CN103359688B - Blue charcoal coke-oven gas is utilized to produce method and the system thereof of different purity grade hydrogen - Google Patents
Blue charcoal coke-oven gas is utilized to produce method and the system thereof of different purity grade hydrogen Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 221
- 239000001257 hydrogen Substances 0.000 title claims abstract description 138
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 138
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003610 charcoal Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 65
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012528 membrane Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000002594 sorbent Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 22
- 230000000694 effects Effects 0.000 claims description 20
- 230000035699 permeability Effects 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 18
- 239000012466 permeate Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002407 reforming Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 4
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 229910020068 MgAl Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- -1 simultaneously Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 235000011089 carbon dioxide Nutrition 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 238000001833 catalytic reforming Methods 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 6
- 239000011269 tar Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910002838 Pt-CeO2 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The method utilizing blue charcoal coke-oven gas to be waste different purity grade hydrogen and a system thereof, belong to technical field of coal chemical industry.Comprise the following steps: the association coke-oven gas refining blue charcoal, first through the freezing removal of impurities of pressurization, next mix the catalytic reforming reaction hydrogen making carrying out methane with excess steam, enter water-gas shift membrane reactor after product cooling, react and be separated.Go out first step hydrogen product through membrane sepn, meanwhile, promote that water-gas reaction carbon monoxide is to the deep conversion of hydrogen, is down to less than 1% by the former concentration.The product of water gas shift reaction enters metal hydride Temp .-changing adsorption tripping device after removing moisture, obtains second stage hydrogen, and finally more easily processes based on the periodic off-gases of nitrogen and carbonic acid gas.The present invention uses blue charcoal coke-oven gas hydrogen making, and utilizes membrane sepn and obtain the hydrogen product of different purity grade based on the Temp .-changing adsorption isolation technique of metal hydride, achieves the dual purpose of Resource recovery and decrement discharge.
Description
Technical field:
The invention belongs to coal chemical technology, relate to a kind of utilize blue charcoal coke-oven gas to produce different purity grade hydrogen method and system.
Background technology:
Blue charcoal, also known as semicoke, is a kind of high-quality carbon material produced by low-temperature pyrolysis of coal technique, can comprising the multiple applications of metallurgical industry.In Low Temperature Pyrolysis Process (carrying out at the temperature of about 600 DEG C), generate by product coke-oven gas simultaneously, its composition is comparatively complicated, in table 1, but it is different from the coke-oven gas of the ordinary meaning that high-temperature coking obtains, in this gas mixture, except nitrogen, other component concentration is all not too high, and overall calorific value is (about 7113 ~ 8368kJ/Nm on the low side also
3), therefore, in the industry except part provides the heat needed for pyrolysis as fuel, in a large number direct lighted by safe torch rear emptying, the wasting of resources caused.
Table 1 blue charcoal coke-oven gas 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 clean and secondary energy that preparation method is various, hydrogen have also been obtained concern and the favor of people as fuel, more has investigator to predict, one is main means of non-electric energy sources with Hydrogen Energy energy structure can become a reality in the near future.Containing considerable hydrogen component in blue charcoal coke-oven gas, methane and carbon monoxide also have the possibility of reforming hydrogen manufacturing in addition, if therefore energy design technology is using coke-oven gas as raw material for preparing hydrogen, not only can to turn waste into wealth, realize effective utilization of resource, can also decreasing pollution thing and greenhouse gas emission, the hydrogen simultaneously obtained may be used for the refining of the another kind of by product-coal tar of blue charcoal refining process, thus lengthening manufacturing chain, to optimize the structure of production, therefore there is significant economic and social benefit.
Hydrogen recovery in common coke oven coal gas (namely high temperature pyrolysis product) is utilized and has had a lot of research reports, comprise article and multinomial relevant patent of invention, the technological line of proposition comprises the multiple methods such as pressure-variable adsorption, membrane sepn and low temperature fractionation.But it should be noted that, density of hydrogen (>50%) in common coke oven coal gas is apparently higher than the blue charcoal coke-oven gas (20 ~ 30%) described in this patent, 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, to make full use of methane wherein and carbon monoxide conversion be hydrogen is necessary, and the Hydrogen Separation method needing the rate of recovery higher.
Summary of the invention:
For above-mentioned defect or deficiency, the invention provides and a kind ofly utilize blue charcoal coke-oven gas for the method for waste different purity grade hydrogen, water gas shift reaction hydrogen making is strengthened by methane steam reforming and membrane sepn, and utilize permeable membrane and metal hydride material adsorbs tripping device to obtain the hydrogen product of different purity grade, realize higher hydrogen recovery rate.
For reaching above object, technical scheme of the present invention is:
Comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, obtain purified gas;
2), purified gas is carried out secondary pressurized after mix with superheated vapour, under the effect of high temperature, pressurization and catalyst A, the methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising hydrogen and carbon monoxide;
3), mixed gas A is after cooling, react under the effect of catalyst B, carbon monoxide in mixed gas A and water are reacted, obtain the mixed gas B comprising hydrogen, simultaneously, hydrogen component in 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 is sloughed water vapor after, pass into the metal hydride material adsorbs device being 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 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, the condition that the methane in purified gas and water are reacted is: temperature range is 600 ~ 900 DEG C, and pressure range is 1 ~ 2MPa.
Described step 2) during methane and superheated vapour react, the ratio range of overheated steam mole number and carbon atom mole number is 2.5 ~ 4.5.
Described catalyst A is with Ni or precious metal for 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
2one or more in catalyzer.
The blue charcoal coke-oven gas of utilization of the present invention produces the system of different purity grade hydrogen:
Comprise methane reforming reactor, First Heat Exchanger, water-gas shift membrane reactor, the first tripping device and metal hydride material adsorbs device, the mixed gas of purified gas and overheated steam reacts in methane reforming reactor, obtain the mixed gas A comprising hydrogen and carbon monoxide, mixed gas A enters water-gas shift membrane reactor after First Heat Exchanger cools, carbon monoxide in mixed gas A and water react in water-gas shift membrane reactor, obtain the mixed gas B comprising 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 water vapor is sloughed in the first tripping device, slough the mixed gas B of water vapor after the absorption of metal hydride material adsorbs device, foreign gas is discharged by relief outlet, hydrogen is adsorbed in the metal hydride sorbents in metal hydride material adsorbs device, metal hydride sorbents is heated, after blowing off residual impurity gas, second stage hydrogen product can be obtained.
Described water-gas shift membrane reactor comprises housing, the two ends of housing are provided with entrance and exit, the selective permeability film be connected with entrance and exit is provided with in housing, housing is divided into reaction side and per-meate side by selective permeability film, reaction is filled with reaction material in side, housing is provided with the per-meate side be connected with per-meate side and exports.
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-makes pottery composite membrane, Pd-silica composite membrane, Pd75Ag25-silica composite membrane.
Described metal hydride material adsorbs device comprises some group reaction device unit, and wherein, at least one group reaction device unit is when opening upstream inlet, adsorbed hydrogen, and remaining reaction device unit is in closes the state that upstream inlet, desorption obtain the second hydrogen.
Also comprise the first compressor be connected with blue charcoal coke-oven gas, the outlet of the first compressor is connected with the cold-side inlet 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 methane reforming reactor 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, to make full use of methane wherein and carbon monoxide conversion be hydrogen is necessary, and the Hydrogen Separation method needing the rate of recovery higher, adopt in the present invention and blue charcoal coke-oven gas is carried out pre-treatment, after obtaining purified gas, mix with superheated vapour after carrying out secondary pressurized, at high temperature, under the effect of high pressure and catalyst A, methane in purified gas and superheated vapour are reacted, methane conversion is made to be hydrogen, secondly, react under the effect of catalyst B, carbon monoxide and water are reacted, obtain the mixed gas comprising carbonic acid gas and hydrogen, simultaneously by selective permeability membrane sepn hydrogen partial wherein, obtain first step hydrogen product, the process of this transfer resultant facilitates the conversion of reactant carbon monoxide conversely, pass into reacted mixed gas the metal hydride material adsorbs device being filled with metal hydride sorbents again to adsorb, obtain the second stage hydrogen that purity reaches more than 99.9999%, make hydrogen in blue charcoal coke-oven gas according to the actual requirements, obtain the hydrogen of different grades, and then, blue charcoal coke-oven gas is made fully to be reclaimed and utilize, save the energy.
The blue charcoal coke-oven gas of the utilization adopted in the present invention produces the system of different purity grade hydrogen, owing to make use of water-gas shift membrane reactor, water-gas is made to go out through membrane sepn the hydrogen product that first burst of purity is about 99% in the reaction, promote that water-gas reaction carbon monoxide is to the deep conversion of hydrogen, is down to less than 1% by the former concentration simultaneously; In addition, the product of water gas shift reaction enters metal hydride Temp .-changing adsorption tripping device after removing moisture, and obtain the high-purity hydrogen product of second stage purity more than 99.9999%, corresponding periodic off-gases composition is with CO
2and N
2be main, easily process, the hydrogen of different purity grade can be obtained, achieve the dual purpose of Resource recovery and decrement discharge.
Accompanying drawing illustrates:
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.
In 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 methane reforming reactor, 6 is First Heat Exchanger, 7 is water-gas shift membrane reactor, and 8 is the first tripping device, and 9 is metal hydride material adsorbs device, 7-1 is reaction side, 7-2 is per-meate side, and 7-3 is selective permeability film, and 7-4 is housing.
Embodiment:
Below in conjunction with accompanying drawing, the present invention is described in further detail.
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 be 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 reactor 5 by the second compressor 4, methane in purified gas and superheated vapour react, obtain the mixed gas A comprising hydrogen and carbon monoxide, the outlet of methane reforming reactor 5 is connected with water-gas shift membrane reactor 7 through First Heat Exchanger 6, after water-gas shift membrane reactor 7, first step hydrogen is discharged by 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 material adsorbs device 9, after metal hydride material adsorbs device 9 adsorbs, foreign gas is discharged by relief outlet, hydrogen is adsorbed in the metal hydride sorbents in metal hydride material adsorbs device 9, metal hydride sorbents is heated, after blowing off residual impurity gas, second stage hydrogen can be obtained, wherein, described metal hydride material adsorbs device 9 comprises some group reaction device unit, wherein, at least one group reaction device unit is opening upstream inlet, during adsorbed hydrogen, remaining reaction device unit is in closedown upstream 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 reactor 5, obtain the mixed gas A comprising hydrogen and carbon monoxide, mixed gas A enters water-gas shift membrane reactor 7 after First Heat Exchanger 6 cools, carbon monoxide in mixed gas A and water react in water-gas shift membrane reactor 7, obtain the mixed gas B comprising 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 water vapor is sloughed in the first tripping device 8, slough the mixed gas B of water vapor after metal hydride material adsorbs device 9 adsorbs, foreign gas is discharged by relief outlet, hydrogen is adsorbed in the metal hydride sorbents in metal hydride material adsorbs device 9, metal hydride sorbents is heated, after blowing off residual impurity gas, second stage hydrogen product can be obtained.
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, the selective permeability film 7-3 be connected with entrance and exit is provided with in housing 7-4, housing 7-4 is divided into reaction side 7-1 and per-meate side 7-2 by selective permeability film 7-3, be filled with reaction material in reaction side 7-1, housing 7-4 be provided with the per-meate side be connected with per-meate side 7-2 and export.Described water-gas shift membrane reactor 7 can adopt concentric tube configuration 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-makes pottery composite membrane, Pd-silica composite membrane, Pd75Ag25-silica composite membrane.
Methane reforming reactor 5 exit gas, through cooling, enters water-gas shift membrane reactor 7.Water-gas shift membrane reactor 7 is divided into reaction side and per-meate side, and the catalyzer of reaction side filled with water gas reforming, per-meate side is then cavity, and both are separated by selective permeability film.The gas mixture of question response is by reacting side charging, and when flowing through beds, water gas shift reaction occurs, CO is combined with water and generates CO
2and H
2; Meanwhile H
2under the effect of film pressure at both sides difference, constantly flowing into per-meate side through film, thus reducing hydrogen reacting concentration and the dividing potential drop of 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 meet the requirement of general hydrogen occasion.
CH in the gas mixture flowed out side is reacted from water-gas shift membrane reactor 7
4all achieve with CO and transform comparatively fully, respective concentration drops to very low level (~ 1%), slough the water vapor component wherein comprised in the first tripping device 8 after, dry gas is introduced the temperature swing absorption unit of filling metal hydride, hydride material selective adsorption hydrogen and not having an effect with other gas, the periodic off-gases composition of directly discharging is with CO
2and N
2be main.Thing to be hydrogenated closes air inlet after reaching the state of saturation of inhaling hydrogen, is discharged in a heated condition by the hydrogen of absorption, blows off the High Purity Hydrogen that a small amount of residual impurity gas just can obtain more than 99.9999%, as second stage hydrogen product.
Wherein, the process of hydride material adsorbs and desorb hydrogen gas is shown below:
Wherein M is hydrogen storage alloy, and MHx is corresponding hydride, and hydrogen abstraction reaction is thermopositive reaction.
Blue charcoal coke-oven gas is utilized to produce different purity grade hydrogen and be described below by concrete preparation method to invention.
Embodiment one:
Utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, as tar, naphthalene, aromatics etc., obtain purified gas;
2) mix with superheated vapour after, purified gas being carried out secondary pressurized, temperature be 600 DEG C, under pressure is the effect of 2MPa and catalyst A, methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising 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 be main active ingredient with Ni, with Al
2o
3for carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is after cooling, react under the effect of Fe-Cr catalyzer, carbon monoxide in mixed gas A and water are reacted, generate carbonic acid gas and hydrogen, product is mixed gas B, meanwhile, the hydrogen component in mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation that carbon monoxide and water react is:
4), mixed gas B is sloughed water vapour after, pass into the metal hydride material adsorbs device being 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 metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment two:
Utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, as tar, naphthalene, aromatics etc., obtain purified gas;
2) mix with superheated vapour after, purified gas being carried out secondary pressurized, temperature be 900 DEG C, under pressure is the effect of 1MPa and catalyst A, methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising 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 be activeconstituents with noble metal Au, is that carrier is prepared from MgO.The chemical equation of reaction is:
3), mixed gas A is after cooling, react under the effect of Co-Mo catalyzer, carbon monoxide in mixed gas A and water are reacted, generate carbonic acid gas and hydrogen, product is mixed gas B, meanwhile, the hydrogen component in mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation that carbon monoxide and water react is:
4), mixed gas B is sloughed water vapour after, pass into the metal hydride material adsorbs device being 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 metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment three:
Utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, as tar, naphthalene, aromatics etc., obtain purified gas;
2) mix with superheated vapour after, purified gas being carried out secondary pressurized, temperature be 700 DEG C, under pressure is the effect of 1.5MPa and catalyst A, methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 3, wherein, described catalyst A is be activeconstituents with precious metals pt, with SiO
2, ZrO
2and TiO
2for carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is after cooling, react under the effect of Pt-CeO2 catalyzer, carbon monoxide in mixed gas A and water are reacted, generate carbonic acid gas and hydrogen, product is mixed gas B, meanwhile, the hydrogen component in mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation that carbon monoxide and water react is:
4), mixed gas B is sloughed water vapour after, pass into the metal hydride material adsorbs device being 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 metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment four:
Utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, as tar, naphthalene, aromatics etc., obtain purified gas;
2) mix with superheated vapour after, purified gas being carried out secondary pressurized, temperature be 900 DEG C, under pressure is the effect of 1.5MPa and catalyst A, methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 3, wherein, described catalyst A is be activeconstituents with precious metals pd, with SiO
2for carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A after cooling, at Pt-CeO
2react under the effect of catalyzer, carbon monoxide in mixed gas A and water are reacted, generate carbonic acid gas and hydrogen, product is mixed gas B, simultaneously, hydrogen component in mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation that carbon monoxide and water react is:
4), mixed gas B is sloughed water vapour after, pass into the metal hydride material adsorbs device being 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 metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Embodiment five:
Utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, as tar, naphthalene, aromatics etc., obtain purified gas;
2) mix with superheated vapour after, purified gas being carried out secondary pressurized, temperature be 600 DEG C, under pressure is the effect of 1.7MPa and catalyst A, methane in purified gas and superheated vapour are reacted, obtain the mixed gas A comprising hydrogen and carbon monoxide, wherein, the ratio of overheated steam mole number and carbon atom mole number is 4, and described catalyst A is be main active ingredient with Rh, with TiO
2for carrier is prepared from.The chemical equation of reaction is:
3), mixed gas A is after cooling, react under the effect of Fe-Cr catalyzer, carbon monoxide in mixed gas A and water are reacted, generate carbonic acid gas and hydrogen, product is mixed gas B, meanwhile, the hydrogen component in mixed gas B is separated through the selective permeability film of water-gas shift membrane reactor, obtains first step hydrogen product;
The equation that carbon monoxide and water react is:
4), mixed gas B is sloughed water vapour after, pass into the metal hydride material adsorbs device being 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 metal hydride sorbents is discharged, and after blowing off residual impurity gas, obtains second stage hydrogen.
Claims (6)
1. utilize blue charcoal coke-oven gas to produce a method for different purity grade hydrogen, it is characterized in that, comprise the following steps:
1), to cooling after blue charcoal coke-oven gas pressurization, isolate the heavy constituent impurity in coke-oven gas, obtain purified gas;
2), purified gas is carried out secondary pressurized after mix with superheated vapour, under the effect of high temperature, pressurization and catalyst A, the methane in purified gas and superheated vapour are reacted, obtain mixed gas A; Described step 2) during methane and superheated vapour react, the ratio range of superheated vapour mole number and carbon atom mole number is 2.5 ~ 4.5; Wherein, under the effect of high temperature, pressurization and catalyst A, the condition that the methane in purified gas and water are reacted is: temperature range is 600 ~ 900 DEG C, and pressure range is 1 ~ 2MPa;
3), mixed gas A is after cooling, react under the effect of catalyst B, carbon monoxide in mixed gas A and water are reacted, obtain the mixed gas B comprising hydrogen, simultaneously, hydrogen component in 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 is sloughed water vapor after, pass into the metal hydride material adsorbs device being 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 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 produces the method for different purity grade hydrogen, it is characterized in that: described catalyst A for Ni or precious metal for 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.
3. the blue charcoal coke-oven gas of utilization according to claim 1 produces the method for different purity grade hydrogen, it is characterized in that: described catalyst B comprises Fe-Cr catalyzer, Co-Mo catalyzer or Pt-CeO
2one or more in catalyzer.
4. produce a system for different purity grade hydrogen method based on the blue charcoal coke-oven gas of utilization according to claim 1, it is characterized in that: comprise methane reforming reactor (5), First Heat Exchanger (6), water-gas shift membrane reactor (7), the first tripping device (8) and metal hydride material adsorbs device (9), the mixed gas of purified gas and overheated steam reacts in methane reforming reactor (5), obtain the mixed gas A comprising hydrogen and carbon monoxide, mixed gas A enters water-gas shift membrane reactor (7) after First Heat Exchanger (6) cools, carbon monoxide in mixed gas A and water react in water-gas shift membrane reactor (7), obtain the mixed gas B comprising 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 water vapor is sloughed in the first tripping device (8), slough the mixed gas B of water vapor after metal hydride material adsorbs device (9) absorption, foreign gas is discharged by relief outlet, hydrogen is adsorbed in the metal hydride sorbents in metal hydride material adsorbs device (9), metal hydride sorbents is heated, after blowing off residual impurity gas, second stage hydrogen product can be obtained, described water-gas shift membrane reactor (7) comprises housing (7-4), the two ends of housing (7-4) are provided with entrance and exit, the selective permeability film (7-3) be connected with entrance and exit is provided with in housing (7-4), housing (7-4) is divided into reaction side (7-1) and per-meate side (7-2) by selective permeability film (7-3), be filled with reaction material in reaction side (7-1), housing (7-4) be provided with the per-meate side be connected with per-meate side (7-2) and export, described metal hydride material adsorbs device (9) comprises some group reaction device unit, wherein, at least one group reaction device unit is when opening upstream inlet, adsorbed hydrogen, and remaining reaction device unit is in the state of closing upstream inlet, desorption acquisition second stage hydrogen.
5. the blue charcoal coke-oven gas of utilization according to claim 4 produces the system of different purity grade hydrogen method, 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.
6. the blue charcoal coke-oven gas of utilization according to claim 4 produces the system of different purity grade hydrogen method, it is characterized in that: also comprise the first compressor (1) be connected with blue charcoal coke-oven gas, the outlet of the first compressor (1) is connected with the cold-side inlet 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 reactor (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 |
| 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 |
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