CN105600752B - A kind of method of purification and its system for being used for hydrogen in biological fuel gas - Google Patents
A kind of method of purification and its system for being used for hydrogen in biological fuel gas Download PDFInfo
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- CN105600752B CN105600752B CN201610186416.6A CN201610186416A CN105600752B CN 105600752 B CN105600752 B CN 105600752B CN 201610186416 A CN201610186416 A CN 201610186416A CN 105600752 B CN105600752 B CN 105600752B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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- C—CHEMISTRY; METALLURGY
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- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/0017—Carbon-based materials
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/002—Other molecular sieve materials
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0042—Making ultrapure specific gas
Abstract
The invention discloses a kind of method of purification and its system for being used for hydrogen in biological fuel gas, the method of purification is made of technique units such as decarburization, drying, pressure-variable adsorptions, the pressure-variable adsorption uses the connection mode of multiple adsorption towers parallel connection, control piper is set between each adsorption tower, the gas between two adsorption towers is controlled to circulate, to reach the exchange of the air pressure between two adsorption towers；Wherein each adsorption tower top exit output products gas, outlet at bottom output stripping gas；Wherein each adsorption tower adsorbed successively, drop, along putting, inverse put, rinse, vacuumize, rising, the circulation step of final rise.The present invention uses principle of pressure swing adsorption, and it is reasonable that technique is set, and the hydrogen purity after purification can reach 99.99%, and hydrogen recovery rate is high.
Description
Technical field
The present invention relates to gas separation technique field, more particularly to a kind of method of purification for being used for hydrogen in biological fuel gas
And its system.
Background technology
The combustion product of hydrogen only has water, is known as " green energy resource " and " most clean fuel ".Current main hydrogen manufacturing
Method has：Fossil fuel hydrogen manufacturing, water electrolysis hydrogen producing, biomass hydrogen preparation and photocatalysis hydrogen production.Fossil fuel (coal, oil, natural gas
Deng) hydrogen production process accounts for more than the 90% of market.But fossil fuel gives off substantial amounts of CO in hydrogen production process2, and hydrogen manufacturing
Process energy consumption is excessive, is unsustainable hydrogen manufacturing path.Biomass hydrogen preparation, is primarily referred to as biomass thermal chemical conversion process system
Hydrogen, is using biomass as raw material, by thermochemical study technology come hydrogen manufacturing, technology relative maturity, is relatively easy to realize industrialization
Production.
Stalk is made of organic matter, a small amount of mineral matter and moisture, its organic matter composition is mainly lignin, cellulose and half
Cellulose, nutritive value are low.After crop maturity, the vitamin in stalk is almost all destroyed.How agriculture is made full use of
Crop material resource, while environmental pollution is avoided, it is the significant problem that modern agriculture faces.
For example, present inventor company is using the biological fuel gas main component that stalk obtained after charing purification
Hydrogen 25%, methane 28%, carbon monoxide 13.5% and carbon dioxide 28.3%, ethane 1.6%, propane 0.57%, ethene
0.95%, propylene 0.37, nitrogen 0.5% etc..But since the explosion limit of hydrogen is 5%-75%, to cater to industrial requirements,
Need to purify hydrogen.
The technique of hydrogen purification has pressure swing adsorption method, membrane separation process and separation by deep refrigeration etc. at present, wherein, UF membrane flow
Also it is simple, but its to obtain hydrogen purity low, and organic film service life is short.And separation by deep refrigeration is generally reforming the first of hydrogen
Applied in step purification.
Pressure swing adsorption is using physical absorption of adsorbent (porosu solid material) interior surface to gas molecule as base
Plinth, high boiling component is easily adsorbed using adsorbent, is not easy to adsorb adsorbance increasing under low boiling component and high pressure at the same pressure
Add, depressurize the characteristic that lower adsorbance reduces, unstripped gas is passed under pressure through it is adsorbent bed, relative to the high-boiling-point impurity of hydrogen
Component is selectively adsorbed, and the hydrogen of low boiling component is not easy absorption by adsorbent bed, reaches point of hydrogen and impurity composition
From；Then desorbing the impurity composition adsorbed under reduced pressure is regenerated adsorbent, in favor of carrying out the absorption of impurity again
Separation.
Why Pressure Swing Adsorption technical process is achieved in that adsorbent is had in this physical absorption
Two attributes：First, different to the adsorption capacity of different component, second, adsorbate adsorbent adsorption capacity with adsorbate
Partial pressure rise and increase.Using first property of adsorbent, it can be achieved that Preferential adsorption to impurity composition in hydrogeneous source of the gas
And hydrogen is set to purify：Using the second individual character matter of adsorbent, it can be achieved that adsorbent is adsorbed and solved under low pressure under high pressure
Regeneration is inhaled, so as to form absorption and the regeneration cycle of adsorbent, achievees the purpose that continuous separating-purifying.
But the Pressure Swing Adsorption technique of the prior art can not realize the efficient hydrogen for purifying out high-purity, especially
It is the purification for being directed to hydrogen in biological fuel gas.
The content of the invention
For the above problem of the prior art, it is a primary object of the present invention to provide a kind of be used in biological fuel gas
The method of purification and its system of hydrogen, using principle of pressure swing adsorption, it is reasonable that technique is set, and the hydrogen purity after purification can reach
99.99%, and hydrogen recovery rate is high, and purification efficiency is obviously improved.
In order to achieve the above object, the present invention adopts the following technical scheme that：It is a kind of to be used for hydrogen in biological fuel gas and carry
Pure method, is made of technique units such as decarburization, drying, pressure-variable adsorptions, and the pressure-variable adsorption uses the company of multiple adsorption towers parallel connection
Mode is connect, control piper is set between each adsorption tower, controls the gas circulation between two adsorption towers, to reach between two adsorption towers
Air pressure exchange；Wherein each adsorption tower top exit output products gas, outlet at bottom output stripping gas；Wherein each adsorption tower according to
It is secondary adsorbed, drop, along put, inverse put, rinse, vacuumize, rise, the circulation step of final rise.
The form of control piper between each adsorption tower is not limited herein, those skilled in the art can select according to the prior art
Suitable pipe fitting, instrument, valve etc. is taken to be attached with suitable connection mode, it is only necessary to realize connection and disconnection between an absorption tower
Automatically control, two absorption towers can be connected within the time of reservation according to technological requirement and be closed within the time of reservation
Connection between two towers.
Adsorption step:Biological fuel gas enters adsorption tower from bottom to top, and impurity composition is loaded in the absorption in adsorption tower
Making choice property of agent is adsorbed, wherein except H2Impurity component in addition is adsorbed, and obtains pure H2；
Step (drops) in drop pressure:After the completion of adsorption step, along absorption direction by elevated pressures hydrogen in adsorption tower
The process of other completed low pressure adsorbent towers is sequentially placed into, this process had both played the role of the decompression of High Pressure Absorption tower, at the same time
Also the hydrogen and pressure in adsorption tower dead space have been recycled；
It is rapid along strideing：Adsorption tower is after step is dropped, along the decompression of absorption direction, the H for depressurizing out2Put into suitable
Surge tank stores；
Inverse put step:Adsorption tower will adsorb tower pressure interior force along after putting, against absorption direction and be down to close to normal pressure, at this time
The impurity adsorbed starts to desorb from adsorbent, is put into surge tank；
Rinsing step：After inverse put, with along the low pressure H in deflation tank2Adsorption tower is rinsed, is at this moment adsorbed
Impurity largely desorbs, and flows into stripping gas surge tank against absorption direction；
Vacuum step:In this course, adsorbent bed is vacuumized against absorption direction with vacuum pump, makes impurity
Thoroughly extraction, the adsorbent allowed in tower are regenerated completely；
Boost pressure (rises) step:It is corresponding with drop pressure step, utilize the drop pressure step of other adsorption towers
Adsorption tower is boosted in the input at the top of the adsorption tower of the gas of output, this process has recycled other adsorbent bed dead spaces
Hydrogen；
Product gas boosting step (final rise):After liter process, adsorption column pressure has been risen to close to adsorptive pressure.This
When, with product H2Adsorption column pressure is risen into adsorptive pressure；After this process, adsorption tower, which just completes, entirely to be regenerated
Journey, gets ready for absorption next time.
Each adsorption tower passes through the above process, completes the adsorption process of each step of adsorption tower, is followed into next
Ring process.
As further preferably, the pressure swing adsorption technique unit is connected in parallel using 8 adsorption towers, every adsorption tower
The drop step carried out is dropped including one down, two down, three, and rising step, including one, liter, two rise, three rise, wherein
Between two adsorption towers, the one down step of first adsorption tower corresponds to the three of another adsorption tower and rises step, first
The two down step of adsorption tower corresponds to the two of another adsorption tower and rises step, and the three of first adsorption tower, which drops step, corresponds to
One in another adsorption tower rises step.
As the further absorption that preferably, multiple adsorption towers carry out successively in the pressure swing adsorption technique unit, drop,
Along put, inverse put, rinse, vacuumize, rising, the same steps in the circulation step of final rise stagger operation in time.
Preferably controlled as further by the control piper between two adsorption towers, wherein adsorption tower is equal
The gas of drop step output rises step for another adsorption tower operation, and the air pressure run at this time in the adsorption tower for dropping step is big
The air pressure in the adsorption tower of step is risen in operation.
As it is further preferably, wherein one down, two down, three drop, inverse put, rinse, vacuumize, liter, two
Rise, three rise, final rise and etc. run time be all a unit interval, wherein along rapid run time of strideing for two
Unit interval, the run time of adsorption step is four unit interval.For example, one rises, two rise, three liter, final rises etc. walk
Rapid run time is all 1 minute, wherein along rapid run time of strideing for 2 minutes, the run time of adsorption step is 4 points
Clock.
As it is further preferably, each adsorption tower along stride it is rapid in the gas of output be temporarily stored in along putting in surge tank,
Along put surge tank supply respectively give each adsorption tower operation rinsing step.It is described along putting surge tank also by control piper and each suction
Attached tower connection, realizes and is automatically controlled with being connected between each adsorption tower with what is disconnected..
Preferably the decarbonization process unit is composed in series using at least two lye absorption towers as further, biological
Matter combustion gas passes sequentially through at least two lye absorption towers, and wherein lye absorption tower inlet pressure control is in 0.3MPa~0.5Mpa；
The drying process unit is composed in series using at least two drying towers；Boosting is 1.5Mpa in adsorption tower in the adsorption step
~2.0MPa, evacuated pressure is -0.05Mpa~-0.01Mpa in the vacuum step.
A kind of purification system for being used for hydrogen in biological fuel gas, it is characterised in that：Including：
At least one lye absorption tower, is connected in series between multiple lye absorption towers, in organism-absorbing matter combustion gas
Carbon dioxide；
At least one drying tower, is connected in series between multiple drying towers, and first drying tower is absorbed with last lye
Tower connects, and is dehydrated for biological fuel gas；
At least two adsorption towers, the adsorption tower includes at least one top exit and at least one outlet at bottom, multiple
It is connected in parallel between adsorption tower；The total mouth of parallel connection of the multiple adsorption tower outlet at bottom is connected with last drying tower, described
The total mouth output products hydrogen of parallel connection of the top exit on multiple absorption towers.
Stripping gas surge tank, is connected with the multiple adsorption tower outlet at bottom, for receiving stripping gas；
Along putting surge tank, and the multiple adsorption tower top exit, for receiving along the gas that exports suddenly of strideing；
Control piper, the control piper is arranged between each adsorption tower and each adsorption tower and stripping gas surge tank, suitable
Between putting surge tank, the gas circulation between two adsorption towers is controlled, to reach the exchange of the air pressure between two adsorption towers.
As further preferably, the quantity of the adsorption tower is 8；The control piper includes pipeline, sequencing valve, pressure
Power table and flowmeter.
As it is further preferably, due to combustion gas being distributed as in adsorption tower：CO2In the bottom, organic gas is in CO2
At the same time at the middle part of adsorption tower above gas, CO is in CH4Above, it is topmost H2；Distributed areas based on combustion gas, the absorption
Adsorbent is placed using layering in tower, is divided into 3 layers, and bottom one layer is all activated carbon, and intermediate layer is activated carbon and 5A molecular sieves
Mixing is placed, and the intermediate layer is using activated carbon and 5A molecular sieves according to 4~2:1 volume ratio mixing is used as adsorbent, most
Upper strata is all 5A molecular sieves.The purpose of adsorbent layering filling is the distribution difference because of the gas during pressure-variable adsorption,
Adsorbent layering can reach more preferable clean-up effect.
The beneficial effects of the invention are as follows：The present invention purifies the hydrogen in biological fuel gas by pressure swing adsorption method, rationally
Adsorption tower quantity and structure are set so that purpose product hydrogen purity can reach 99.99%, and hydrogen recovery rate and carry
Pure efficiency is obviously improved.
1st, according to the component of biological fuel gas, it reasonably have selected that adsorption tower is sorbent used and its proportioning.CO in combustion gas2
Content it is big.Activated carbon is very big to the adsorption capacity of carbon dioxide, and adsorbance is fairly obvious with the eustasy of pressure, is
The good adsorbent of carbon dioxide, 5A molecular sieves are quite different, it is under low pressure with regard to a large amount of absorbing carbon dioxides, and with pressure
Adsorbance change unobvious are raised, under low pressure difficult desorption, therefore the adsorbent of carbon dioxide cannot be made, therefore will in adsorbent
Active charcoal.5A molecular sieves are very strong for the adsorption capacity of methane, it is when pressure amplitude is identical, the change of equilibrium adsorption capacity
Change it is essentially identical, can be as the adsorbent of methane.Molecular sieve is very strong for the adsorption capacity of organic gas and nitrogen at the same time,
Suitable for this biological fuel gas.Activated carbon and 5A molecular sieves are used as the adsorbent of carbon monoxide, the High Pressure Absorption of activated carbon
Amount is bigger than molecular sieve, and low pressure desorption is easy, but the adsorption capacity of molecular sieve is stronger, suitable for requiring carbon monoxide product
Very low situation, the two absorption for CO can reach requirement.The power of regeneration of activated carbon is strong, based on cost consideration and experiment
As a result, adsorbent is paved with adsorbent bed using activated carbon and 5A molecular sieves in this technique.
2nd, the distributed areas based on combustion gas, adsorbent of the present invention are placed using layering, are divided into 3 layers, one layer of bottom
Activated carbon is all, intermediate layer is activated carbon and 5A molecular sieves according to 4~2:1 volume ratio mixing is placed, and the superiors are all 5A
Molecular sieve.Valve is program-controlled valve.Adsorption tower is GB150 pressure vessels.Pressure gauge and flowmeter are equipped with, comes control pressure and combustion
The flow of gas.It was proved that adsorption effect can reach required requirement, hydrogen purity reaches 99.99%.Adsorbent point
The purpose of layer filling is that adsorbent layering can reach preferably net because the distribution of gas is different during pressure-variable adsorption
Change effect.
3rd, the present invention can be lifted to rise using eight adsorption towers drops number so that the purity of hydrogen is up to standard, presses number
It is set as 3 times, i.e., drops and rise each 3 times.
4th, the adsorptive pressure in each adsorption tower is identical, is controlled by exterior compressor and vacuum pump.Compressor liter
Pressure, vacuum pump decompression.Easily adsorb high boiling component at the same pressure using adsorbent, be not easy to adsorb low boiling component and high pressure
The characteristic that the increase of lower adsorbance, the lower adsorbance of decompression reduce, unstripped gas is passed under pressure through it is adsorbent bed, relative to hydrogen
High-boiling-point impurity component is selectively adsorbed, and the hydrogen of low boiling component is not easy absorption by adsorbent bed, reaches hydrogen and miscellaneous
The separation of matter component；Then desorbing the impurity composition adsorbed under reduced pressure is regenerated adsorbent, in favor of carrying out again
The adsorbing separation of impurity.
5th, drop pressure process of the present invention:After the completion of adsorption process, along absorption direction by elevated pressures hydrogen in adsorbent bed
Gas is sequentially placed into the process of other completed low pressure adsorbent beds, this process both plays the role of decompression, while also recycles
Hydrogen and pressure in adsorbent bed dead space, this flow includes drop pressure process three times altogether, therefore can ensure hydrogen
Fully recycling.
6th, boost pressure process of the present invention:It is corresponding with drop pressure process, utilize the drop pressure gas of other adsorbent beds
Body boosts adsorbent bed from top, this process has recycled the hydrogen of other adsorbent bed dead spaces.Hydrogen recycling of the present invention
Rate can reach 89%.
Brief description of the drawings
Fig. 1 is the flow chart that the embodiment of the present application is used for the method for purification of hydrogen in biological fuel gas.
Fig. 2 is the structure diagram that the embodiment of the present application is used for hydrogen purification system in biological fuel gas.
What is marked in attached drawing is described as follows：The first lye of 1- absorption tower, the second lye of 2- absorption tower, the first drying towers of 3-,
The second drying towers of 4-, 5- stripping gas surge tank, 6- adsorption tower devices, 7- vacuum pumps, 8- are suitable to put surge tank, 9- product gas tanks.
Embodiment
The present invention is by providing a kind of method of purification and its system for being used for hydrogen in biological fuel gas, using pressure-variable adsorption
Principle, it is reasonable that technique is set, and the hydrogen purity after purification can reach 99.99%, and hydrogen recovery rate is high.
In order to better understand the above technical scheme, in conjunction with appended figures and specific embodiments to upper
Technical solution is stated to be described in detail.
As shown in Figure 1, the embodiment of the present application is used for the method for purification of hydrogen in biological fuel gas, by decarburization, drying, transformation
The technique units such as absorption composition, the pressure-variable adsorption use the connection mode of multiple adsorption towers parallel connection, are set between each adsorption tower
Control piper, controls the gas circulation between two adsorption towers, to reach the exchange of the air pressure between two adsorption towers；Wherein each adsorption tower
Top exit output products hydrogen, outlet at bottom output stripping gas；Wherein each adsorption tower adsorbed successively, drop, along put,
Inverse put, rinse, vacuumize, rising, the circulation step of final rise.
Adsorption step:Biological fuel gas enters adsorption tower from bottom to top, and the adsorbent that impurity composition is loaded makes choice
Property absorption, wherein except H2Impurity component in addition is adsorbed, and obtains pure H2, adsorption process proceed to absorption forward position close to
Terminate during adsorption tower top exit；
Step (drops) in drop pressure:After the completion of adsorption step, along absorption direction by elevated pressures hydrogen in adsorption tower
The process of other completed low pressure adsorbent towers is sequentially placed into, this process had both played the role of the decompression of High Pressure Absorption tower, at the same time
Also the hydrogen and pressure in adsorbent bed dead space have been recycled, this flow can carry out repeatedly pressing according to the quantity in parallel of adsorption tower
Pressure reduction, one of preferred embodiment are to select eight absorption in parallel, can be included drop pressure three times altogether
Process, therefore can ensure the abundant recycling of hydrogen；
It is rapid along strideing：Adsorption tower is after dropping, along the decompression of absorption direction, the H for depressurizing out2Slow down punching into suitable
Tank stores；
Inverse put step:Adsorption tower will adsorb tower pressure interior force along after putting, against absorption direction and be down to close to normal pressure, at this time
The impurity adsorbed starts to desorb from adsorbent, is put into surge tank；
Rinsing step：After inverse put, with along the low pressure H in deflation tank2Adsorption tower is rinsed, is at this moment adsorbed
Impurity largely desorbs, and flows into stripping gas surge tank against absorption direction；
Vacuum step:In this course, adsorbent bed is vacuumized against absorption direction with vacuum pump, makes impurity
Thoroughly extraction, the adsorbent allowed in tower are regenerated completely；
Boost pressure (rises) step:It is corresponding with drop pressure step, utilize the drop pressure gas of other adsorption towers
Boost from top to adsorbent bed, this process has recycled the hydrogen of other adsorption tower dead spaces, the number of the step with
Press the number of depressurization step corresponding；
Product gas boost process (final rise):After liter process, adsorption column pressure has been risen to close to adsorptive pressure.This
When, with product H2Adsorption column pressure is risen into adsorptive pressure；After this process, adsorption tower, which just completes, entirely to be regenerated
Journey, gets ready for absorption next time.
Single adsorption tower temporally runs above-mentioned steps successively, and two adsorption tower operation above-mentioned steps stagger in time,
Purpose makes the different step between two towers run at the same time, so as to other exchanges are carried out between two towers, for example the operation of a wherein tower is equal
When dropping step, by the folding of sequencing valves in control piper, the tower gas vent is set to rise another tower of step with operation
Gas feed connects, at this time since pressure difference has just carried out gas exchanges between two towers, untill two tower air pressures are equal, and this process
After after control piper automatically disconnect two towers between connection, make two towers can be with normal operation next step.
By the above process, the adsorption process of each step of adsorption tower is completed, into next cyclic process.
Preferable one embodiment, the pressure swing adsorption technique unit are connected in parallel using 8 adsorption towers, every adsorption tower
The drop step carried out is dropped including one down, two down, three, and rising step, including one, liter, two rise, three rise.Using 8
A adsorption tower, which can be lifted, to be risen, drops number so that the purity of hydrogen is up to standard.
Select 8 adsorption tower groups into pressure swing adsorption technique unit, pass through the rational technology controlling and process of control piper, realize single
A adsorption tower can be dropped process three times respectively and rise process three times, and such a processing arrangement can limited lifting hydrogen
Purification purity, while purification efficiency is influenced little, is the process choice optimized at present.
Multiple adsorption towers carry out successively in the pressure swing adsorption technique unit absorption, drop, along put, inverse put, flushing, pumping
Vacuum, rise, the same steps in the circulation step of final rise stagger operation in time.
Controlled by the control piper between two adsorption towers, wherein the gas for dropping step output of an adsorption tower supplies
Another adsorption tower operation rises step, runs the air pressure in the adsorption tower for dropping step at this time and is more than the suction that operation rises step
Air pressure in attached tower.
Wherein one down, two down, three drop, inverse put, rinse, vacuumize, one rise, two rise, three liter, final rises etc.
The run time of step is all a unit interval, wherein suitable rapid run time of strideing is two unit interval, adsorption step
Run time be four unit interval.
Flushing gas needed for the rinsing step is derived from along the gas exported suddenly of strideing.
The decarbonization process unit is composed in series using at least two lye absorption towers, and biological fuel gas passes sequentially through at least
Two lye absorption towers, wherein lye absorption tower inlet pressure are controlled in 0.3MPa~0.5Mpa；The drying process unit is adopted
It is composed in series with least two drying towers.
It is 1.5Mpa~2.0MPa to boost in the adsorption step in adsorption tower, evacuated pressure in the vacuum step
For -0.05Mpa~-0.01Mpa.
Each adsorption tower is temporarily stored in along putting in surge tank along the gas for rapid middle output of strideing, and is supplied respectively along surge tank is put
Rinsing step is run to each adsorption tower.
As shown in Fig. 2, the embodiment of the present application is used for the purification system of hydrogen in biological fuel gas, it is characterised in that：Including：
First lye absorption tower 1, the second lye absorption tower 2, are connected in series between two lye absorption towers, for absorbing life
Carbon dioxide in substance combustible gas；
First drying tower 3, the second drying tower 4, are connected in series between two drying towers, the first drying tower 3 and the second lye
Absorption tower 2 connects, and is dehydrated for biological fuel gas；
Multiple adsorption towers 6, the adsorption tower include at least one top exit and at least one outlet at bottom, multiple absorption
It is connected in parallel between tower；The total mouth of parallel connection of the multiple adsorption tower outlet at bottom is connected with the second drying tower 4, the multiple absorption
The total mouth output products gas of parallel connection of the top exit of tower.
Control piper, between the control piper sets each adsorption tower, controls the gas circulation between two adsorption towers, with up to
Exchanged to the air pressure between two adsorption towers.
The quantity of the adsorption tower is 8.
The control piper includes pipeline, sequencing valve, pressure gauge and flowmeter.
Stripping gas surge tank 5 is further included, is connected with the total mouth of the parallel connection of the multiple adsorption tower outlet at bottom, is solved for receiving
Air-breathing.
Further include along surge tank 8 is put, be connected with the total mouth of the parallel connection of the multiple adsorption tower top exit, for receiving suitable put
The gas of step output.
Adsorbent is placed using layering in the adsorption tower, is divided into 3 layers, and bottom one layer is activated carbon, and intermediate layer is to live
Property charcoal and 5A molecular sieves mixing place, the superiors are 5A molecular sieves.
The intermediate layer is using activated carbon and 5A molecular sieves according to 4~2:1 volume ratio mixing is used as adsorbent.
In the present embodiment, 8 adsorption towers are respectively A, B, C, D, E, F, G and H tower, the concrete technology of 8 adsorption towers
The visible table 1 below of flow:
Table 1
The now adsorption process of citing adsorption tower A：A towers proceed by one down, with D tower phases after the absorption of 4 minutes is carried out
Even.A pressure towers reduce, the rise of D pressure towers.After pressing, two pressure towers are of substantially equal.After one down, it is equal to carry out two
Drop.A towers are connected with E towers, same process.Then three drop A towers are connected with F towers, same process.It is all 1 minute to drop the time.Three
After secondary drop, A towers along journey is let off, be connected with H towers, H towers are rinsed, while pressure is also reducing, and gas is flowed into
Along in deflation tank.It is set as 2 minutes along the time is put.Inverse put process is carried out along rear A towers are put, gas is stripping gas, enters desorption
In gas surge tank.Then process is rinsed, A towers are connected with B towers at this time, and the suitable deflation in B towers flows through A towers, rear to enter suitable put
Gas tank.A towers are vacuumized after the completion of flushing, discharge the adsorbent gas of A towers, are recycled, are improved pure
Degree and the rate of recovery.Start three afterwards to rise, be connected with D towers, pressed, lift A pressure towers, the decompression of D towers.Two rise and E
Tower is connected, and liter is connected with F towers, and process is the same, boost pressure.It is all 1 minute to rise the time.Final pressure boosting is finally carried out,
Boost to the pressure of absorption, 1 minute time.Then adsorbed again.Each tower undergoes this 12 processes, and circulation carries out.
Pressure is carried out between tower and tower, and in each period, only two towers are being adsorbed, and this design treatment amount is big, and
Each step linking is reasonable.
1 each parameter of embodiment is as follows:Activated carbon of sorbent and 5A molecular sieves ratio are 2:1, inlet pressure 0.4MPa, one
A washing tower, two drying towers, vacuumize as -0.02MPa, boost as 1.5MPa, purify H2Purity be 99.892%, recycling
Rate 82%, has reached necessary requirement.
2 each parameter of embodiment is as follows:Activated carbon of sorbent and 5A molecular sieves ratio are 3:1, inlet pressure 0.3MPa, two
A washing tower, two drying towers, vacuumize as -0.03Mpa, boost as 1.7MPa, purify H2Purity be 99.894%, recycling
Rate 84%, basically reaches requirement.
3 each parameter of embodiment is as follows:Activated carbon of sorbent and 5A molecular sieves ratio are 4:1, inlet pressure 0.5MPa, two
A washing tower, a drying tower, vacuumizes as -0.04MPa, boosts as 1.9MPa, purifies H2Purity be 99.898%, recycling
Rate 85%, has reached necessary requirement.
4 each parameter of embodiment is as follows:Activated carbon of sorbent and 5A molecular sieves ratio are 4:1, inlet pressure 0.5MPa, two
A washing tower, two drying towers, vacuumize as -0.05MPa, boost as 2.0MPa, purify H2Purity be 99.993%, recycling
Rate 89%, has reached necessary requirement.
By data statistics orthogonal experiment, the embodiment of the present application uses activated carbon and 5A molecular sieves ratio as 4:1, inlet-pressure
Power is 0.5MPa, and washing tower is two, and drying tower is two, and evacuated pressure is -0.015MPa in pressure-swing absorption process, boosting
For 2.0Mpa technological parameter when, purify H2Purity reached required requirement, hydrogen recovery rate reaches 89%, based on into
This technique, can be adsorbed the optimal work of biological fuel gas purifying hydrogen of hydrogen by this consideration and the requirement of hydrogen commercial Application for eight towers
Skill.
Technical solution in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：Biomass hydrogen preparation
Technology can utilize abundant living resources, and pollution is small, is a kind of wide environmentally friendly hydrogen production process of development prospect.This Shen
Please biological fuel gas is purified by pressure swing adsorption method so that the purity of hydrogen reaches more than 99.99%, has reached industry
Application requirement：
1st, according to the component of biological fuel gas, it reasonably have selected that adsorption tower is sorbent used and its proportioning.CO in combustion gas2
Content it is big.Activated carbon is very big to the adsorption capacity of carbon dioxide, and adsorbance is fairly obvious with the eustasy of pressure, is
The good adsorbent of carbon dioxide, 5A molecular sieves are quite different, it is under low pressure with regard to a large amount of absorbing carbon dioxides, and with pressure
Adsorbance change unobvious are raised, under low pressure difficult desorption, therefore the adsorbent of carbon dioxide cannot be made, therefore will in adsorbent
Active charcoal.5A molecular sieves are very strong for the adsorption capacity of methane, it is when pressure amplitude is identical, the change of equilibrium adsorption capacity
Change it is essentially identical, can be as the adsorbent of methane.Molecular sieve is very strong for the adsorption capacity of organic gas and nitrogen at the same time,
Suitable for this biological fuel gas.Activated carbon and 5A molecular sieves are used as the adsorbent of carbon monoxide, the High Pressure Absorption of activated carbon
Amount is bigger than molecular sieve, and low pressure desorption is easy, but the adsorption capacity of molecular sieve is stronger, suitable for requiring carbon monoxide product
Very low situation, the two absorption for CO can reach requirement.The power of regeneration of activated carbon is strong, based on cost consideration and experiment
As a result, adsorbent is paved with adsorbent bed using activated carbon and 5A molecular sieves in this technique.
2nd, the distributed areas based on combustion gas, adsorbent of the present invention are placed using layering, are divided into 3 layers, one layer of bottom
Activated carbon is all, intermediate layer is activated carbon and 5A molecular sieves according to 4~2:1 volume ratio mixing is placed, and the superiors are all 5A
Molecular sieve.Valve is program-controlled valve.Adsorption tower is GB150 pressure vessels.Pressure gauge and flowmeter are equipped with, comes control pressure and combustion
The flow of gas.It was proved that adsorption effect can reach required requirement, hydrogen purity reaches 99.99%.Adsorbent point
The purpose of layer filling is that adsorbent layering can reach preferably net because the distribution of gas is different during pressure-variable adsorption
Change effect.
3rd, the present invention can be lifted to rise using eight adsorption towers drops number so that the purity of hydrogen is up to standard, presses number
It is set as 3 times, i.e., drops and rise each 3 times.
4th, the adsorptive pressure in each adsorption tower is identical, is controlled by exterior compressor and vacuum pump.Compressor liter
Pressure, vacuum pump decompression.Easily adsorb high boiling component at the same pressure using adsorbent, be not easy to adsorb low boiling component and high pressure
The characteristic that the increase of lower adsorbance, the lower adsorbance of decompression reduce, unstripped gas is passed under pressure through it is adsorbent bed, relative to hydrogen
High-boiling-point impurity component is selectively adsorbed, and the hydrogen of low boiling component is not easy absorption by adsorbent bed, reaches hydrogen and miscellaneous
The separation of matter component；Then desorbing the impurity composition adsorbed under reduced pressure is regenerated adsorbent, in favor of carrying out again
The adsorbing separation of impurity.
5th, drop pressure process of the present invention:After the completion of adsorption process, along absorption direction by elevated pressures hydrogen in adsorbent bed
Gas is sequentially placed into the process of other completed low pressure adsorbent beds, this process both plays the role of decompression, while also recycles
Hydrogen and pressure in adsorbent bed dead space, this flow includes drop pressure process three times altogether, therefore can ensure hydrogen
Fully recycling.
6th, boost pressure process of the present invention:It is corresponding with drop pressure process, utilize the drop pressure gas of other adsorbent beds
Body boosts adsorbent bed from top, this process has recycled the hydrogen of other adsorbent bed dead spaces.Hydrogen recycling of the present invention
Rate can reach 89%.
Although preferred embodiments of the present invention have been described, but those skilled in the art once know basic creation
Property concept, then can make these embodiments other change and modification.So appended claims be intended to be construed to include it is excellent
Select embodiment and fall into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these modification and variations
It is interior.
Claims (9)
1. a kind of method of purification for being used for hydrogen in biological fuel gas, is made of decarburization, drying, pressure swing adsorption technique unit, its
It is characterized in that:Pressure-variable adsorption uses the connection mode of multiple adsorption towers parallel connection, and control piper, control two are set between each adsorption tower
Gas circulation between adsorption tower, to reach the exchange of the air pressure between two adsorption towers；Wherein each adsorption tower top exit output production
Product gas, outlet at bottom output stripping gas；Wherein each adsorption tower adsorbed successively, drop, along put, inverse put, flushing, take out it is true
Sky, rise, the circulation step of final rise；
3 layers of placement of adsorbent point in the adsorption tower, bottom one layer is activated carbon, and intermediate layer is mixed for activated carbon and 5A molecular sieves
Close and place, the superiors are 5A molecular sieves.
2. the method for purification according to claim 1 for being used for hydrogen in biological fuel gas, it is characterised in that：The transformation is inhaled
Attached technique unit is connected in parallel using 8 adsorption towers, and the drop step that every adsorption tower carries out includes one down, two down, three
Drop, rising step, including one, liter, two rise, three rise.
3. it is used for the method for purification of hydrogen in biological fuel gas according to claim 1-2 any one of them, it is characterised in that：Become
Pressure absorbing process unit in multiple adsorption towers carry out successively absorption, drop, along put, inverse put, rinse, vacuumize, rise, final rise
Circulation step in same steps stagger in time operation.
4. it is used for the method for purification of hydrogen in biological fuel gas according to claim 1-2 any one of them, it is characterised in that：It is logical
The control piper control between two adsorption towers is crossed, wherein the gas for dropping step output of an adsorption tower is for another absorption
Tower operation rises step, runs the air pressure in the adsorption tower for dropping step at this time and is more than gas of the operation in the adsorption tower of liter step
Pressure.
5. the method for purification according to claim 2 for being used for hydrogen in biological fuel gas, it is characterised in that：Wherein one is equal
Drop, two down, three drop, inverse put, rinse, vacuumize, one rise, two rise, three rise, the run times of final rise step be all
One unit interval, wherein being two unit interval along rapid run time of strideing, the run time of adsorption step is four lists
The position time.
6. it is used for the method for purification of hydrogen in biological fuel gas according to claim 1-2 any one of them, it is characterised in that：Respectively
Adsorption tower is temporarily stored in along putting in surge tank along the gas for rapid middle output of strideing, and is supplied respectively to each adsorption tower along surge tank is put
Run rinsing step.
7. it is used for the method for purification of hydrogen in biological fuel gas according to claim 1-2 any one of them, it is characterised in that：
The decarbonization process unit is composed in series using at least two lye absorption towers, and biological fuel gas passes sequentially through at least two
Lye absorption tower, wherein lye absorption tower inlet pressure are controlled in 0.3MPa~0.5Mpa；
The drying process unit is composed in series using at least two drying towers；
Boosting is 1.5Mpa~2.0MPa in adsorption tower in adsorption step in the pressure swing adsorption technique unit, described to vacuumize step
Evacuated pressure is -0.05Mpa~-0.01Mpa in rapid.
A kind of 8. purification system for being used for hydrogen in biological fuel gas, it is characterised in that：Including：
At least one lye absorption tower, is connected in series between multiple lye absorption towers, for the dioxy in organism-absorbing matter combustion gas
Change carbon；
At least one drying tower, is connected in series between multiple drying towers, and first drying tower connects with last lye absorption tower
Connect, be dehydrated for biological fuel gas；
At least two adsorption towers, the adsorption tower include at least one top exit and at least one outlet at bottom, multiple absorption
It is connected in parallel between tower；The total mouth of parallel connection of the multiple adsorption tower outlet at bottom is connected with last drying tower, the multiple
The total mouth output products hydrogen of parallel connection of the top exit on absorption tower；
Stripping gas surge tank, is connected with the multiple adsorption tower outlet at bottom, for receiving stripping gas；
Along surge tank is put, it is connected with the multiple adsorption tower top exit, for receiving the suitable gas striden and exported suddenly；
Control piper, the control piper is arranged between each adsorption tower and each adsorption tower and stripping gas surge tank, along slowing down
Rush between tank, control the gas circulation between two adsorption towers, to reach the exchange of the air pressure between two adsorption towers；
3 layers of placement of adsorbent point in the adsorption tower, bottom one layer is activated carbon, and intermediate layer is mixed for activated carbon and 5A molecular sieves
Close and place, the superiors are 5A molecular sieves.
9. the purification system according to claim 8 for being used for hydrogen in biological fuel gas, it is characterised in that：The adsorption tower
Quantity be 8；
The control piper includes pipeline, sequencing valve, pressure gauge and flowmeter.
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| CN109276973A (en) * | 2018-10-08 | 2019-01-29 | 福建福源凯美特气体有限公司 | It drops a hint the method for middle separating-purifying hydrogen from refinery |
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