CN107338075A - A kind of system of gasification of biomass co-producing hydrogen and porous carbon materials - Google Patents

A kind of system of gasification of biomass co-producing hydrogen and porous carbon materials Download PDF

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Publication number
CN107338075A
CN107338075A CN201710702904.2A CN201710702904A CN107338075A CN 107338075 A CN107338075 A CN 107338075A CN 201710702904 A CN201710702904 A CN 201710702904A CN 107338075 A CN107338075 A CN 107338075A
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gasification
gas
delivery line
biomass
subsystem
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CN107338075B (en
Inventor
陈汉平
陈伟
陈应泉
杨海平
王贤华
邵敬爱
张�雄
曾阔
张世红
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals

Abstract

The invention discloses a kind of system for gasification of biomass co-producing hydrogen and porous carbon materials, it is related to gasification of biomass field, including interconnected fluid bed steam gasification activation subsystem, gasification gas reform isolated subsystem, gasification gas cycling and reutilization subsystem.Fluid bed steam gasification activation subsystem carries out gasification activation process to biomass, and produces preliminary gasification gas and the porous carbon materials with flourishing pore structure；The gas that gasifies reforms isolated subsystem and carries out methanation reformation, water-gas shift reaction and separating-purifying to gasification gas, obtains hydrogen product；The gas cycling and reutilization subsystem that gasifies carries out cycling and reutilization to remnants gasification gas and cooling water, improves whole system Material and energy utilization rate.The present invention can realize that the high-valued greenization of biomass utilizes, while prepare the porous carbon materials of hydrogen product and high added value, effectively promote the high-quality conversion of biomass efficient.

Description

A kind of system of gasification of biomass co-producing hydrogen and porous carbon materials
Technical field
The present invention relates to gasification of biomass field, and in particular to a kind of gasification of biomass co-producing hydrogen and porous carbon materials System.
Background technology
Biomass energy is important regenerative resource, has the characteristics that green, low-carbon, cleaning, unique renewable carbon source. 《Biomass Energy Development " 13 " is planned》Biomass energy utilization will be accelerated, as promote production of energy and consumption revolution, The important content for improve environmental quality, developing a circular economy.Gasification of biomass is the main way of current biomass recovery energy One of footpath, it can convert biomass into clean gas fuel or the synthesis gas for synthesis clean liquid fuel.Compared to sky Gas or CO2Gasification, steam gasification can effectively lift H in gasification gas by gasification, aqueous vapor conversion and reforming reaction2Content, from And lift gasification gas calorific value or improve synthesis gas quality, therefore steam gasification is widely studied and applied.
Semicoke can be inevitably formed in biomass steam gasification.In order to ensure gasification efficiency, semicoke it is complete Full gasification is often the decisive step of gasification, but semicoke is gasified totally can form a large amount of CO and CO2, this, which will be reduced, gasifies H in gas2Relative amount.Therefore, in order to improve H2Yield, the de- CO of In-sltu reinforcement gasification2Or reformation decarburization is carried out to gasification gas and obtained To widely studied.
But above-mentioned decarbonization method all causes waste from carbon atom utilization rate.Meanwhile there is researcher to point out biomass Gas coke is a kind of porous carbon material；And porous carbon is very promising platform material, complex functionality can be widely used for Material, such as electrode material for super capacitor, Li or Na ion battery electrode materials etc..And prepare carbon electrode material in biomass In research, KOH, ZnCl are commonly used2And H3PO4Lift coke specific surface area Deng activator and control its pore-size distribution, but due to it With stronger alkaline or acid, equipment corrosion is easily caused in high reaction temperatures.
Therefore, it is badly in need of finding environmentally friendly activator to replace.And current biomass steam gasification system is big More to prepare synthesis gas as target, STRENGTH ON COKE byproduct is not paid close attention to too much, causes the overall utilization rate of biomass to decline.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the present invention propose a kind of gasification of biomass co-producing hydrogen and The system of porous carbon materials, the device overcome current biomass gasification device to cause resource as target using single syngas product Using it is insufficient the problem of, apparatus of the present invention can realize biomass higher value application, while prepare hydrogen and high added value Porous carbon materials.
To achieve the above object, the present invention provides a kind of system of gasification of biomass co-producing hydrogen and porous carbon materials, its Lived for carrying out steam gasification to biomass with co-producing hydrogen and porous carbon materials, the system including fluid bed steam gasification Sub-systems and the gasification gas being connected respectively with the fluid bed steam gasification subsystem reform isolated subsystem, gasification gas Cycling and reutilization subsystem, wherein, the fluid bed steam gasification activation subsystem is used in vapor and activator filler Under the conditions of existing for common, steam gasification priming reaction is carried out to biomass, to obtain preliminary gasification gas and gas coke, Coke is melted down simultaneously and carries out multiple priming reaction, to obtain the flourishing porous carbon products of hole；The gasification gas reforms separation Subsystem is used to activate preliminary gasifying gas progress methane reforming, water caused by subsystem from the fluid bed steam gasification Syngas conversion reactor, and refrigerated separation is carried out to obtain pure hydrogen product；The gasification gas cycling and reutilization subsystem is used for Remaining gasification gas caused by isolated subsystem will be reformed from the gasification gas, and (remnants gasification gas bags include carbon dioxide, carbon monoxide And methane) and cooling water be heated at high temperature, and be sent into fluid bed steam gasification activation subsystem, enter with biomass Capable secondary response again, realizes the recycling of material, while further activate coke product.
As the improvement of the present invention, the feed that the fluid bed steam gasification activation subsystem includes being sequentially connected twists Dragon, feed hopper, fluidized gasification activation furnace, gasification gas delivery line, cyclone separator, tentatively gasify gas delivery line, the biology Matter and activator bed material enter fluidized gasification activation furnace by the feed hopper and feed auger, in high-temperature vapor and activation In the presence of agent, biomass fermentation angerization priming reaction, produces gasification gas and gas coke enters cyclone separator, gasify gas from Preliminary gasification gas delivery line output.
As the improvement of the present invention, the fluid bed steam gasification activation subsystem also includes under the cyclone separator It is the coke outlet at end and the porous carbon discharging auger being connected with the cyclone separator, porous carbon cooling water ingress pipe, more Hole carbon cooling water delivery line, the gas coke in the cyclone separator are again introduced into the fluidized gasification through coke outlet Activation furnace, further gasification priming reaction is carried out, to obtain the flourishing porous carbon materials of porosity, caused porous carbon materials Exported in porous carbon discharging auger after cooling down water cooling；The cooling water after porous carbon heat is absorbed to lead from porous carbon cooling water Outlet pipe exports.
As the present invention improvement, it is described gasification gas reform isolated subsystem include be sequentially connected methane reforming stove, one It is secondary to reform gasification gas delivery line, water gas change-over stove, secondary reformed gasification gas delivery line, the methane reforming stove and the fluid bed The preliminary gasification gas delivery line connection of steam gasification activation subsystem, the gasification gas that gasification of biomass activates to obtain is in methane weight Under catalyst action in whole stove, methane reforming reaction is carried out, to reduce methane and carbon dioxide content, produces more hydrogen Gas, the gasification gas after once reforming enter in water gas change-over stove through once reforming gasification gas delivery line, further carry out aqueous vapor Conversion reaction so that carbon monoxide content reduces, and generates more hydrogen, and the hydrogen-rich after secondary reformed gasifies gas through secondary reformed The gas delivery line that gasifies output.
As the improvement of the present invention, the gasification gas reforms the gasification air cooling water that isolated subsystem also includes being sequentially communicated Ingress pipe, cooling tower, gasification air cooling water delivery line, low temperature gasification gas delivery line, gasification air film separate reactor, remaining gasification Gas delivery line, hydrogen delivery line, the hydrogen-rich gasification gas after the secondary reformed enters in cooling tower, fast in the presence of cooling water Speed is cooled to lower temperature, then is imported through low temperature gasification gas delivery line in gasification air film separate reactor and carry out gas separation, point The purified hydrogen come is separated out to export through hydrogen delivery line；Not separated carbon dioxide, carbon monoxide, methane gasify gas from remnants Delivery line exports, and absorbs the cooling water of high-temperature gasification gas heat through air cooling water delivery line export of gasifying.
As the improvement of the present invention, the gasification gas cycling and reutilization subsystem include the high-temperature heat-exchanging being sequentially connected and High-temperature vapor and remaining gasification gas delivery line, the high-temperature heat-exchanging reform the gasification gas of isolated subsystem with the gasification gas Cooling water delivery line connects with remnants gasifications gas delivery line, the high-temperature vapor and remaining gasification gas delivery line and the fluidisation The fluidized gasification activation furnace of bed steam gasification activation subsystem is connected with porous carbon cooling water delivery line, described remnants Cooling water after gasification gas and caloric receptivity is heated to form high-temperature gasification activated gas in high-temperature heat-exchanging, imports the fluid bed gas Change in activation furnace, carry out gasification priming reaction with biomass again so that gasification gas product and system capacity cycling and reutilization.
As the improvement of the present invention, the gasification gas cycling and reutilization subsystem also includes combustion furnace, the height being sequentially communicated Warm flue gas delivery line, low-temperature flue gas delivery line, high-temperature flue gas caused by the combustion furnace, through described in the entrance of low-temperature flue gas delivery line In high-temperature heat-exchanging, the cooling water after remaining gasification gas and caloric receptivity is heated, is supplemented for biomass steam gasification priming reaction Institute's calorific requirement.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show Beneficial effect：
(1) system of the invention realizes biomass by fluid bed while the priming reaction that gasifies occurs, that is, promotes hydrogen production It is raw, reaming can be carried out with STRENGTH ON COKE again, and by controlling coke to melt down the porosity of the i.e. controllable porous carbon of number, operation letter It is single, it is convenient and reliable, it is capable of the porous carbon materials of gasification gas and high porosity of the greenization preparation rich in hydrogen；
(2) in system of the invention, gasification gas is further reformed using methane reforming stove and water gas change-over stove Processing, can greatly improve hydrogen output and concentration, provide condition for later stage UF membrane, and then prepare hydrogen product；
(3) present invention is heated using using cooling gasification gas and porous carbon materials to cooling water, and then is passed through fluidisation In bed gasification activation furnace, the waste heat of gasification product is taken full advantage of, the abundant of energy is realized and efficiently utilizes；
(4) the remaining gasification (carbon dioxide, carbon monoxide, methane) after hydrogen will be isolated in present system and is passed through stream Change in bed gasification activation furnace, the material of realization makes full use of, while carbon dioxide, carbon monoxide, methane are to gasify well Agent and physically activated dose, on the one hand can carry out gasification priming reaction with biomass, improve hydrogen output and coke hole Gap rate, the remaining gasification gas of another aspect can suppress carbon dioxide, carbon monoxide, methanogenesis, so as to improve density of hydrogen.
Brief description of the drawings
Fig. 1 is a kind of structural representation of embodiment of the system of gasification of biomass co-producing hydrogen and porous carbon materials of the present invention Figure；
In all of the figs, identical reference is used for representing identical element or structure, wherein：
Wherein：1st, it is fed auger, 2, feed hopper, 3, fluidized gasification activation furnace, 4, gasification gas delivery line, 5, cyclonic separation Device, 6, tentatively gasify gas delivery line, 7, methane reforming stove, 8, once reform gasification gas delivery line, 9, water gas change-over stove, 10, two It is secondary to reform gasification gas delivery line, 11, gasification air cooling water ingress pipe, 12, cooling tower, 13, gasification air cooling water delivery line, 14, Low temperature gasification gas delivery line, 15, gasification air film separate reactor, 16, remaining gasification gas delivery line, 17, low-temperature flue gas delivery line, 18th, high-temperature heat-exchanging, 19, high-temperature vapor and remaining gasification gas delivery line, 20, porous carbon discharging auger, 21, porous carbon cooling Water ingress pipe, 22, porous carbon outlet, 23, combustion furnace, 24, hydrogen delivery line, 25, high-temperature flue gas delivery line, 26, porous carbon Cooling water delivery line.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below Conflict can is not formed each other to be mutually combined.
Fig. 1 is a kind of for gasification of biomass co-producing hydrogen and the structure of the system of porous carbon materials in the embodiment of the present invention Schematic diagram, as shown in figure 1, a kind of system for gasification of biomass co-producing hydrogen and porous carbon materials of the present embodiment includes phase Intercommunicated fluid bed steam gasification activates subsystem, gasification gas reforms isolated subsystem, gasification gas cycling and reutilization subsystem System.
Wherein, fluid bed steam gasification activation subsystem includes feed auger 1, feed hopper 2, the fluid bed being sequentially connected Gasify activation furnace 3, gasification gas delivery line 4, cyclone separator 5, preliminary gasification gas delivery line 6.Biomass, green activating dose (such as NaHCO3、CaCl2Deng) and fluid bed bed material fluidized gasification activation furnace 3 is entered by feed hopper 2 and feed auger 1, in high temperature In the presence of vapor and activator, the activation double reaction of biomass fermentation angerization, the gasification gas for being largely rich in hydrogen is produced, together When under the collective effect of gasifying agent and activator, gas coke also has more flourishing pore structure, and and then gasify gas Enter cyclone separator 5 with gas coke and carry out gas solid separation, the gasification gas separated is defeated from preliminary gasification gas delivery line 6 Go out.
Fluid bed steam gasification activation subsystem also including the lower end of cyclone separator 5 coke outlet 22 and with rotation The connected porous carbon discharging auger 20 of wind separator 5, porous carbon cooling water ingress pipe 21 is provided with porous carbon discharging auger 20 With porous carbon cooling water delivery line 26, the gas coke in cyclone separator 5 is again introduced into fluid bed gas through coke outlet 22 Change activation furnace 3, carry out further gasification priming reaction with gasifying agent and activator, by control plus heat number, can obtain Porosity porous carbon materials flourishing enough, caused porous carbon materials are in porous carbon discharging auger 20 after cooling down water cooling Output；The cooling water after porous carbon heat is absorbed simultaneously to export from porous carbon cooling water delivery line 26, waste heat is fully used, Whole system capacity usage ratio can be improved.
Gasification gas reform isolated subsystem include be sequentially connected methane reforming stove 7, once reform gasification gas delivery line 8, Water gas change-over stove 9 and secondary reformed gasification gas delivery line 10.Methane reforming stove 7 and fluid bed steam gasification activation subsystem Preliminary gasification gas delivery line 6 connect, the gasification gas that gasification of biomass activates to obtain in methane reforming stove 7, catalyst make Under, methane reforming reaction is carried out, to reduce methane and carbon dioxide content, produces more hydrogen, after once reforming Gasification gas enters in water gas change-over stove 9 through once reforming gasification gas delivery line 8, and aqueous vapor is further carried out under catalyst action Conversion reaction so that carbon monoxide content reduces, so as to which hydrogen output further improves, the hydrogen-rich gasification gas warp after secondary reformed Secondary reformed gasification gas delivery line 10 exports.
The gas that gasifies, which reforms isolated subsystem, also includes gasification air cooling water ingress pipe 11, cooling tower 12, gasification air cooling water Delivery line 13, low temperature gasification gas delivery line 14, gasification air film separate reactor 15, remaining gasification gas delivery line 16 and hydrogen are led Outlet pipe 24, the hydrogen-rich gasification gas after secondary reformed enter in cooling tower 12, are quickly cooled in the presence of cooling water compared with low temperature Degree, then imported through low temperature gasification gas delivery line 14 in gasification air film separate reactor 15 and carry out gas separation, it is ensured that hydrogen passes through Membrane separator is kept completely separate out, and remaining gas is remained in gasification gas, and the purified hydrogen separated exports through hydrogen Pipe 24 exports；Separated carbon dioxide, carbon monoxide, methane do not export from remnants gasifications gas delivery line 16, absorb High Temperature Gas The cooling water for changing gas heat exports through the air cooling water delivery line 13 that gasifies, and realizes making full use of for material and heat.
Gasification gas cycling and reutilization subsystem includes high-temperature heat-exchanging 18 and high-temperature vapor and the residual gas being sequentially connected Change gas delivery line 19, high-temperature heat-exchanging 18 reforms the gasification air cooling water delivery line 13 and residual gas of isolated subsystem with gasification gas Change gas delivery line 16 to connect, high-temperature vapor and remaining gasification gas delivery line 19 and fluid bed steam gasification activation subsystem Fluidized gasification activation furnace 3 is connected with porous carbon cooling water delivery line 26, and the cooling water after remnants gasification gas and caloric receptivity exists High-temperature heat-exchanging 18 is heated to form high-temperature gasification activated gas, imports in fluidized gasification activation furnace 3 so that gasification gas product and System capacity cycling and reutilization.Wherein, remaining gasification gas (including carbon dioxide, carbon monoxide, methane) is good gasifying agent With physically activated dose, on the one hand can carry out gasification priming reaction with biomass, promote hydrogen generation and improve coke Porosity, the remaining gasification gas of another aspect can suppress carbon dioxide, carbon monoxide, methanogenesis, so as to improve density of hydrogen.
Gasification gas cycling and reutilization subsystem also includes combustion furnace 23, high-temperature flue gas delivery line 25 and the low temperature being sequentially communicated Flue gas delivery line 17.High-temperature flue gas caused by combustion furnace 23, enter through low-temperature flue gas delivery line 17 in the high-temperature heat-exchanging 18, Cooling water after the remaining gasification gas of heating and caloric receptivity, institute's calorific requirement is supplemented for biomass steam gasification priming reaction.
Specifically, the concrete engineering process of present system is：
Biomass, green activating dose (such as NaHCO3, CaCl2), fluid bed bed material (such as quartz sand) through feed hopper 2 and Feed auger 1 is entered in fluidized gasification activation furnace 3, and after high-temperature vapor heats, biomass is in green activating dose and water Under the collective effect of steam gasifying agent, strong gasification priming reaction occurs rapidly, produces the gasification gas for being largely rich in hydrogen, together When under the collective effect of gasifying agent and activator, gas coke also has more flourishing pore structure, and and then gasify gas Enter cyclone separator 5 with gas coke and carry out gas solid separation, the gasification gas separated is defeated from preliminary gasification gas delivery line 6 Go out.
Gas coke in cyclone separator 5 is again introduced into fluidized gasification activation furnace 3 through coke outlet 22, with gasification Agent and activator carry out further gasification priming reaction, by control plus heat number, to obtain the more of porosity prosperity enough Hole carbon material, caused porous carbon materials are in porous carbon discharging auger 20, while cooling water is from porous carbon cooling water ingress pipe It is sufficiently cool to porous carbon materials progress in 21 importing porous carbon discharging augers 20, obtain porous carbon materials product；Absorb porous Cooling water after carbon heat exports from porous carbon cooling water delivery line 26.
Enter through the preliminary derived gasification gas of gasification gas delivery line 6 in methane reforming stove 7, under catalyst action, carry out Methane reformingization is reacted, and to reduce methane and carbon dioxide content, produces more hydrogen, and the once gasification gas after reformation Enter through once reforming gasification gas delivery line 8 in water gas change-over stove 9, it is anti-that aqueous vapor conversion is further carried out under catalyst action Should so that carbon monoxide content reduces, and so as to which hydrogen output further improves, the hydrogen-rich after secondary reformed gasifies gas through secondary heavy Whole gasification gas delivery line 10 exports.
After secondary reformed hydrogen-rich gasification gas enter cooling tower 12 in, while cooling water from gasification air cooling water ingress pipe 11 Import in cooling tower 12, the hydrogen-rich gasification gas after secondary reformed is quickly cooled to lower temperature in the presence of cooling water, then passes through Low temperature gasification gas delivery line 14 imports in gasification air film separate reactor 15 and carries out gas separation, it is ensured that hydrogen passes through membrane separator It is kept completely separate out, and remaining gas is remained in gasification gas, the purified hydrogen separated exports through hydrogen delivery line 24, Obtain hydrogen product；Separated carbon dioxide, carbon monoxide, methane do not export from remnants gasifications gas delivery line 16, absorb high The cooling water of wet gas heat exports through the air cooling water delivery line 13 that gasifies.
Through derived from the air cooling water delivery line 13 that gasifies, remaining gasification gas delivery line 16, porous carbon cooling water delivery line 26 Cooling water after remnants gasification gas and caloric receptivity enters in high-temperature heat-exchanging 18, while high-temperature flue gas caused by combustion furnace 23, warp Low-temperature flue gas delivery line 17 enters in the high-temperature heat-exchanging 18, fully the cooling water after the remaining gasification gas of heating and caloric receptivity, Institute's calorific requirement is supplemented for biomass steam gasification priming reaction, the high-temperature flue gas after heat is discharged and is arranged from high-temperature flue gas delivery line Go out；The high-temperature gasification activated gas (vapor, carbon dioxide, carbon monoxide, methane) after heat is absorbed, imports fluid bed again Gasify in activation furnace 3 so that gasification gas product and system capacity cycling and reutilization；Meanwhile remaining gasification gas (carbon dioxide, one Carbonoxide, methane) it is good gasifying agent and physically activated dose, it is anti-that gasification activation on the one hand can be carried out with biomass Should, promote the generation of hydrogen and improve coke porosity, on the other hand remaining gasification gas can suppress carbon dioxide, an oxidation Carbon, methanogenesis, so as to improve density of hydrogen.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included Within protection scope of the present invention.

Claims (7)

1. the system of a kind of gasification of biomass co-producing hydrogen and porous carbon materials, it is characterised in that the system includes fluid bed water Steam gasification activation subsystem and respectively the gasification gas reformation with fluid bed steam gasification activation subsystem connection separate Subsystem, gasification gas cycling and reutilization subsystem, wherein,
Fluid bed steam gasification activation subsystem be used for vapor and activator filler it is common it is existing under the conditions of, it is right Biomass carries out steam gasification priming reaction, to obtain preliminary gasification gas and gas coke, while for coke to be melted down Multiple priming reaction is carried out, to obtain the flourishing porous carbon products of hole；
The gasification gas reforms isolated subsystem and is used to activate from the fluid bed steam gasification caused by subsystem tentatively Gasifying gas carries out methane reforming and water gas shift reaction, and carries out refrigerated separation to obtain pure hydrogen product；
The gasification gas cycling and reutilization subsystem is used to that remaining gasification caused by isolated subsystem will to be reformed from the gasification gas Gas and cooling water are heated at high temperature, and are sent into the fluid bed steam gasification activation subsystem, are carried out again with biomass Reaction, realizes the recycling of material, while further activates coke product,
The remaining gasification gas bag includes the one or more in carbon dioxide, carbon monoxide and methane.
2. the system of a kind of gasification of biomass co-producing hydrogen according to claim 1 and porous carbon materials, it is characterised in that The fluid bed steam gasification activation subsystem includes the feed auger (1), feed hopper (2), fluidized gasification being sequentially connected Activation furnace (3), gasification gas delivery line (4), cyclone separator (5) and the gas delivery line (6) that tentatively gasifies,
Biomass and activator bed material enter fluidized gasification activation furnace (3) by the feed hopper (2) and feed auger (1), In the presence of high-temperature vapor and activator, biomass fermentation angerization priming reaction, caused gasification gas and gas coke enter Enter cyclone separator (5), gasification gas exports from preliminary gasification gas delivery line (6).
3. the system of a kind of gasification of biomass co-producing hydrogen according to claim 2 and porous carbon materials, it is characterised in that The fluid bed steam gasification activation subsystem also includes the coke outlet (22) positioned at the cyclone separator (5) lower end And the porous carbon discharging auger (20) being connected with the coke outlet (22), it is provided with porous carbon discharging auger (20) Porous carbon cooling water ingress pipe (21) and porous carbon cooling water delivery line (26),
During work, the gas coke in the cyclone separator (5) is again introduced into the fluid bed gas through coke outlet (22) Change activation furnace (3), carry out further gasification priming reaction, it is caused porous to obtain the flourishing porous carbon materials of porosity Carbon material exports in porous carbon discharging auger (20) after cooling down water cooling；
Absorb the cooling water after porous carbon heat to export from porous carbon cooling water delivery line (26), in case recycling.
4. the system of a kind of gasification of biomass co-producing hydrogen according to claim 1 or 2 and porous carbon materials, its feature exist In, it is described gasification gas reform isolated subsystem include be sequentially connected methane reforming stove (7), once reform gasification gas delivery line (8), water gas change-over stove (9) and secondary reformed gasification gas delivery line (10),
The methane reforming stove (7) and the preliminary gasification gas delivery line (6) of fluid bed steam gasification activation subsystem connect It is logical,
During work, the gasification gas that gasification of biomass activates to obtain carries out methane weight in methane reforming stove (7) through catalyst action Integralization is reacted, and to reduce methane and carbon dioxide content, produces more hydrogen,
Gasification gas after once reforming enters in water gas change-over stove (9) through once reforming gasification gas delivery line (8), further enters Water-filling gas shift reaction so that carbon monoxide content reduces, and generates more hydrogen,
Hydrogen-rich gasification gas after secondary reformed is through secondary reformed gasification gas delivery line (10) output.
5. the system of a kind of gasification of biomass co-producing hydrogen according to claim 4 and porous carbon materials, it is characterised in that The gasification gas reforms gasification air cooling water ingress pipe (11), cooling tower (12), the gas that isolated subsystem also includes being sequentially communicated Change air cooling water delivery line (13), low temperature gasification gas delivery line (14), gasification air film separate reactor (15), remaining gasification conductance Outlet pipe (16) and hydrogen delivery line (24),
During work, the hydrogen-rich gasification gas after the secondary reformed enters in cooling tower (12), the fast quickly cooling in the presence of cooling water But to lower temperature, then imported through low temperature gasification gas delivery line (14) and gas point is carried out in gasification air film separate reactor (15) From the purified hydrogen separated exports through hydrogen delivery line (24)；
Separated carbon dioxide, carbon monoxide and methane do not absorb High Temperature Gas from remnants gasification gas delivery lines (16) export Change the cooling water of gas heat through air cooling water delivery line (13) export of gasifying, in case follow-up Btu utilization.
6. the system of a kind of the gasification of biomass co-producing hydrogen and porous carbon materials according to any one of claim 5, its Be characterised by, the gasification gas cycling and reutilization subsystem include interconnected high-temperature heat-exchanging (18) and high-temperature vapor and Remnants gasification gas delivery lines (19),
The high-temperature heat-exchanging (18) and the gasification gas reform the gasification air cooling water delivery line (13) of isolated subsystem and residual Residual air gas delivery line (16) connects, the high-temperature vapor and remaining gasification gas delivery line (19) and the fluid bed vapor The fluidized gasification activation furnace (3) of gasification activation subsystem is connected with porous carbon cooling water delivery line (26),
During work, the cooling water after remnants gasification gas and absorption heat is heated to form high-temperature gasification activation in high-temperature heat-exchanging (18) Gas, import in the fluidized gasification activation furnace (3), carry out gasification priming reaction with biomass again so that gasification gas production Thing and system capacity cycling and reutilization.
7. the system of a kind of gasification of biomass co-producing hydrogen according to claim 6 and porous carbon materials, it is characterised in that The gasification gas cycling and reutilization subsystem also includes combustion furnace (23), high-temperature flue gas delivery line (25) and the low temperature being sequentially communicated Flue gas delivery line (17),
During work, high-temperature flue gas caused by the combustion furnace (23) enters the high-temperature heat-exchanging through low-temperature flue gas delivery line (17) (18) in, heat remaining gasification gas and absorb the cooling water after heat, for needed for biomass steam gasification priming reaction supplement Heat.
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