CN103359688A - Method for preparing hydrogen with different purity levels by use of semi-coke coke oven gas and system thereof - Google Patents

Method for preparing hydrogen with different purity levels by use of semi-coke coke oven gas and system thereof Download PDF

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CN103359688A
CN103359688A CN2013102895524A CN201310289552A CN103359688A CN 103359688 A CN103359688 A CN 103359688A CN 2013102895524 A CN2013102895524 A CN 2013102895524A CN 201310289552 A CN201310289552 A CN 201310289552A CN 103359688 A CN103359688 A CN 103359688A
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gas
hydrogen
coke
reaction
metal hydride
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CN2013102895524A
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CN103359688B (en
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杨福胜
李云
王玉琪
张诗伟
张凡
魏凌霄
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西安交通大学
西北大学
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Abstract

The invention discloses a method for preparing hydrogen with different purity levels by use of semi-coke coke oven gas and a system thereof, belonging to the technical field of coal chemical industry. The method comprises the following steps of: refining the associated coke oven gas of semi-coke; performing pressurization, freezing and impurity removal; mixing the associated coke oven gas with excessive water vapor, and carrying out a catalytic reforming reaction of methane to obtain hydrogen; after the product is cooled, feeding the product into a water gas shift membrane reactor for reaction as well as separation; performing membrane separation to obtain a first-level hydrogen product, and meanwhile, promoting the water gas reaction to realize deep conversion from carbon monoxide to hydrogen and reduce the concentration of the carbon monoxide to below 1%; dehydrating the product of the water gas conversion reaction, and feeding into a metal hydride temperature swing adsorption separation device to obtain the second-level hydrogen; and finally, treating the purge gas mainly containing nitrogen and carbon dioxide easily. According to the method disclosed by the invention, hydrogen is prepared by use of semi-coke coke oven gas, and hydrogen products with different purity levels are obtained by use of membrane separation and the temperature swing adsorption separation technology based on metal hydride, thereby achieving double aims of resource recovery and emission reduction.

Description

Utilize blue charcoal coke-oven gas to produce method and the system thereof of different purity grade hydrogen
Technical field:
The invention belongs to coal chemical technology, relate to a kind of method and system thereof that utilizes blue charcoal coke-oven gas to produce different purity grade hydrogen.
Background technology:
Blue charcoal claims again semicoke, is a kind of high-quality carbon material of producing by low-temperature pyrolysis of coal technique, can comprise the multiple applications of metallurgical industry.In Low Temperature Pyrolysis Process (approximately carrying out under 600 ℃ the temperature), generated simultaneously the by product coke-oven gas, its composition is comparatively complicated, see Table 1, but the coke-oven gas of the ordinary meaning that obtains from high-temperature coking is different, in this gas mixture except nitrogen other component concentration all not too high, overall calorific value is (about 7113~8368kJ/Nm on the low side also 3), therefore, in industry, act as a fuel and provide the required heat of pyrolysis except part, directly light by safe torch in a large number rear emptying, the wasting of resources that has caused.
The blue charcoal coke-oven gas of table 1 typical composition
Hydrogen is important industrial chemicals, all has a wide range of applications in synthetic ammonia, oil refining, electronics and metallurgical industry.In addition, as a kind of cleaning and the various secondary energy of preparation method, concern and favor that hydrogen acts as a fuel and also obtained people more have the investigator to predict, the energy structure take Hydrogen Energy as main means of non-electric energy sources can become a reality in the near future.Contain considerable hydrogen component in the blue charcoal coke-oven gas, methane and carbon monoxide also have the possibility of reforming hydrogen manufacturing in addition, if therefore can design technology with coke-oven gas as raw material for preparing hydrogen, not only can turn waste into wealth, realize efficient utilization of resource, can also reduce pollutent and greenhouse gas emission, the hydrogen that obtains simultaneously can be used for the refining of the another kind of by product-coal tar of blue charcoal refining process, thereby lengthening manufacturing chain, optimize the structure of production, therefore have significant economic and social benefit.
For the hydrogen recovery utilization in the common coke oven coal gas (high temperature pyrolysis product namely) a lot of research reports has been arranged, comprise article and multinomial relevant patent of invention, the technological line of proposition comprises the several different methods such as pressure-variable adsorption, membrane sepn and low temperature fractionation.But it should be noted that, density of hydrogen (〉 50% in the common coke oven coal gas) apparently higher than the described blue charcoal coke-oven gas of this patent (20~30%), the content of nitrogen is then far fewer than the latter, and therefore relevant technology has direct reference significance hardly for the recovery of blue charcoal coke-oven gas.
The hydrogen recovery difficult point of blue charcoal coke-oven gas is that its complicated component, hydrogen content are relatively low, and therefore, the methane and the carbon monoxide conversion that take full advantage of wherein are that hydrogen is necessary, and need the higher Hydrogen Separation method of the rate of recovery.
Summary of the invention:
For defects or deficiency, the invention provides and a kind ofly utilize blue charcoal coke-oven gas to be the method for waste different purity grade hydrogen, strengthen the water gas shift reaction hydrogen making by methane steam reforming and membrane sepn, and utilize permeable membrane and metal hydride adsorption separation device to obtain the hydrogen product of different purity grade, realize higher hydrogen recovery rate.
For reaching above purpose, technical scheme of the present invention is:
May further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, obtains purified gas;
2), purified gas is carried out mixing with superheated vapour behind the secondary pressurized, under the effect of high temperature, pressurization and catalyst A, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide;
3), mixed gas A is through after cooling, under the effect of catalyst B, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, obtain comprising the mixed gas B of hydrogen, simultaneously, hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
4), mixed gas B sloughed water vapor after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Described step 2) under the effect of high temperature, pressurization and catalyst A, make methane and the living condition of reacting of steeping in water for reconstitution in the purified gas be: temperature range is 600~900 ℃, and pressure range is 1~2MPa in.
Described step 2) during methane and superheated vapour reacted, the ratio range of overheated steam mole number and carbon atom mole number was 2.5~4.5.
Described catalyst A is for take Ni or precious metal as activeconstituents, with Al 2O 3, MgO, SiO 2, ZrO 2, TiO 2Or MgAl 2O 4One or more be prepared from for carrier, wherein, described precious metal comprises Au, Pt, Pd or Rh.
Described catalyst B comprises Fe-Cr catalyzer, Co-Mo catalyzer or Pt-CeO 2In the catalyzer one or more.
The blue charcoal coke-oven gas of utilization of the present invention is produced the system of different purity grade hydrogen:
Comprise methane reforming reaction device, First Heat Exchanger, water-gas shift membrane reactor, the first tripping device and metal hydride adsorption unit; The mixed gas of purified gas and overheated steam reacts in the methane reforming reaction device, obtain comprising the mixed gas A of hydrogen and carbon monoxide, mixed gas A is through the First Heat Exchanger laggard water-gas shift membrane reactor that enters that cools, carbon monoxide among the mixed gas A and water react in the water-gas shift membrane reactor, obtain comprising the mixed gas B of hydrogen, hydrogen is discharged by the per-meate side outlet of water-gas shift membrane reactor, obtain first step hydrogen product, mixed gas B enters the first tripping device, and in the first tripping device, slough water vapor, after sloughing the mixed gas B process metal hydride adsorption unit absorption of water vapor, foreign gas is discharged by relief outlet, hydrogen is adsorbed on the metal hydride sorbents in the metal hydride adsorption unit, metal hydride sorbents is heated, after blowing off residual impurity gas, can obtain second stage hydrogen product.
Described water-gas shift membrane reactor comprises housing, the two ends of housing are provided with entrance and exit, be provided with the selective permeability film that is connected with entrance and exit in the housing, the selective permeability film is divided into reaction side and per-meate side with housing, be filled with reaction material in the reaction side, be provided with the per-meate side outlet that is connected with per-meate side on the housing.
Described selective permeability film comprises metal or alloy density film, inorganic materials porous-film or metal-inorganic porous composite membrane, wherein, described alloy density film comprises Pd, Pd75Ag25, V-Ni, described inorganic materials porous-film comprises pottery or silica material porous-film, and described composite membrane comprises Pd-ceramic composite membrane, Pd75Ag25-pottery composite membrane, Pd-silica composite membrane, Pd75Ag25-silica composite membrane.
Described metal hydride adsorption unit comprises some group reaction devices unit, and wherein, upstream air inlet, absorption are being opened during hydrogen at least one group reaction device unit, and remaining reaction device unit is in the state that upstream air inlet, desorption obtain the second hydrogen of closing.
Also comprise the first compressor that is connected with blue charcoal coke-oven gas, the outlet of the first compressor is connected with the cold junction entrance of the second interchanger, the cold side outlet of the second interchanger is connected with the entrance of the second tripping device, and the outlet of the second tripping device is connected with the methane reforming reaction device by the second compressor.
Compared with prior art, beneficial effect of the present invention is:
Because the hydrogen recovery difficult point of blue charcoal coke-oven gas is its complicated component, hydrogen content is relatively low, therefore, the methane and the carbon monoxide conversion that take full advantage of wherein are that hydrogen is necessary, and need the higher Hydrogen Separation method of the rate of recovery, adopt among the present invention blue charcoal coke-oven gas is carried out pre-treatment, after obtaining purified gas, carry out mixing with superheated vapour behind the secondary pressurized, at high temperature, under the effect of high pressure and catalyst A, methane and superheated vapour in the purified gas are reacted, so that methane conversion is hydrogen, secondly, under the effect of catalyst B, react, make carbon monoxide and steeping in water for reconstitution give birth to reaction, obtain comprising the mixed gas of carbonic acid gas and hydrogen, simultaneously by selective permeability membrane sepn hydrogen partial wherein, obtain first step hydrogen product, this process that shifts resultant has promoted the conversion of reactant carbon monoxide conversely, again reacted mixed gas being passed into the metal hydride adsorption unit that is filled with metal hydride sorbents adsorbs, acquisition purity reaches the second stage hydrogen more than 99.9999%, so that the hydrogen in the blue charcoal coke-oven gas according to the actual requirements, obtain the hydrogen of different grades, and then, so that blue charcoal coke-oven gas is fully reclaimed and utilizes, saved the energy.
The blue charcoal coke-oven gas of the utilization of adopting among the present invention is produced the system of different purity grade hydrogen, owing to having utilized the water-gas shift membrane reactor, so that going out first burst of purity through membrane sepn in reaction, water-gas is about 99% hydrogen product, promote simultaneously the water-gas reaction carbon monoxide to the deep conversion of hydrogen, the former concentration is down to below 1%; In addition, the product of water gas shift reaction enters metal hydride Temp .-changing adsorption tripping device after removing moisture, obtains second stage purity at the high-purity hydrogen product more than 99.9999%, and the outgassing constituent of speeding accordingly is with CO 2And N 2Be main, easily process, can obtain the hydrogen of different purity grade, realized reclaiming the dual purpose of resource and decrement discharge.
Description of drawings:
Fig. 1 is that the present invention utilizes blue charcoal coke-oven gas to produce the system architecture schematic diagram of different purity grade hydrogen;
Fig. 2 is that the present invention utilizes blue charcoal coke-oven gas to produce the water-gas shift membrane reactor structural representation of the system of different purity grade hydrogen.
Among the figure, 1 is the first compressor, and 2 is the second interchanger, 3 is the second tripping device, and 4 is the second compressor, and 5 is the methane reforming reaction device, 6 is First Heat Exchanger, 7 are the water-gas shift membrane reactor, and 8 is the first tripping device, and 9 is the metal hydride adsorption unit, 7-1 is the reaction side, 7-2 is per-meate side, and 7-3 is the selective permeability film, and 7-4 is housing.
Embodiment:
Below in conjunction with accompanying drawing the present invention is described in further detail.
Referring to shown in Figure 1, the invention provides and a kind ofly utilize blue charcoal coke-oven gas to produce the system of different purity grade hydrogen, comprise the first compressor 1 that is connected with blue charcoal coke-oven gas, the outlet of the first compressor 1 is connected with the second tripping device 3 by the second interchanger 2, the outlet of the second tripping device 3 is connected with methane reforming reaction device 5 by the second compressor 4, react through methane and superheated vapour in the purified gas, obtain comprising the mixed gas A of hydrogen and carbon monoxide, the outlet of methane reforming reaction device 5 is connected with water-gas shift membrane reactor 7 through First Heat Exchanger 6, through behind the water-gas shift membrane reactor 7 first step hydrogen being discharged by the per-meate side outlet, the reaction side outlet of water-gas shift membrane reactor 7 is connected with the first tripping device 8, the pneumatic outlet of the first tripping device 8 is connected with the gas inlet of metal hydride adsorption unit 9, after 9 absorption of metal hydride adsorption unit, foreign gas is discharged by relief outlet, hydrogen is adsorbed on the metal hydride sorbents in the metal hydride adsorption unit 9, metal hydride sorbents is heated, after blowing off residual impurity gas, can obtain second stage hydrogen, wherein, described metal hydride adsorption unit 9 comprises some group reaction devices unit, wherein, the upstream air inlet is being opened at least one group reaction device unit, during absorption hydrogen, remaining reaction device unit is in closes the upstream air inlet, desorption obtains the state of the second hydrogen.
The working process of native system is:
The mixed gas of purified gas and overheated steam reacts in methane reforming reaction device 5, obtain comprising the mixed gas A of hydrogen and carbon monoxide, mixed gas A is through the First Heat Exchanger 6 laggard water-gas shift membrane reactor 7 that enters that cools, carbon monoxide among the mixed gas A and water react in water-gas shift membrane reactor 7, obtain comprising the mixed gas B of hydrogen, hydrogen is discharged by the per-meate side outlet of water-gas shift membrane reactor 7, obtain first step hydrogen product, mixed gas B enters the first tripping device 8, and in the first tripping device 8, slough water vapor, after sloughing mixed gas B process metal hydride adsorption unit 9 absorption of water vapor, foreign gas is discharged by relief outlet, hydrogen is adsorbed on the metal hydride sorbents in the metal hydride adsorption unit 9, metal hydride sorbents is heated, after blowing off residual impurity gas, can obtain second stage hydrogen product.
Referring to shown in Figure 2, described water-gas shift membrane reactor 7 comprises housing 7-4, the two ends of housing 7-4 are provided with entrance and exit, be provided with the selective permeability film 7-3 that is connected with entrance and exit in the housing 7-4, selective permeability film 7-3 is divided into reaction side 7-1 and per-meate side 7-2 with housing 7-4, be filled with reaction material among the reaction side 7-1, be provided with the per-meate side outlet that is connected with per-meate side 7-2 on the housing 7-4.Described water-gas shift membrane reactor 7 can adopt concentric tube structure or slab construction; Described selective permeability film 7-3 comprises density metal film, inorganic materials porous-film or metal-inorganic porous composite membrane, wherein, described density metal film comprises Pd, Pd75Ag25 or V-Ni, described inorganic materials porous-film comprises pottery or silica material porous-film, and described composite membrane comprises Pd-ceramic composite membrane, Pd75Ag25-pottery composite membrane, Pd-silica composite membrane, Pd75Ag25-silica composite membrane.
Methane reforming reaction device 5 exit gass enter water-gas shift membrane reactor 7 through cooling.Water-gas shift membrane reactor 7 is divided into reaction side and per-meate side, the catalyzer of reaction side filled with water gas reforming, and per-meate side then is cavity, both are separated by the selective permeability film.Water gas shift reaction occurs by the charging of reaction side in the gas mixture of question response when flowing through beds, CO is combined with water and is generated CO 2And H 2H meanwhile 2Under the poor effect of film pressure at both sides, constantly see through film and flow into per-meate side, thereby reduced concentration and the dividing potential drop of hydrogen in the reaction side, be conducive to molecular balance and move right, realize the deep conversion of CO.Be first step hydrogen from the hydrogen of membrane sepn, purity is relatively low, can satisfy general requirement with the hydrogen occasion.
CH in the gas mixture that water-gas shift membrane reactor 7 reaction effluents go out 4All realized transforming comparatively fully with CO, concentration separately drops to very low level (~1%), in the first tripping device 8, slough after the water vapour composition that wherein comprises, dry gas is introduced the Temp .-changing adsorption device of filling metal hydride, hydride material selective adsorption hydrogen and not having an effect with other gas, the outgassing constituent of speeding of directly discharging is with CO 2And N 2Be main.Close air inlet after reaching the state of saturation of inhaling hydrogen until hydride, the hydrogen of absorption is discharged under heating condition, blow off a small amount of residual impurity gas and just can obtain High Purity Hydrogen more than 99.9999%, as second stage hydrogen product.
Wherein, the process of hydride adsorption and desorption hydrogen is shown below:
Wherein M is hydrogen storage alloy, and MHx is corresponding hydride, and hydrogen abstraction reaction is thermopositive reaction.
Utilize blue charcoal coke-oven gas to produce different purity grade hydrogen and describe below by concrete preparation method to invention.
Embodiment one:
A kind ofly utilize blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, such as tar, naphthalene, aromatics etc., obtains purified gas;
2), purified gas is carried out mix with superheated vapour behind the secondary pressurized, be that 600 ℃, pressure are under the effect of 2MPa and catalyst A in temperature, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 2.5, and described catalyst A is take Ni as main active ingredient, with Al 2O 3For carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is through after cooling, under the effect of Fe-Cr catalyzer, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, the hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation of carbon monoxide and water reaction is:
4), mixed gas B sloughed water vapour after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment two:
A kind ofly utilize blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, such as tar, naphthalene, aromatics etc., obtains purified gas;
2), purified gas is carried out mix with superheated vapour behind the secondary pressurized, be that 900 ℃, pressure are under the effect of 1MPa and catalyst A in temperature, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 4.5, wherein, described catalyst A is prepared from take MgO as carrier for take noble metal Au as activeconstituents.The chemical equation of reaction is:
3), mixed gas A is through after cooling, under the effect of Co-Mo catalyzer, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, the hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation of carbon monoxide and water reaction is:
4), mixed gas B sloughed water vapour after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment three:
A kind ofly utilize blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, such as tar, naphthalene, aromatics etc., obtains purified gas;
2), purified gas is carried out mix with superheated vapour behind the secondary pressurized, be that 700 ℃, pressure are under the effect of 1.5MPa and catalyst A in temperature, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 3, wherein, described catalyst A is take precious metals pt as activeconstituents, with SiO 2, ZrO 2And TiO 2For carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is through after cooling, under the effect of Pt-CeO2 catalyzer, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, the hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation of carbon monoxide and water reaction is:
4), mixed gas B sloughed water vapour after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment four:
A kind ofly utilize blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, such as tar, naphthalene, aromatics etc., obtains purified gas;
2), purified gas is carried out mix with superheated vapour behind the secondary pressurized, be that 900 ℃, pressure are under the effect of 1.5MPa and catalyst A in temperature, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 3, wherein, described catalyst A is take precious metals pd as activeconstituents, with SiO 2For carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is through after cooling, at Pt-CeO 2React under the effect of catalyzer, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation of carbon monoxide and water reaction is:
4), mixed gas B sloughed water vapour after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment five:
A kind ofly utilize blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, such as tar, naphthalene, aromatics etc., obtains purified gas;
2), purified gas is carried out mix with superheated vapour behind the secondary pressurized, be that 600 ℃, pressure are under the effect of 1.7MPa and catalyst A in temperature, methane and superheated vapour in the purified gas are reacted, obtain comprising the mixed gas A of hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 4, and described catalyst A is take Rh as main active ingredient, with TiO 2For carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is through after cooling, under the effect of Fe-Cr catalyzer, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, the hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation of carbon monoxide and water reaction is:
4), mixed gas B sloughed water vapour after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.

Claims (10)

1. one kind is utilized blue charcoal coke-oven gas to produce the method for different purity grade hydrogen, it is characterized in that, may further comprise the steps:
1), to cooling after the pressurization of blue charcoal coke-oven gas, the restructuring of isolating in the coke-oven gas divides impurity, obtains purified gas;
2), purified gas is carried out mixing with superheated vapour behind the secondary pressurized, under the effect of high temperature, pressurization and catalyst A, methane and superheated vapour in the purified gas are reacted, obtain mixed gas A;
3), mixed gas A is through after cooling, under the effect of catalyst B, react, make carbon monoxide and steeping in water for reconstitution among the mixed gas A give birth to reaction, obtain comprising the mixed gas B of hydrogen, simultaneously, hydrogen component among the mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
4), mixed gas B sloughed water vapor after, pass into the metal hydride adsorption unit that is filled with metal hydride sorbents and adsorb, after metal hydride sorbents reaches capacity state, stop mixed gas B air inlet;
5), to metal hydride sorbents heating, the hydrogen in the metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
2. the blue charcoal coke-oven gas of utilization according to claim 1 is produced the method for different purity grade hydrogen, it is characterized in that: described step 2) under the effect of high temperature, pressurization and catalyst A, make methane and the living condition of reacting of steeping in water for reconstitution in the purified gas be: temperature range is 600~900 ℃, and pressure range is 1~2MPa.
3. the blue charcoal coke-oven gas of utilization according to claim 1 is produced the method for different purity grade hydrogen, it is characterized in that: during described step 2) methane and superheated vapour reacted, the ratio range of superheated vapour mole number and carbon atom mole number was 2.5~4.5.
4. the blue charcoal coke-oven gas of utilization according to claim 1 is produced the method for different purity grade hydrogen, it is characterized in that: described catalyst A is for take Ni or precious metal as activeconstituents, with Al 2O 3, MgO, SiO 2, ZrO 2, TiO 2Or MgAl 2O 4One or more be prepared from for carrier, wherein, described precious metal comprises Au, Pt, Pd or Rh.
5. the blue charcoal coke-oven gas of utilization according to claim 1 is produced the method for different purity grade hydrogen, and it is characterized in that: described catalyst B comprises Fe-Cr catalyzer, Co-Mo catalyzer or Pt-CeO 2In the catalyzer one or more.
6. a system that produces different purity grade hydrogen based on the blue charcoal coke-oven gas of utilization claimed in claim 1 is characterized in that: comprise methane reforming reaction device (5), First Heat Exchanger (6), water-gas shift membrane reactor (7), the first tripping device (8) and metal hydride adsorption unit (9); The mixed gas of purified gas and overheated steam reacts in methane reforming reaction device (5), obtain comprising the mixed gas A of hydrogen and carbon monoxide, mixed gas A is through First Heat Exchanger (6) the laggard water-gas shift membrane reactor (7) that enters that cools, carbon monoxide among the mixed gas A and water react in water-gas shift membrane reactor (7), obtain comprising the mixed gas B of hydrogen, hydrogen is discharged by the per-meate side outlet of water-gas shift membrane reactor (7), obtain first step hydrogen product, mixed gas B enters the first tripping device (8), and in the first tripping device (8), slough water vapor, after sloughing mixed gas B process metal hydride adsorption unit (9) absorption of water vapor, foreign gas is discharged by relief outlet, hydrogen is adsorbed on the metal hydride sorbents in the metal hydride adsorption unit (9), metal hydride sorbents is heated, after blowing off residual impurity gas, can obtain second stage hydrogen product.
7. the blue charcoal coke-oven gas of utilization according to claim 6 is produced the system of different purity grade hydrogen, it is characterized in that: described water-gas shift membrane reactor (7) comprises housing (7-4), the two ends of housing (7-4) are provided with entrance and exit, be provided with the selective permeability film (7-3) that is connected with entrance and exit in the housing (7-4), selective permeability film (7-3) is divided into reaction side (7-1) and per-meate side (7-2) with housing (7-4), be filled with reaction material in the reaction side (7-1), be provided with the per-meate side outlet that is connected with per-meate side (7-2) on the housing (7-4).
8. the blue charcoal coke-oven gas of utilization according to claim 7 is produced the system of different purity grade hydrogen, it is characterized in that: described selective permeability film (7-3) comprises density metal film, inorganic materials porous-film or metal-inorganic porous composite membrane, wherein, described density metal film comprises Pd, Pd75Ag25 or V-Ni, described inorganic materials porous-film comprises pottery or silica material porous-film, and described porous composite film comprises Pd-ceramic composite membrane, Pd75Ag25-ceramic composite membrane, Pd-silica composite membrane, Pd75Ag25-silica composite membrane.
9. the blue charcoal coke-oven gas of utilization according to claim 6 is produced the system of different purity grade hydrogen, it is characterized in that: described metal hydride adsorption unit (9) comprises some group reaction devices unit, wherein, at least one group reaction device unit is when opening upstream air inlet, absorption hydrogen, and remaining reaction device unit is in the state of closing upstream air inlet, desorption acquisition second stage hydrogen.
10. the blue charcoal coke-oven gas of utilization according to claim 6 is produced the system of different purity grade hydrogen, it is characterized in that: also comprise the first compressor (1) that is connected with blue charcoal coke-oven gas, the outlet of the first compressor (1) is connected with the cold junction entrance of the second interchanger (2), the cold side outlet of the second interchanger (2) is connected with the entrance of the second tripping device (3), and the outlet of the second tripping device (3) is connected with methane reforming reaction device (5) by the second compressor (4).
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CN105316010A (en) * 2014-07-30 2016-02-10 宝鸡市泰和化工科技有限公司 Two-stage semi-coke furnace, and process for recovering furnace gas and producing synthetic ammonia
CN105621358A (en) * 2014-10-27 2016-06-01 中国石油化工股份有限公司 Methane-reforming and hydrogen-production method
CN105621358B (en) * 2014-10-27 2017-07-25 中国石油化工股份有限公司 A kind of methane reforming hydrogen production process
CN105110291A (en) * 2015-07-21 2015-12-02 河南环宇石化装备科技股份有限公司 Method for preparation of LNG from recovered coke oven gas and co-production of synthetic ammonia
CN105800556A (en) * 2016-02-26 2016-07-27 西北大学 Method for cogenerating activated carbon and hydrogen by coal char gasification and methane reforming coupling technology
CN106283272A (en) * 2016-10-25 2017-01-04 西北大学 A kind of method that lower carbon number hydrocarbons catalytic pyrolysis prepares carbon fiber and hydrogen

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