under high pressure absorption and desorption and regeneration under low pressure, thus form the absorption and regeneration circulation of adsorbent, reachTo the object of continuous separating-purifying.
But the Pressure Swing Adsorption technique of prior art cannot realize the high efficiency highly purified hydrogen of purifying out,Especially for the purification of hydrogen in biological fuel gas.
Summary of the invention
For the problems referred to above of the prior art, it is a kind of for biomass fuel that main purpose of the present invention is to provideThe method of purification of hydrogen and system thereof in gas, adopt pressure-variable adsorption principle, and technique arranges rationally, the hydrogen after purificationGas purity can reach 99.99%, and hydrogen recovery rate is high, and purification efficiency has obtained significant lifting.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of for biological fuel gas hydrogenMethod of purification, formed by technique units such as decarburization, dry, pressure-variable adsorptions, described pressure-variable adsorption adopts multipleThe connected mode of adsorption tower parallel connection, arranges control piper between each adsorption tower, controls the gas between two adsorption towersCirculation, to reach the air pressure exchange between two adsorption towers; Wherein each adsorption tower top exit output products gas, the endPortion's outlet output stripping gas; Wherein each adsorption tower adsorb successively, all fall, along putting, inverse put, flushing,Vacuumize, all rise, the circulation step of final rise.
Do not limit the form of control piper between each adsorption tower herein, those skilled in the art can be according to existing skillArt is chosen suitable pipe fitting, instrument, valve etc. and is connected with suitable connected mode, only needs to realize an absorption towerBetween connect with disconnect automatic control, according to technological requirement can reservation time in be communicated with two absorptionsTower is also closed the connection between two towers within the time of subscribing.
Adsorption step: biological fuel gas enters adsorption tower from bottom to top, and impurity composition is loaded in adsorption towerAdsorbent carries out selective absorption, wherein except H2Impurity component is in addition adsorbed, and obtains pure H2；
Drop pressure (all falling) step: after adsorption step completes, along absorption direction by adsorption tower in higher pressurePower hydrogen is put into the process of other completed low pressure adsorption tower successively, and this process had both played High Pressure Absorption tower and fallenThe effect of pressing, has also reclaimed hydrogen and the pressure in adsorption tower dead space simultaneously;
Rapid along strideing: adsorption tower is all falling after step finishes, along the decompression of absorption direction, decompression H out2Enter along slowing down and rush tank stores;
Inverse put step: adsorption tower, along putting after end, is down to adsorption tower internal pressure to approach normal pressure against absorption direction,The impurity being now adsorbed starts to desorb from adsorbent, puts in surge tank;
Rinsing step: after inverse put finishes, with the low pressure H along in venting tank2Adsorption tower is rinsed, at this momentThe impurity being adsorbed desorbs in a large number, and flows into stripping gas surge tank against absorption direction;
Vacuumize step: in this course, with vavuum pump against absorption direction adsorbent bed is vacuumized,Impurity is thoroughly extracted out, allowed the adsorbent in tower be regenerated completely;
Boost pressure (all rising) step: corresponding with drop pressure step, utilize the equal pressure drop of other adsorption towerPress the gas of step output from this adsorption tower top input, adsorption tower to be boosted, this process has reclaimed otherThe hydrogen of adsorbent bed dead space;
The gas product step (final rise) of boosting: by all rising after process, adsorption column pressure has risen to close to absorptionPressure. Now, use product H2Adsorption column pressure is risen to adsorptive pressure; After this process, adsorption towerJust completed whole regenerative process, for absorption is next time got ready.
Each adsorption tower all passes through said process, has completed the adsorption process of each step of adsorption tower, enters nextIndividual cyclic process.
As further preferred, described pressure swing adsorption technique unit adopts 8 adsorption towers to be connected in parallel, everyStep that what adsorption tower carried out all fall comprises one all falls, two all falls, three all falls, all rise step comprise one all rise, twoAll liter, three all rises, and wherein, between two adsorption towers, one of first adsorption tower all falls step corresponding to anotherThree of adsorption tower all rises step, and two of first adsorption tower all falls step and all rises corresponding to two of another adsorption towerStep, three of first adsorption tower all falls step and all rises step corresponding to one of another adsorption tower.
As further preferably, absorption that in described pressure swing adsorption technique unit, multiple adsorption towers carry out successively,All fall, along putting, inverse put, rinse, vacuumize, all rise, same steps in the circulation step of final rise is in the timeOn the operation of staggering.
As further preferably, by the control piper control between two adsorption towers, a wherein adsorption towerThe gas that all falls step output all rise step for another adsorption tower operation, the absorption of step all falls in now operationAir pressure in tower is greater than the air pressure in the adsorption tower that operation all rises step.
As further preferably, wherein one all fall, two all fall, three all fall, inverse put, rinse, vacuumize,One all rise, two all rise, three be all a unit interval, wherein suitable putting the running time of the step such as liters, final riseBe two unit interval the running time of step, and be four unit interval the running time of adsorption step. For example,One all rise, two all rise, three be all 1 minute the running time of the step such as liters, final rise, wherein suitable stride rapidBe 2 minutes running time, and be 4 minutes the running time of adsorption step.
As further preferred, each adsorption tower is stored in the suitable surge tank of putting along the gas of the rapid middle output of strideing temporarilyIn, along putting surge tank difference air feed to each adsorption tower operation rinsing step. Described also passes through control along putting surge tankTubulation road is connected with each adsorption tower, realizes and being communicated with between each adsorption tower and the automatic control disconnecting. .
As further preferred, described decarbonization process unit adopts at least two alkali liquor absorption towers to be composed in series,Biological fuel gas is successively by least two alkali liquor absorption towers, and wherein alkali liquor absorption tower inlet pressure is controlled at0.3MPa～0.5Mpa; Described drying process unit adopts at least two drying towers to be composed in series; Described absorption stepIn rapid, in adsorption tower, boost as 1.5Mpa～2.0MPa, described in vacuumize evacuated pressure in step and be-0.05Mpa～-0.01Mpa。
For a purification system for biological fuel gas hydrogen, it is characterized in that: comprising:
At least one alkali liquor absorption tower, is connected in series between multiple alkali liquor absorption towers, for the combustion gas of organism-absorbing matterIn carbon dioxide;
At least one drying tower, is connected in series between multiple drying towers, first drying tower and last alkali lyeAbsorption tower connects, and dewaters for biological fuel gas;
At least two adsorption towers, described adsorption tower comprises at least one top exit and at least one outlet at bottom,Between multiple adsorption towers, be connected in parallel; Total mouthful of the parallel connection of described multiple adsorption tower outlet at bottoms is dry with lastTower connects, total mouthful of output products hydrogen of parallel connection of the top exit on described multiple absorption towers.
Stripping gas surge tank, is connected with described multiple adsorption tower outlet at bottoms, for receiving stripping gas;
Along putting surge tank, with described multiple adsorption tower top exits, for receiving the gas along the rapid output of strideing;
Control piper, described control piper is arranged between each adsorption tower and each adsorption tower and stripping gas bufferingTank, suitable putting between surge tank, control the gas communication between two adsorption towers, to reach the gas between two adsorption towersPress exchange.
As further preferred, the quantity of described adsorption tower is 8; Described control piper comprises pipeline, journeyControl valve, Pressure gauge and flowmeter.
As further preferably, due to combustion gas being distributed as in adsorption tower: CO2At the bottom, You JiqiBody is at CO2Above gas, simultaneously at the middle part of adsorption tower, CO is at CH4Above, be topmost H2; Based onThe distributed areas of combustion gas, in described adsorption tower, adsorbent adopts layering to place, and is divided into 3 layers, and bottom one deck is completeFor active carbon, intermediate layer is that active carbon and 5A molecular sieve mix placement, and described intermediate layer adopts active carbon and 5AMolecular sieve mixes as adsorbent according to the volume ratio of 4～2:1, and the superiors are 5A molecular sieve entirely. AdsorbentThe object that layering is filled is that adsorbent layering can reach because of the distribution difference of gas in the process of pressure-variable adsorptionTo better clean-up effect.
The invention has the beneficial effects as follows: the hydrogen that the present invention purifies in biological fuel gas by pressure swing adsorption method,Adsorption tower quantity and structure are rationally set, make object product hydrogen purity can reach 99.99%, and hydrogenGas recovery rate and purification efficiency are promoted significantly.
1,, according to the composition of biological fuel gas, reasonably selected the sorbent used and proportioning of adsorption tower. CombustionCO in gas2Content large. Active carbon is very large to the adsorption capacity of carbon dioxide, and adsorbance is with pressureEustasy is fairly obvious, is the good adsorbent of carbon dioxide, and 5A molecular sieve is quite different, and it is in low pressureLower just a large amount of absorbing carbon dioxide, and not obvious with the variation of pressure rising adsorbance, under low pressure desorption difficulty,Therefore can not make the adsorbent of carbon dioxide, therefore will have active carbon in adsorbent. 5A molecular sieve is for methaneAdsorption capacity is very strong, and it is in the time that pressure amplitude is identical, and the variation of equilibrium adsorption capacity is basic identical, Ke YizuoFor the adsorbent of methane. Molecular sieve is all very strong for the adsorption capacity of organic gas and nitrogen simultaneously, is applicable to thisBiological fuel gas. Active carbon and 5A molecular sieve all can be used as the adsorbent of carbon monoxide, and the high pressure of active carbon is inhaledAttached amount is larger than molecular sieve, and low pressure desorption is easy, but the adsorption capacity of molecular sieve is stronger, is applicable to require to produceThe very low situation of carbon monoxide in product, the two absorption for CO all can reach requirement. The Regenerated energy of active carbonPower is strong, and based on cost consideration and experimental result, in this technique, adsorbent adopts active carbon and 5A molecular sieve to be paved withIn adsorbent bed.
2, the distributed areas based on combustion gas, adsorbent of the present invention adopts layering to place, and is divided into 3 layers,One deck is active carbon entirely below, and intermediate layer is that active carbon and 5A molecular sieve mix according to the volume ratio of 4～2:1Place, the superiors are 5A molecular sieve entirely. Valve is program-controlled valve. Adsorption tower is GB150 pressure vessel.Be equipped with Pressure gauge and flowmeter, carry out the flow of controlled pressure and combustion gas. Through experiment showed, that adsorption effect is passableReach required requirement, hydrogen purity reaches 99.99%. The object that adsorbent layering is filled is because in transformationThe distribution difference of gas in the process of absorption, adsorbent layering can reach better clean-up effect.
3, the present invention adopts eight adsorption towers can promote all and rises and all falls number of times, makes the purity of hydrogen up to standard, allPress number of times to be set as 3 times, all fall and all rise each 3 times.
4, the adsorptive pressure in each adsorption tower is identical, all controls by outside compressor and vavuum pump. PressContracting machine boosts, vavuum pump step-down. Utilize adsorbent easily absorption high boiling component, difficult absorption under uniform pressureThe characteristic that under low boiling component and high pressure, adsorbance increases, the lower adsorbance of decompression reduces, by unstripped gas under pressureBy adsorbent bed, selectively adsorbed with respect to the high-boiling-point impurity component of hydrogen, the hydrogen of low boiling component is notEasily adsorb and by adsorbent bed, reach separating of hydrogen and impurity composition; Then under reduced pressure desorb is adsorbedImpurity composition make adsorbent obtain regeneration, be beneficial to again carry out the adsorbing separation of impurity.
5, drop pressure process of the present invention: after adsorption process completes, along absorption direction by adsorbent bed in higher pressurePower hydrogen is put into the process of other completed low pressure adsorbent bed successively, and this process had both played the effect of step-down,Also reclaimed hydrogen and the pressure in adsorbent bed dead space, this flow process has comprised drop pressure mistake altogether three times simultaneouslyJourney, therefore can ensure the abundant recovery of hydrogen.
6, boost pressure process of the present invention: corresponding with drop pressure process, utilize the equal pressure drop of other adsorbent bedThe body of calming the anger boosts to adsorbent bed from top, and this process has reclaimed the hydrogen of other adsorbent bed dead space. ThisInvention hydrogen recovery rate can reach 89%.
Brief description of the drawings
Fig. 1 is the flow chart of the embodiment of the present application for the method for purification of biological fuel gas hydrogen.
Fig. 2 is the structural representation of the embodiment of the present application for biological fuel gas hydrogen purification system.
Being described as follows of mark in accompanying drawing: 1-the first alkali liquor absorption tower, 2-the second alkali liquor absorption tower, 3-the first drying tower,4-the second drying tower, 5-stripping gas surge tank, 6-adsorption tower device, 7-vavuum pump, 8-are along putting surge tank, 9-Product gas tank.
Detailed description of the invention
The present invention, by a kind of method of purification for biological fuel gas hydrogen and system thereof are provided, adopts transformationAbsorption principle, technique arranges rationally, and the hydrogen purity after purification can reach 99.99%, and hydrogen recovery rateHigh.
In order better to understand technique scheme, below in conjunction with Figure of description and concrete embodimentTechnique scheme is described in detail.
As shown in Figure 1, the embodiment of the present application is for the method for purification of biological fuel gas hydrogen, by decarburization, dryThe technique unit compositions such as dry, pressure-variable adsorption, described pressure-variable adsorption adopts the connected mode of multiple adsorption tower parallel connections,Between each adsorption tower, control piper is set, controls the gas communication between two adsorption towers, with reach two adsorption towers itBetween air pressure exchange; Wherein each adsorption tower top exit output products hydrogen, outlet at bottom output stripping gas; ItsIn each adsorption tower adsorb successively, all fall, along putting, inverse put, rinse, vacuumize, all rise, final riseCirculation step.
Adsorption step: biological fuel gas enters adsorption tower from bottom to top, the adsorbent that impurity composition is loaded carries outSelective absorption, wherein except H2Impurity component is in addition adsorbed, and obtains pure H2, adsorption process is being carried outFinish during close to adsorption tower top exit to absorption forward position;
Drop pressure (all falling) step: after adsorption step completes, along absorption direction by adsorption tower in higher pressurePower hydrogen is put into the process of other completed low pressure adsorption tower successively, and this process had both played High Pressure Absorption tower and fallenThe effect of pressing, has also reclaimed hydrogen and the pressure in adsorbent bed dead space simultaneously, and this flow process according to adsorption tower alsoConnection quantity can be carried out repeatedly drop pressure process, and one of them preferred embodiment is to select eight absorption alsoConnection, can comprise drop pressure process altogether three times, therefore can ensure the abundant recovery of hydrogen;
Rapid along strideing: adsorption tower is all falling after end, along the decompression of absorption direction, decompression H out2EnterRush tank stores along slowing down;
Inverse put step: adsorption tower, along putting after end, is down to adsorption tower internal pressure to approach normal pressure against absorption direction,The impurity being now adsorbed starts to desorb from adsorbent, puts in surge tank;
Rinsing step: after inverse put finishes, with the low pressure H along in venting tank2Adsorption tower is rinsed, at this momentThe impurity being adsorbed desorbs in a large number, and flows into stripping gas surge tank against absorption direction;
Vacuumize step: in this course, with vavuum pump against absorption direction adsorbent bed is vacuumized,Impurity is thoroughly extracted out, allowed the adsorbent in tower be regenerated completely;
Boost pressure (all rising) step: corresponding with drop pressure step, utilize the equal pressure drop of other adsorption towerThe body of calming the anger boosts to adsorbent bed from top, and this process has reclaimed the hydrogen of other adsorption tower dead space, shouldThe number of times of step is corresponding with the number of times of drop pressure step;
The gas product process (final rise) of boosting: by all rising after process, adsorption column pressure has risen to close to absorptionPressure. Now, use product H2Adsorption column pressure is risen to adsorptive pressure; After this process, adsorption towerJust completed whole regenerative process, for absorption is next time got ready.
Single adsorption tower moves above-mentioned steps successively by the time, and two adsorption tower operation above-mentioned steps are wrong in timeOpen, object is moved the different step between two towers simultaneously, so that between two towers, carry out other exchanges, and such as itIn a tower operation while all falling step, by the folding of sequencing valves in control piper, make this tower gas vent and fortuneRow all rise step another tower gas feed be communicated with, now between two towers because pressure reduction has just carried out gas friendshipChange, until two tower air pressure are equal, after this process, rear control piper disconnects the connection between two towers automatically,Make two towers can normally move next step.
Through said process, complete the adsorption process of each step of adsorption tower, enter next cyclic process.
A preferred embodiment, described pressure swing adsorption technique unit adopts 8 adsorption towers to be connected in parallel, everyStep that what adsorption tower carried out all fall comprises one all falls, two all falls, three all falls, all rise step comprise one all rise, twoAll liter, three all rises. Adopt 8 adsorption towers can promote all to rise, all fall number of times, make the purity of hydrogen up to standard.
Select the pressure swing adsorption technique unit of 8 adsorption tower compositions, by the rational technology controlling and process of control piper,Realize single adsorption tower and can both carry out respectively the process of all falling for three times and all rise process three times, this kind of processing arrangement bothThe purification purity of the limited lifting hydrogen of energy, simultaneously little on purification efficiency impact, be current optimized technique choosingSelect.
Absorption that in described pressure swing adsorption technique unit, multiple adsorption towers carry out successively, all fall, along putting, inverse put,Rinse, vacuumize, all rise, same steps in the circulation step of final rise staggers operation in time.
By the control piper control between two adsorption towers, the wherein gas that all falls step output of an adsorption towerBody all rises step for another adsorption tower operation, and the air pressure now moving in the adsorption tower that all falls step is greater than operationAll rise the air pressure in the adsorption tower of step.
Wherein one all fall, two all fall, three all fall, inverse put, rinse, vacuumize, one all rise, two all rise, threeAll being all a unit interval running time of the step such as liter, final rise, is wherein two along the rapid running time of strideingThe individual unit interval, be four unit interval the running time of adsorption step.
The required purge gas of described rinsing step derives from the gas along the rapid output of strideing.
Described decarbonization process unit adopts at least two alkali liquor absorption towers to be composed in series, and biological fuel gas passes through successivelyAt least two alkali liquor absorption towers, wherein alkali liquor absorption tower inlet pressure is controlled at 0.3MPa～0.5Mpa; Described dryDrying process unit adopts at least two drying towers to be composed in series.
In described adsorption step, in adsorption tower, boost as 1.5Mpa～2.0MPa, described in vacuumize in step and vacuumizePressure is-0.05Mpa～-0.01Mpa.
Each adsorption tower is stored in along putting in surge tank along the gas of the rapid middle output of strideing temporarily, along putting surge tank respectivelyAir feed is given each adsorption tower operation rinsing step.
As shown in Figure 2, the embodiment of the present application, for the purification system of biological fuel gas hydrogen, is characterized in that:Comprise:
Between the first alkali liquor absorption tower 1,2, two alkali liquor absorption towers of the second alkali liquor absorption tower, be connected in series, useCarbon dioxide in the combustion gas of organism-absorbing matter;
Between the first drying tower 3,4, two drying towers of the second drying tower, be connected in series, the first drying tower 3 withThe second alkali liquor absorption tower 2 connects, and dewaters for biological fuel gas;
Multiple adsorption towers 6, described adsorption tower comprises at least one top exit and at least one outlet at bottom, manyBetween individual adsorption tower, be connected in parallel; Total mouthful of parallel connection and second drying tower 4 of described multiple adsorption tower outlet at bottomsConnect total mouthful of output products gas of parallel connection of the top exit on described multiple absorption towers.
Control piper, described control piper arranges between each adsorption tower, controls the gas communication between two adsorption towers,To reach the air pressure exchange between two adsorption towers.
The quantity of described adsorption tower is 8.
Described control piper comprises pipeline, sequencing valve, Pressure gauge and flowmeter.
Also comprise stripping gas surge tank 5, be connected with the total mouth of parallel connection of described multiple adsorption tower outlet at bottoms, forReceive stripping gas.
Also comprise along putting surge tank 8, be connected with the total mouth of parallel connection of described multiple adsorption tower top exits, for connecingReceive the gas along the rapid output of strideing.
In described adsorption tower, adsorbent adopts layering to place, and is divided into 3 layers, and bottom one deck is active carbon, centreLayer is that active carbon and 5A molecular sieve mix placement, and the superiors are 5A molecular sieve.
Described intermediate layer adopts active carbon and 5A molecular sieve to mix as adsorbent according to the volume ratio of 4～2:1.
In the present embodiment, 8 adsorption towers are respectively A, B, C, D, E, F, G and H tower, described 8The concrete technology flow process of individual adsorption tower can see the following form 1:
Table 1
The now adsorption process of adsorption tower A for example: A tower is carrying out after the absorption of 4 minutes, starts to carry out one equalFall, be connected with D tower. A pressure tower reduces, and D pressure tower raises. After all pressure finishes, two pressure towers are basicEquate. One all falls after end, carries out two and all falls. A tower is connected with E tower, same process. Then three all fall ATower is connected with F tower, same process. The time of all falling is all 1 minute. After all falling for three times, A tower carries out along letting slipJourney, is connected with H tower, and H tower is rinsed, and pressure is also reducing simultaneously, and gas flow into along venting tankIn. The suitable time of putting is set as 2 minutes. Carry out inverse put process along putting rear A tower, gas is stripping gas, entersIn stripping gas surge tank. Then carry out flushing process, now A tower is connected with B tower, suitable the putting in B towerAir-flow is through A tower, after enter along venting tank. After flushing completes, A tower is vacuumized, make A tower adsorbentThe air release of absorption out, is recycled, and improves purity and the rate of recovery. Start afterwards three and all rise, with DTower is connected, and all presses, and A pressure tower is promoted, the step-down of D tower. Two all rise with E tower and are connected, and one all risesBe connected with F tower, process is the same, boost pressure. The time that all rises is all 1 minute. Finally carry out final pressure and boost,Boost to the pressure of absorption, 1 minute time. And then adsorb. Each tower experiences this 12 processes,Loop. All pressing is to carry out between tower and tower, in each time period, only has two towers adsorbing,This design treating capacity is large, and each step is connected rationally.
The each parameter of embodiment 1 is as follows: activated carbon of sorbent and 5A molecular sieve ratio are 2:1, and inlet pressure is0.4MPa, a washing tower, two drying towers, vacuumize as-0.02MPa, boost as 1.5MPa, purifyH2Purity be 99.892%, the rate of recovery 82%, has reached necessary requirement.
The each parameter of embodiment 2 is as follows: activated carbon of sorbent and 5A molecular sieve ratio are 3:1, and inlet pressure is0.3MPa, two washing towers, two drying towers, vacuumize as-0.03Mpa, boost as 1.7MPa, purifyH2Purity be 99.894%, the rate of recovery 84%, reaches requirement substantially.
The each parameter of embodiment 3 is as follows: activated carbon of sorbent and 5A molecular sieve ratio are 4:1, and inlet pressure is0.5MPa, two washing towers, a drying tower, vacuumizes as-0.04MPa, boosts as 1.9MPa, purifiesH2Purity be 99.898%, the rate of recovery 85%, has reached necessary requirement.
The each parameter of embodiment 4 is as follows: activated carbon of sorbent and 5A molecular sieve ratio are 4:1, and inlet pressure is0.5MPa, two washing towers, two drying towers, vacuumize as-0.05MPa, boost as 2.0MPa, purifyH2Purity be 99.993%, the rate of recovery 89%, has reached necessary requirement.
Through data statistics orthogonal experiment, it is 4:1 that the embodiment of the present application adopts active carbon and 5A molecular sieve ratio,Inlet pressure is 0.5MPa, and washing tower is two, and drying tower is two, vacuumizes pressure in pressure-swing absorption processPower is-0.015MPa, while boosting technological parameter into 2.0Mpa, and purification H2Purity reached required and wantedAsk, hydrogen recovery rate reaches 89%, and the requirement of the consideration based on to cost and hydrogen commercial Application, can be by thisTechnique is the optimised process of eight tower absorption biological fuel gas purifying hydrogen of hydrogen.
Technical scheme in above-mentioned the embodiment of the present application, at least has following technique effect or advantage: living beingsHydrogen producing technology can utilize abundant living resources, pollutes littlely, is wide environmentally friendly of a kind of development prospectHydrogen production process. The application purifies to biological fuel gas by pressure swing adsorption method, and the purity of hydrogen is reachedMore than 99.99%, reach commercial Application requirement:
1,, according to the composition of biological fuel gas, reasonably selected the sorbent used and proportioning of adsorption tower. CombustionCO in gas2Content large. Active carbon is very large to the adsorption capacity of carbon dioxide, and adsorbance is with pressureEustasy is fairly obvious, is the good adsorbent of carbon dioxide, and 5A molecular sieve is quite different, and it is in low pressureLower just a large amount of absorbing carbon dioxide, and not obvious with the variation of pressure rising adsorbance, under low pressure desorption difficulty,Therefore can not make the adsorbent of carbon dioxide, therefore will have active carbon in adsorbent. 5A molecular sieve is for methaneAdsorption capacity is very strong, and it is in the time that pressure amplitude is identical, and the variation of equilibrium adsorption capacity is basic identical, Ke YizuoFor the adsorbent of methane. Molecular sieve is all very strong for the adsorption capacity of organic gas and nitrogen simultaneously, is applicable to thisBiological fuel gas. Active carbon and 5A molecular sieve all can be used as the adsorbent of carbon monoxide, and the high pressure of active carbon is inhaledAttached amount is larger than molecular sieve, and low pressure desorption is easy, but the adsorption capacity of molecular sieve is stronger, is applicable to require to produceThe very low situation of carbon monoxide in product, the two absorption for CO all can reach requirement. The Regenerated energy of active carbonPower is strong, and based on cost consideration and experimental result, in this technique, adsorbent adopts active carbon and 5A molecular sieve to be paved withIn adsorbent bed.
2, the distributed areas based on combustion gas, adsorbent of the present invention adopts layering to place, and is divided into 3 layers,One deck is active carbon entirely below, and intermediate layer is that active carbon and 5A molecular sieve mix according to the volume ratio of 4～2:1Place, the superiors are 5A molecular sieve entirely. Valve is program-controlled valve. Adsorption tower is GB150 pressure vessel.Be equipped with Pressure gauge and flowmeter, carry out the flow of controlled pressure and combustion gas. Through experiment showed, that adsorption effect is passableReach required requirement, hydrogen purity reaches 99.99%. The object that adsorbent layering is filled is because in transformationThe distribution difference of gas in the process of absorption, adsorbent layering can reach better clean-up effect.
3, the present invention adopts eight adsorption towers can promote all and rises and all falls number of times, makes the purity of hydrogen up to standard, allPress number of times to be set as 3 times, all fall and all rise each 3 times.
4, the adsorptive pressure in each adsorption tower is identical, all controls by outside compressor and vavuum pump. PressContracting machine boosts, vavuum pump step-down. Utilize adsorbent easily absorption high boiling component, difficult absorption under uniform pressureThe characteristic that under low boiling component and high pressure, adsorbance increases, the lower adsorbance of decompression reduces, by unstripped gas under pressureBy adsorbent bed, selectively adsorbed with respect to the high-boiling-point impurity component of hydrogen, the hydrogen of low boiling component is notEasily adsorb and by adsorbent bed, reach separating of hydrogen and impurity composition; Then under reduced pressure desorb is adsorbedImpurity composition make adsorbent obtain regeneration, be beneficial to again carry out the adsorbing separation of impurity.
5, drop pressure process of the present invention: after adsorption process completes, along absorption direction by adsorbent bed in higher pressurePower hydrogen is put into the process of other completed low pressure adsorbent bed successively, and this process had both played the effect of step-down,Also reclaimed hydrogen and the pressure in adsorbent bed dead space, this flow process has comprised drop pressure mistake altogether three times simultaneouslyJourney, therefore can ensure the abundant recovery of hydrogen.
6, boost pressure process of the present invention: corresponding with drop pressure process, utilize the equal pressure drop of other adsorbent bedThe body of calming the anger boosts to adsorbent bed from top, and this process has reclaimed the hydrogen of other adsorbent bed dead space. ThisInvention hydrogen recovery rate can reach 89%.
Although described the preferred embodiments of the present invention, once those skilled in the art cicada basicCreative concept, can make other change and amendment to these embodiment. So, claims meaningWant to be interpreted as comprising preferred embodiment and to fall into all changes and the amendment of the scope of the invention. Obviously, this areaTechnical staff can carry out various changes and modification and not depart from the spirit and scope of the present invention the present invention. ThisSample, if of the present invention these amendment and modification belong to the claims in the present invention and equivalent technologies thereof scope itIn, the present invention be also intended to comprise these change and modification interior.
Claims (10)
1. for the method for purification of biological fuel gas hydrogen, by works such as decarburization, dry, pressure-variable adsorptionsSkill unit composition, is characterized in that: pressure-variable adsorption adopts the connected mode of multiple adsorption tower parallel connections each adsorption towerBetween control piper is set, control the gas communication between two adsorption towers, to reach the air pressure between two adsorption towersExchange; Wherein each adsorption tower top exit output products gas, outlet at bottom output stripping gas; Wherein each absorptionTower adsorbs successively, all falls, along putting, inverse put, rinse, vacuumize, all rise, the circulation step of final rise.
2. the method for purification for biological fuel gas hydrogen according to claim 1, is characterized in that:Described pressure swing adsorption technique unit adopts 8 adsorption towers to be connected in parallel, and what every adsorption tower carried out all falls step bagDraw together and one all fall, two all fall, three all fall, all rise step and comprise and one all rise, two all rise, three all rise.
3. according to the method for purification for biological fuel gas hydrogen described in claim 1-2 any one, itsBe characterised in that: absorption that in pressure swing adsorption technique unit, multiple adsorption towers carry out successively, all fall, along putting, inverse put,Rinse, vacuumize, all rise, same steps in the circulation step of final rise staggers operation in time.
4. according to the method for purification for biological fuel gas hydrogen described in claim 1-2 any one, itsBe characterised in that: by the control piper control between two adsorption towers, wherein an adsorption tower all to fall step defeatedThe gas that goes out all rises step for another adsorption tower operation, and it is large that air pressure in the adsorption tower of step all falls in now operationAir pressure in moving the adsorption tower that all rises step.
5. the method for purification for biological fuel gas hydrogen according to claim 2, is characterized in that:Wherein one all fall, two all fall, three all fall, inverse put, rinse, vacuumize, one all rise, two all rise, three all rise,Being all a unit interval running time of the steps such as final rise, is wherein Liang Ge unit along the rapid running time of strideingTime, be four unit interval the running time of adsorption step.
6. according to the method for purification for biological fuel gas hydrogen described in claim 1-2 any one, itsBe characterised in that: each adsorption tower is stored in along putting in surge tank along the gas of the rapid middle output of strideing temporarily, along slowing down punchingTank respectively air feed is given each adsorption tower operation rinsing step.
7. according to the method for purification for biological fuel gas hydrogen described in claim 1-2 any one, itsBe characterised in that:
Described decarbonization process unit adopts at least two alkali liquor absorption towers to be composed in series, and biological fuel gas passes through successivelyAt least two alkali liquor absorption towers, wherein alkali liquor absorption tower inlet pressure is controlled at 0.3MPa～0.5Mpa;
Described drying process unit adopts at least two drying towers to be composed in series;
In described pressure swing adsorption technique unit, in adsorption step, in adsorption tower, boost as 1.5Mpa～2.0MPa, described inVacuumizing evacuated pressure in step is-0.05Mpa～-0.01Mpa.
8. for a purification system for biological fuel gas hydrogen, it is characterized in that: comprising:
At least one alkali liquor absorption tower, is connected in series between multiple alkali liquor absorption towers, for the combustion gas of organism-absorbing matterIn carbon dioxide;
At least one drying tower, is connected in series between multiple drying towers, first drying tower and last alkali lyeAbsorption tower connects, and dewaters for biological fuel gas;
At least two adsorption towers, described adsorption tower comprises at least one top exit and at least one outlet at bottom,Between multiple adsorption towers, be connected in parallel; Total mouthful of the parallel connection of described multiple adsorption tower outlet at bottoms is dry with lastTower connects, total mouthful of output products hydrogen of parallel connection of the top exit on described multiple absorption towers;
Stripping gas surge tank, is connected with described multiple adsorption tower outlet at bottoms, for receiving stripping gas;
Along putting surge tank, be connected with described multiple adsorption tower top exits, for receiving the gas along the rapid output of strideingBody;
Control piper, described control piper is arranged between each adsorption tower and each adsorption tower and stripping gas bufferingTank, suitable putting between surge tank, control the gas communication between two adsorption towers, to reach the gas between two adsorption towersPress exchange.
9. the purification system for biological fuel gas hydrogen according to claim 8, is characterized in that:The quantity of described adsorption tower is 8;
Described control piper comprises pipeline, sequencing valve, Pressure gauge and flowmeter.
10. the purification system for biological fuel gas hydrogen according to claim 8, is characterized in that:In described adsorption tower, adsorbent divides 3 layers of placement, and bottom one deck is active carbon, and intermediate layer is active carbon and 5AMolecular sieve mixes to be placed, and the superiors are 5A molecular sieve; Wherein the active carbon in intermediate layer and 5A molecular sieve according toThe volume ratio of 4～2:1 mixes.
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