CN106853372A - A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil - Google Patents

A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil Download PDF

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CN106853372A
CN106853372A CN201510953625.4A CN201510953625A CN106853372A CN 106853372 A CN106853372 A CN 106853372A CN 201510953625 A CN201510953625 A CN 201510953625A CN 106853372 A CN106853372 A CN 106853372A
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hydrogen
oil
reaction
water
reactor
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李全新
吴小平
刘俊旭
姜沛汶
薛鹤
朱丽娟
张义恒
金凤
夏彤岩
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University of Science and Technology of China USTC
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention belongs to biomass hydrogen preparation field, more particularly to a kind of nickel-base catalyst and method that hydrogen is prepared using bio oil.The nickel-base catalyst that the present invention is provided, in terms of parts by weight, including：20~25 parts of NiO；Fe2O310~15 parts；CeO26~8 parts；5~6 parts of MgO；Al2O346~59 parts.The method that the present invention is provided is comprised the following steps：A), bio oil and water are reacted in the presence of above-mentioned nickel-base catalyst, obtain hydrogeneous gaseous mixture；B), the hydrogeneous gaseous mixture is reacted in the presence of copper zinc catalyst, obtains hydrogen.Test result indicate that, when the method provided using the present invention carries out bio-oil hydrogen making, its reaction temperature is 300~650 DEG C, bio oil conversion ratio reaches as high as 95.9%, hydrogen yield reaches as high as 12.9g/ (100g bio oils), and the highest content of hydrogen is up to 99.98vol% in hydrogen product.

Description

A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil
Technical field
The invention belongs to biomass hydrogen preparation field, more particularly to a kind of nickel-base catalyst and utilization bio oil system The method of standby hydrogen.
Background technology
The annual material produced through photosynthesis of the earth has 173,000,000,000 tons, wherein the energy equivalence for containing is in complete 10 times of world energy consumption total amount.As the pressure of energy demand and environmental protection is increased rapidly, utilize Reproducible biomass energy is greatly paid close attention to by people.The development and utilization of biomass energy both contributes to promote Enter energy variation, moreover it is possible to reduce greenhouse gas emission, alleviate the pressure to environment, represent energy work The important development trend of industry.Hydrogen is one of current optimal high heating value clean energy resource, with aboundresources, Environment-friendly, reproducible biomass prepare hydrogen will turn into a kind of New Hydrogen with great development future Source.
In the prior art, biomass hydrogen preparation approach is mainly based upon hydrogen generation by biological process and based on biomass thermalization Method hydrogen producing technology.Raw material used by hydrogen generation by biological process is house refuse, municipal sewage, animal wastes etc. Organic waste, microorganism is by the biochemical reaction product such as enzymic catalytic reaction or light decomposition at normal temperatures and pressures Raw hydrogen, hydrogen generation by biological process is a hydrogen manufacturing approach for meeting environmental protection and mankind's long term growth, at present Complex process and hydrogen manufacturing cycle deficiency long are still suffered from, it is necessary to cultivate the dominant bacteria of hydrogen generation efficiency high and excellent Change process for making hydrogen flow.
Biomass thermal chemical method hydrogen producing technology has reaction fast and the characteristics of big hydrogen output, with higher Prospects for commercial application.In the prior art, mainly there are two kinds from biomass hydrogen making using heat chemistry mode Technological approaches：The first technological approaches is biomass gasifying hydrogen making method；Second technological approaches is using life The catalyzing and reforming biologic oil silicol process that material fast pyrolysis are formed.Biomass gasifying hydrogen making technology is generally sharp With fluidized-bed gasification furnace or fixed-bed gasification furnace, in air, oxygen or water vapour atmosphere and 800~1200 Under DEG C hot conditions, hydrogen containing synthesis gas or combustion gas are converted biomass into.In gasification of biomass product gas Mainly including hydrogen, carbon monoxide, carbon dioxide, a small amount of methane and composition etc. tar.Using difference Gasifying medium, product gas composition and tar composition content it is different, use air as gasification During agent, due to containing substantial amounts of nitrogen in combustion gas, the difficulty of hydrogen purification is increased；And use water vapour Be conducive to producing the purification of the hydrogen-rich gas and hydrogen of higher hydrogen gas concentration as gasifying medium.Biomass Gasification hydrogen-producing technology has the advantages that equipment and technology is simple, adaptability to raw material is wide and hydrogen production potential is big, but It is to still suffer from many weak points：As density of hydrogen and yield are relatively low, reaction temperature is high, energy consumption is big and Product separates the problems to be solved of still needing such as difficulty.
The raw material used in catalyzing and reforming biologic oil silicol process is the liquid prepared using biomass fast pyrolysis Body product bio oil.Biomass fast pyrolysis can produce 60-75wt% liquid bio-oils, 15-25wt% to give birth to Material solid carbon and 10-20wt% cracking tail gas.Wherein, bio oil be by containing cellulose, hemicellulose and The fluid product that the lignocellulose type biomass of lignin are produced by fast pyrolysis liquefaction process, it is raw Thing oil be it is a kind of with acid brownish black liquid organic mixture, its elemental constituent be mainly carbon, oxygen and Hydrogen；Meanwhile, the chemical composition of bio oil is considerably complicated, the organic species that analysis finds more than 300 kinds, Including acid, alcohol, aldehyde, ketone, fat, phenol, candy, furans, fragrant oligomer and other oxygen-bearing organic matters. Catalyzing and reforming biologic oil silicol process is will be multiple in bio oil using catalytic reforming reaction and water-gas shift reaction Miscellaneous oxygen-bearing organic matter is converted into the thermochemical process of hydrogen, the catalyst for using typically nickel-base catalyst And transition-metal catalyst, generally utilize fixed bed or fluidized-bed reactor, in water vapour atmosphere and Under 600-800 DEG C of medium temperature condition, bio oil is converted into the hydrogen-rich gaseous mixture based on hydrogen and carbon dioxide, Catalyzing and reforming biologic oil hydrogen production process includes that thermal cracking, catalytic pyrolysis, reforming reaction, water-gas shift are anti- Should be generally included in the product gas using the acquisition of catalyzing and reforming biologic oil silicol process with various reactions such as carbon distribution The compositions such as hydrogen, carbon monoxide, carbon dioxide and methane, and density of hydrogen is usually less than in gaseous product 70vol%.
Compared with biomass gasifying hydrogen making technology, higher hydrogen can be obtained using catalyzing and reforming biologic oil silicol process The gaseous mixture of gas concentration and hydrogen yield higher, meanwhile, bio oil has easily collecting, easily stores and easy Advantage in terms of transport, bio oil derived energy chemical product can small-scale pyrolysis liquefying be (raw on the spot using biomass The production of thing oil) and the pattern for refining (bio oil is converted into derived energy chemical product) is concentrated on a large scale, be conducive to Biomass dispersiveness, inconvenience storage and long-distance transport for being run into during the actual biomass economy of solution etc. are asked Topic.But, it is high to remain reaction temperature in existing catalyzing and reforming biologic oil hydrogen production process, and energy consumption is big, And hydrogen purification difficulty it is big the problems such as.
The content of the invention
In view of this, hydrogen is prepared it is an object of the invention to provide a kind of nickel-base catalyst and using bio oil The method of gas, the method that the present invention is provided can at a lower reaction temperature realize bio oil catalyzing manufacturing of hydrogen, And CH in obtained hydrogen product4It is less with the by-products content such as CO.
The invention provides a kind of nickel-base catalyst, in terms of parts by weight, including：
Preferably, in terms of parts by weight, the nickel-base catalyst includes：
The invention provides a kind of method that utilization bio oil prepares hydrogen, comprise the following steps：
A), bio oil and water are reacted in the presence of the nickel-base catalyst described in above-mentioned technical proposal, are obtained To hydrogeneous gaseous mixture；
B), the hydrogeneous gaseous mixture is reacted in the presence of copper zinc catalyst, obtains hydrogen.
Preferably, in step a), the temperature of the bio oil and water reaction is 300~650 DEG C.
Preferably, in step a), the mass ratio of the bio oil and water is 1：(3~4).
Preferably, in step b), the temperature that the hydrogeneous gaseous mixture is reacted is 150~350 DEG C.
Preferably, the hydrogeneous gaseous mixture also includes after being reacted：
The hydrogen-rich gaseous mixture and CO of the hydrogeneous mixing solid/liquid/gas reactions generation2Absorbing liquid hybrid reaction, obtains hydrogen Gas.
Preferably, the CO2Absorbing liquid includes calcium oxide aqueous solution, calcium hydroxide aqueous solution, sodium carbonate One or more in solution and sodium hydrate aqueous solution.
Compared with prior art, hydrogen is prepared the invention provides a kind of nickel-base catalyst and using bio oil Method.The nickel-base catalyst that the present invention is provided, in terms of parts by weight, including：20~25 parts of NiO；Fe2O3 10~15 parts；CeO26~8 parts；5~6 parts of MgO；Al2O346~59 parts.What the present invention was provided utilizes life The method that thing oil prepares hydrogen is comprised the following steps：A), bio oil and water exist in above-mentioned nickel-base catalyst Under reacted, obtain hydrogeneous gaseous mixture；B), the hydrogeneous gaseous mixture enters in the presence of copper zinc catalyst Row reaction, obtains hydrogen.In the method that the present invention is provided, reacted by catalyzing and reforming biologic oil first Hydrogeneous gaseous mixture is obtained, the CO in the hydrogeneous gaseous mixture is removed using water-gas shift reaction afterwards, obtain To purity hydrogen product higher.The present invention is by urging for being used during bio oil catalytic reforming reaction Agent composition is optimized, and the temperature of catalyzing and reforming biologic oil reaction is reduced, so that the bio oil system of reduction The energy consumption of hydrogen, while coupled by by catalyzing and reforming biologic oil reaction process and water-gas shift reaction technique, Improve the purity of hydrogen product.In the preferred embodiment that the present invention is provided, also including by water-gas Hydrogen product and CO that conversion reaction technique is obtained2Absorbing liquid hybrid reaction, so that in removing hydrogen product CO2, further improve the purity of hydrogen product.Test result indicate that, the side provided using the present invention When method carries out bio-oil hydrogen making, its reaction temperature is 300~650 DEG C, and bio oil conversion ratio is reached as high as 95.9%, hydrogen yield reaches as high as 12.9g/ (100g bio oils), and the highest of hydrogen contains in hydrogen product Amount is up to 99.98vol%.And density of hydrogen leads in utilizing the gaseous product of existing bio-oil hydrogen making technology acquisition Often it is less than 70vol%, it is seen that be much larger than existing biology using hydrogen purity obtained in the method that the present invention is provided Oil hydrogen making technology obtain hydrogen purity, and hydrogen purification operation is simple.
Specific embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that institute The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.Based on this hair Embodiment in bright, what those of ordinary skill in the art were obtained under the premise of creative work is not made Every other embodiment, belongs to the scope of protection of the invention.
The invention provides a kind of nickel-base catalyst, in terms of parts by weight, including：
The nickel-base catalyst that the present invention is provided includes NiO, Fe2O3、CeO2, MgO and γ-Al2O3, wherein, Contents of the NiO in nickel-base catalyst is 20~25 weight portions, preferably 20.4~24.5 weight portions；Institute State Fe2O3Content in nickel-base catalyst is 10~15 weight portions, preferably 10.3~14.8 weight portions；Institute State CeO2Content in nickel-base catalyst is 6~8 weight portions, preferably 6.5~7.7 weight portions；The MgO Content in nickel-base catalyst is 5~6 weight portions, preferably 5.3~5.8 weight portions；γ-the Al2O3Grain Footpath is preferably 2~3mm；γ-the Al2O3Specific surface area be preferably 200~220m2/g；γ-the Al2O3 Density be preferably 0.6~0.7g/cm3；γ-the Al2O3Pore volume be preferably 0.4~0.5ml/g；It is described γ-Al2O3Content in nickel-base catalyst is 46~59 weight portions, preferably 47.5~55.1 weight portions.At this In one embodiment that invention is provided, the γ-Al2O3Model KA405, the γ-Al of the model2O3It is preferred that There is provided by Pingxiang Zhongtian Chemical Filler Co., Ltd..
In one embodiment that the present invention is provided, the nickel-base catalyst, in terms of parts by weight, including：
In another embodiment that the present invention is provided, the nickel-base catalyst, in terms of parts by weight, bag Include：
In the other embodiment that the present invention is provided, the nickel-base catalyst, in terms of parts by weight, including：
In the other embodiment that the present invention is provided, the nickel-base catalyst, in terms of parts by weight, including：
In the present invention, the nickel-base catalyst preferably also includes binding agent, and the binding agent is preferably height Ridge soil and/or field fine powder.In the present invention, the physical aspect of the nickel-base catalyst is preferably particle, institute The particle diameter for stating nickel-base catalyst is preferably 60~80 mesh.
In the present invention, directly by nickel source compound, Fe source compound, cerium source compound, magnesium source chemical combination Thing and Al2O3Carrier is calcined after being well mixed in a solvent in proportion, you can obtain present invention offer Nickel-base catalyst, the process is specially：
First, nickel source compound, Fe source compound, cerium source compound, magnesium source compound and solvent are mixed Close, obtain mixed liquor.Wherein, the nickel source compound is preferably nickel nitrate and/or Nickelous nitrate hexahydrate； The Fe source compound is preferably ferric nitrate and/or Fe(NO3)39H2O；The cerium source compound is preferably nitre Sour cerium and/or six nitric hydrate ceriums；The magnesium is preferably magnesium nitrate and/or magnesium nitrate hexahydrate；The solvent Preferably water.Afterwards, by Al2O3Carrier impregnation in mixed liquor, wherein, the Al2O3Preferably γ-Al2O3。
After dipping is finished, to Al2O3The mixed system of carrier and mixed liquor composition is calcined.The roasting Temperature be preferably 550~600 DEG C；The time of the roasting is preferably 8~10h.In the present invention, it is preferred to Before being calcined to the mixed system, it is dried.The dry detailed process is： Mixed system is first placed in solvent evaporated in 100 DEG C of water-baths, drying in baking oven is put into afterwards, the drying Temperature is preferably 120~140 DEG C；The time of the drying is preferably 10~12h.
After roasting is finished, product of roasting is obtained, the product of roasting is nickel-base catalyst.In the present invention, What preferred pair roasting was obtained is granulated by burning product, obtains nickel-base catalyst particle.In the present invention, It is preferred that being granulated using following manner：
Roasting is obtained into product of roasting and binding agent mixed grinding, mixed-powder is obtained.Wherein, it is described viscous Knot agent is preferably kaolin and/or field fine powder.Content of the binding agent in the mixed-powder is preferably 10~20wt%, more preferably 15wt%.Compressing tablet, drying and mistake are carried out successively to the mixed-powder afterwards Sieve, obtains nickel-base catalyst particle.Wherein, the dry temperature is preferably 100~120 DEG C；It is described dry The dry time is preferably 10~12h, and the screen-aperture of the sieving is preferably 60~80 mesh.
The present invention optimizes design by the composition to catalyst, is catalyzed by making it at a lower temperature Bio oil reaction generation hydrogen, so as to reduce the reaction temperature of bio-oil hydrogen making, and then reduces bio oil The energy consumption of hydrogen manufacturing.Test result indicate that, when the catalyst provided using the present invention carries out bio-oil hydrogen making Reaction temperature is 300~650 DEG C, and bio oil conversion ratio reaches as high as 95.9%, and hydrogen yield is reached as high as 12.6g/ (100g bio oils).
The invention provides a kind of method that utilization bio oil prepares hydrogen, comprise the following steps：
A), bio oil and water are reacted in the presence of the nickel-base catalyst described in above-mentioned technical proposal, are obtained To hydrogeneous gaseous mixture；
B), the hydrogeneous gaseous mixture is reacted in the presence of copper zinc catalyst, obtains hydrogen.
In the method for preparing hydrogen that the present invention is provided, will be raw first in the presence of the nickel-base catalyst Thing oil and water hybrid reaction.Wherein, the bio oil is made up of biomass flash pyrolysis, its main component It is oxygen-bearing organic matter and water.It is oxygen-containing organic in the bio oil in one embodiment that the present invention is provided The main component of thing be C, H and O, wherein, contents of the C in the oxygen-bearing organic matter is The content of 35~45wt%, H in the oxygen-bearing organic matter is 5~10wt%, and O is in the oxygen-bearing organic matter Content be 45~55wt%；It is oxygen-containing in the bio oil to have in another embodiment that the present invention is provided The main component of machine thing be C, H and O, wherein, contents of the C in the oxygen-bearing organic matter is The content of 39.92~41.71wt%, H in the oxygen-bearing organic matter is 7.71~8.15wt%, and O contains described Content in oxygen organic is 50.3~51.29wt%.In one embodiment that the present invention is provided, the life The water content of thing oil is 25~35wt%；In another embodiment that the present invention is provided, the bio oil Water content is 27.7~30.3wt%.The present invention is not particularly limited to the source of the bio oil, can be voluntarily Prepare, it is also possible to purchase commercial goods.In the present invention, during the bio oil and water react, The bio oil and the temperature of water reaction are preferably 300~650 DEG C；The mass ratio of the bio oil and water is preferred It is 1：(3~4).
In the present invention, the bio oil and water react used reactor referred to as catalyzing and reforming biologic oil Reactor, the catalyzing and reforming biologic oil reactor is preferably fixed bed catalytic reactor.The present invention is to institute The specification and model for stating fixed bed catalytic reactor are not particularly limited, and those skilled in the art are according to reality Operating mode selects the fixed bed catalytic reactor of appropriate size and model.In the reality that the present invention is provided Apply in example, the fix bed catalyst reactor for being used is a tubular with external heat and heat-insulation layer Fixed bed catalytic reactor, the access tube of bio-oil feedstock and carrier gas (vapor) is connected with its two ends Road and product output channel, bio oil holding vessel are connected with liquid addition device (liquid injection pump), Carrier gas channel is passed through pipeline connection with reactant, and is respectively equipped with gas control valve and reactant flow control Device, be passed through pipeline outer wall be provided with for preheat external heating device；On product output channel according to It is secondary to be connected with including double-condenser, liquid product collection device and gas collection of products tank.
In the present invention, the tool that the bio oil and water are reacted in catalyzing and reforming biologic oil reactor Body process is：
First, the nickel-base catalyst is filled in the center constant temperature of the catalyzing and reforming biologic oil reactor Area.Then, catalyst is purged using nitrogen.The temperature of the purging is preferably room temperature；It is described The time of purging is preferably 30~90min.Afterwards, the catalyst is reduced using also Primordial Qi.Institute The gaseous mixture of also Primordial Qi preferably hydrogen and argon gas is stated, the volumetric concentration of hydrogen is preferably in the gaseous mixture 10~15%；The temperature of the reduction is preferably 600~650 DEG C；The time of the reduction is preferably 3~7h. Then, reactor is purged using vapor.The time of the steam purging is preferably 30~90min.After steam purging is finished, the center flat-temperature zone of the fixed bed catalytic reactor is adjusted Temperature, makes the temperature of center flat-temperature zone be preferably controlled in 300~650 DEG C.After temperature stabilization in question response device, The valve of the feeder on bio-oil feedstock holding vessel outlet is opened, bio oil and vapor are through access tube Road enters catalytic reactor inner chamber, and is reacted in the presence of nickel-base catalyst.Wherein, it is described anti- The mass ratio of bio oil and vapor in device is answered to be preferably controlled in 1：(3~4)；It is biological in the reactor That the consumption of nickel-base catalyst is preferably 100 (g/h) in the inlet amount and the reactor of oil：10~20 (g).
Bio oil and water are deposited after the completion of reaction in the nickel-base catalyst, obtain hydrogeneous gaseous mixture, and this contains Hydrogen gaseous mixture can be used as primary hydrogen product, i.e., unpurified hydrogen product.In the present invention, the life The reaction that thing oil and water are carried out in the presence of the nickel-base catalyst referred to as catalyzing and reforming biologic oil reaction, it is raw Thing oil and water are removed by generating hydrogeneous gaseous mixture after catalyzing and reforming biologic oil reaction in the hydrogeneous gaseous mixture Containing outside hydrogen, also contain CO2, CO and a small amount of CH4。
After obtaining hydrogeneous gaseous mixture, the hydrogeneous gaseous mixture is set to be reacted in the presence of copper zinc catalyst. Wherein, the composition of the copper zinc catalyst preferably includes CuO, ZnO and Al2O3Carrier.Carried in the present invention In one embodiment of confession, the content of CuO is 30~35wt% in the copper zinc catalyst；Carried in the present invention In another embodiment for supplying, the content of CuO is 33.2~35wt% in the copper zinc catalyst.In this hair In one embodiment of bright offer, the content of ZnO is 10~15wt% in the copper zinc catalyst；In this hair In another embodiment of bright offer, the content of ZnO is 12.8~15wt% in the copper zinc catalyst. In one embodiment that the present invention is provided, Al in the copper zinc catalyst2O3The content of carrier is 50~60wt%；In another embodiment that the present invention is provided, Al in the copper zinc catalyst2O3Carrier Content is 54~60wt%.The present invention is not particularly limited to the source of the copper zinc catalyst, purchases commercially available Commodity.In the present invention, the Gas Mixtures Containing Hydrogen is reacted in the presence of copper zinc catalyst During, the temperature of the reaction is preferably 150~350 DEG C.
In the present invention, the hydrogeneous gaseous mixture is reacted used reactor referred to as Water gas shift/WGS Reactor, the water-gas shift reactor is preferably fixed bed catalytic reactor.The present invention is to described solid The specification and model of fixed bed catalytic reactor are not particularly limited, and those skilled in the art are according to actual condition The fixed bed catalytic reactor of selection appropriate size and model.In one embodiment that the present invention is provided In, the fix bed catalyst reactor for being used is that a tubular with external heat and heat-insulation layer is fixed Bed catalytic reactor, is connected with raw material and is passed through pipeline and product output channel at its two ends, is passed through anti- It is bio oil and the hydrogeneous gaseous mixture of water reaction generation to answer the raw material of device, and be respectively equipped with gas control valve and Reaction stream amount controller, be passed through pipeline outer wall be provided with for preheat external heating device；Produced in reaction It is connected with turn on thing output channel including double-condenser, liquid product collection device and gas collection of products tank.
In the present invention, the specific mistake that the hydrogeneous gaseous mixture is reacted in water-gas shift Cheng Wei：
First, the copper zinc catalyst is filled in the center flat-temperature zone of the water-gas shift. Then, the temperature of the center flat-temperature zone of the water-gas shift is adjusted, makes the temperature of center flat-temperature zone Degree is preferably controlled in 150~350 DEG C.After temperature stabilization in question response device, open raw material and be passed through on pipeline The valve of feeder, hydrogeneous gaseous mixture is catalyzed through being passed through pipeline into catalytic reactor inner chamber in copper zinc Reacted in the presence of agent.Wherein, in the water-gas shift consumption of copper zinc catalyst with The ratio of the consumption of nickel-base catalyst is preferably 10~20 (g) in the catalyzing and reforming biologic oil reactor：10~20 (g)。
Hydrogeneous gaseous mixture is deposited after the completion of reaction in the copper zinc catalyst, obtains hydrogen-rich gaseous mixture, described Hydrogen-rich gaseous mixture is the hydrogen product that the present invention is prepared.In the present invention, the hydrogeneous gaseous mixture The reaction carried out in the presence of copper zinc catalyst referred to as water gas shift reaction, CO in hydrogeneous gaseous mixture and Vapor is by generating hydrogen and CO after water gas shift reaction2.In the present invention, it is described hydrogeneous by making There is water gas shift reaction in the CO in gaseous mixture, obtain with hydrogen and CO2Based on hydrogen-rich gaseous mixture.
In order to further improve the purity of hydrogen in the hydrogen product, the present invention is in the hydrogeneous gaseous mixture After being reacted, preferably also include：The hydrogen-rich gaseous mixture and CO of the hydrogeneous mixing solid/liquid/gas reactions generation2Absorb Liquid hybrid reaction, obtains hydrogen.
In the present invention, the hydrogen-rich gaseous mixture is hydrogeneous gaseous mixture anti-in the presence of the copper zinc catalyst The product that should be generated.The CO2Absorbing liquid preferably include calcium oxide aqueous solution, calcium hydroxide aqueous solution, One or more in aqueous sodium carbonate and sodium hydrate aqueous solution.The CO2Solute is dense in absorbing liquid Degree is preferably 10~30wt%.
In the present invention, the hydrogen-rich gaseous mixture and CO2The reactor that absorbing liquid hybrid reaction is used is referred to as CO2Absorbing reaction device.The present invention is to the CO2The specification and model of absorbing reaction device are not particularly limited, Those skilled in the art select the CO of appropriate size and model according to actual condition2Absorbing reaction device. In one embodiment that the present invention is provided, the CO for being used2Absorbing reaction device is one with outer loop water The barrel reactor of cooling, pipeline and product output channel are passed through what its two ends was connected with raw material, It is passed through CO2The raw material of absorbing reaction device be by hydrogen-rich gaseous mixture, the output channel of water-gas shift reaction with CO2The pipeline that is passed through of absorbing reaction device is connected, and is respectively equipped with gas control valve and reactant flow control Device；It is connected with turn on product output channel including double-condenser and gas collection of products tank.
In the present invention, the hydrogen-rich gaseous mixture is in CO2The detailed process reacted in absorbing reaction device For：
First by CO2Absorbing liquid is added to CO2In absorbing reaction device, hydrogeneous gaseous mixture is urged in copper zinc afterwards The hydrogen-rich gaseous mixture that generation is reacted in the presence of agent is passed through CO2In absorbing reaction device, in making hydrogen-rich gaseous mixture CO2With CO2Absorbing liquid is reacted.
Hydrogen-rich gaseous mixture is in CO2After absorbing liquid hybrid reaction terminates, high-purity hydrogen, the high-purity hydrogen are obtained The hydrogen product for purifying again that as present invention is prepared.In the present invention, the hydrogen-rich gaseous mixture By with CO2Absorbing liquid is reacted, and eliminates the CO in hydrogen-rich gaseous mixture2, obtain the hydrogen of high-purity.
In the present invention, it is preferred to also include to preparing the nickel-base catalyst and CO that are used during hydrogen2Absorb Liquid carries out regeneration treatment, wherein, the nickel-base catalyst regeneration treating method is：First, by inactivation The nickel-base catalyst carries out coke-burning regeneration treatment, the temperature of the coke-burning regeneration treatment in oxygen atmosphere Preferably 600~650 DEG C, the time of the coke-burning regeneration treatment is preferably 2~5h；Then, by coke-burning regeneration The catalyst after treatment carries out reduction treatment under reducing atmosphere, the nickel-base catalyst after being regenerated； The reducing atmosphere is preferably the gaseous mixture of hydrogen and argon gas, and the volume content of hydrogen is excellent in the gaseous mixture Elect 10~20% as, the time of the reduction treatment is preferably 2~5h.The CO2Regeneration of absorption solution treatment Method is：First, CO is extracted2Carbonate sediment in absorbing reaction device；Then to the sediment according to Secondary to be dried and sinter, the sintered product for obtaining is dissolved in water, the CO after being regenerated2Absorbing liquid；It is described Dry temperature is preferably 100~150 DEG C, and the dry time is preferably 2~6h, the temperature of the sintering Preferably 700~900 DEG C, the time of the sintering is preferably 4~8h.
In the method that the present invention is provided, reacted by catalyzing and reforming biologic oil hydrogeneous gaseous mixture is obtained first, The CO in the hydrogeneous gaseous mixture is removed using water-gas shift reaction afterwards, purity hydrogen higher is obtained Product.The present invention is optimized by the catalyst component used during bio oil catalytic reforming reaction, The temperature of catalyzing and reforming biologic oil reaction is reduced, so that the energy consumption of bio-oil hydrogen making is reduced, while passing through Catalyzing and reforming biologic oil reaction process and water-gas shift reaction technique are coupled, hydrogen product is improve Purity.In the preferred embodiment that the present invention is provided, also including water-gas shift reaction technique is obtained Hydrogen product and CO2Absorbing liquid hybrid reaction, so as to remove the CO in hydrogen product2, further carry The purity of hydrogen product high.Test result indicate that, the method provided using the present invention carries out bio-oil hydrogen making When, its reaction temperature is 300~650 DEG C, and bio oil conversion ratio reaches as high as 95.9%, hydrogen yield highest Up to 12.9g/ (100g bio oils), the highest content of hydrogen is up to 99.98vol% in hydrogen product.And 70vol% is usually less than using density of hydrogen in the gaseous product that existing bio-oil hydrogen making technology is obtained, it is seen that Using hydrogen purity obtained in the method that the present invention is provided much larger than the hydrogen that existing bio-oil hydrogen making technology is obtained Gas purity, and hydrogen purification operation is simple.
In the hydrogen production process that the present invention is provided, four main techniques are referred to：1) bio oil and water are certainly The reaction hydrogeneous gaseous mixture of generation, i.e. catalyzing and reforming biologic oil reaction hydrogen manufacturing are carried out in the presence of nickel-base catalyst processed； 2) hydrogeneous gaseous mixture carries out reaction generation hydrogen-rich gaseous mixture, i.e. water-gas shift in the presence of copper zinc catalyst Reaction removes CO；3) hydrogen-rich gaseous mixture and CO2Absorbent hybrid reaction generates High Purity Hydrogen, i.e. hydrogen-rich gaseous mixture Except CO2；4) decaying catalyst and CO2The regeneration treatment of absorbent, realizes catalyst and CO2Absorbent Recycle.
In the hydrogen production process that the present invention is provided, according to the requirement to hydrogen product purity, can individually adopt Process for making hydrogen is reacted with catalyzing and reforming biologic oil and prepare hydrogen product, it is also possible to which catalyzing and reforming biologic oil is anti- Answer process for making hydrogen and water-gas shift reaction technique coupling to prepare hydrogen product, bio oil can also be catalyzed Reforming reaction process for making hydrogen, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2Technique coupling prepares hydrogen Gas product.
Process for making hydrogen measured result shows：
1) when, individually preparing hydrogen product using catalyzing and reforming biologic oil reaction process for making hydrogen, bio oil is worked as When reforming reaction temperature is 600 DEG C, bio oil conversion ratio is 92.9%, and hydrogen yield is 11.5g hydrogen/(100g Bio oil), the product for obtaining is by 67.4vol% hydrogen, 25.6vol% carbon dioxide and 6.9vol% and 0.05 The Gas Mixtures Containing Hydrogen of vol% methane.
2) catalyzing and reforming biologic oil, is reacted into process for making hydrogen and water-gas shift reaction technique coupling prepares hydrogen It is raw when biological oil reforming reaction temperature is 650 DEG C and water gas reaction temperature is 250 DEG C during gas product Thing oil conversion ratio be 95.4%, hydrogen yield be 12.9g hydrogen/(100g bio oils), the product for obtaining be with 72.9vol% hydrogen and 27.1vol%CO2Based on hydrogen-rich mixed gas, CO and CH4Content is less than 0.01vol%.It can be seen that, catalyzing and reforming biologic oil reacts the CO to be formed can be almost by water gas shift reaction It is fully converted to CO2And hydrogen, reacted by biological oil reforming and water gas reaction coupling process is not only eliminated CO, while improve bio-oil hydrogen making yield.
3) catalyzing and reforming biologic oil, is reacted into process for making hydrogen, water-gas shift reaction technique and hydrogen-rich to mix Gas removes CO2When technique coupling prepares hydrogen product, with 15%CaO/15%Na2CO3Solution is CO2Absorbing liquid, When biological oil reforming reaction temperature be 650 DEG C, water gas reaction temperature be 250 DEG C and CO2Room temperature normal pressure is inhaled In the time receiving, CO is removed by biological oil reforming reaction, water gas reaction and hydrogen-rich gaseous mixture2It is raw after coupling process The conversion ratio of thing oil is 95.4%, and hydrogen yield is 12.9g hydrogen/(100g bio oil), and the product for obtaining is 99.97vol% high-purity hydrogen products.It can be seen that, shape during catalyzing and reforming biologic oil reaction and water gas reaction Into CO2CO is removed by hydrogen-rich gaseous mixture2Process can be removed almost completely, and the reformation for passing through bio oil Reaction, water gas reaction and hydrogen-rich gaseous mixture remove CO2Coupling process can prepare high-purity hydrogen.
For the sake of becoming apparent from, it is described in detail below by following examples.
Embodiment 1
Prepare nickel-base catalyst
79.41g nickel nitrate (molecular formula purchased in market are weighed respectively：Ni(NO3)2·6H2O, purity：Analysis is pure AR), 15.43g ferric nitrates (molecular formula：Fe(NO3)3·9H2O, purity：Analyze pure AR), 16.40g Cerous nitrate (molecular formula：Ce(NO3)2·6H2O, purity：Analyze pure AR) and 36.85g magnesium nitrates (point Minor：Mg(NO3)2·6H2O, purity：Analyze pure AR), 500mL deionized waters are added, it is configured to Nitrate mixed solution；Then by 55.0g γ-Al purchased in market2O3Molecular sieve powder (day chemical industry in Pingxiang City Filler Co., Ltd, model KA405) add above-mentioned nitrate solution, stir 5 hours, then stand Dipping is after 24 hours；Then the moisture in being evaporated solution in 100 DEG C of water-baths, is put into 120 in baking oven DEG C drying 12 hours；Finally it is calcined 8 hours in 550 DEG C and air atmosphere using Muffle furnace, is wrapped The mixed oxide catalyst presoma of nickeliferous, iron, cerium, magnesium and aluminium；The complex catalyst precursor that will be prepared again Body and Kaolin binder (Guang Yuan Ultramicro-powders Co., Ltd of Jiangyin City, model GY915) carry out mixing and grind Mill obtains mixed-powder, and wherein binding agent accounts for the 15wt% of total mixed-powder quality, by above-mentioned mixed powder Dried 12 hours under conditions of 120 DEG C of temperature after last compressing tablet, sieving obtains the nickel that particle diameter is 60~80 mesh Base catalyst microparticle, sealing preserve is standby.
According to raw material dosage and preparation process, the content to each component in above-mentioned catalyst precursor is carried out Calculate, as a result for：NiO 20.4wt%, Fe2O312.2wt%, CeO26.5wt%, MgO 5.8wt%, Al2O355.1wt%.
Embodiment 2
Prepare nickel-base catalyst
95.38g nickel nitrate (molecular formula purchased in market are weighed respectively：Ni(NO3)2·6H2O, purity：Analysis is pure AR), 18.72g ferric nitrates (molecular formula：Fe(NO3)3·9H2O, purity：Analyze pure AR), 19.42g Cerous nitrate (molecular formula：Ce(NO3)2·6H2O, purity：Analyze pure AR) and 36.85g magnesium nitrates (point Minor：Mg(NO3)2·6H2O, purity：Analyze pure AR)；Add 600mL deionized waters, configuration Into nitrate mixed solution；Then by 47.5g γ-Al purchased in market2O3Molecular sieve powder (day in Pingxiang City Work filler Co., Ltd, model KA405) add above-mentioned nitrate solution, stir 5 hours, then it is quiet Put after impregnating 24 hours；Then the moisture in being evaporated solution in 100 DEG C of water-baths, is put into 120 in baking oven DEG C drying 12 hours；Finally it is calcined 8 hours in 550 DEG C and air atmosphere using Muffle furnace, is wrapped The mixed oxide catalyst presoma of nickeliferous, iron, cerium, magnesium and aluminium；The complex catalyst precursor that will be prepared again Body and field fine powder binding agent (Kosé treasured company, model BP60) carry out mixed grinding and obtain mixed-powder, Wherein binding agent accounts for the 15wt% of total mixed-powder quality, by after above-mentioned mixed-powder compressing tablet in temperature 120 Dried 12 hours under conditions of DEG C, sieving obtains the nickel-base catalyst microparticle that particle diameter is 60~80 mesh, close Envelope is saved backup.
According to raw material dosage and preparation process, the content to each component in above-mentioned catalyst precursor is carried out Calculate, as a result for：NiO 24.5wt%, Fe2O314.8wt%, CeO27.7wt%, MgO 5.5wt%, Al2O347.5wt%.
Embodiment 3
Prepare nickel-base catalyst
88.39g nickel nitrate (molecular formula purchased in market are weighed respectively：Ni(NO3)2·6H2O, purity：Analysis is pure AR), 13.03g ferric nitrates (molecular formula：Fe(NO3)3·9H2O, purity：Analyze pure AR), 17.66g Cerous nitrate (molecular formula：Ce(NO3)2·6H2O, purity：Analyze pure AR) and 33.66g magnesium nitrates (point Minor：Mg(NO3)2·6H2O, purity：Analyze pure AR)；Add 600mL deionized waters, configuration Into nitrate mixed solution；Then by 54.7g γ-Al purchased in market2O3Molecular sieve powder (day in Pingxiang City Work filler Co., Ltd, model KA405) add above-mentioned nitrate solution, stir 5 hours, then it is quiet Put after impregnating 24 hours；Then the moisture in being evaporated solution in 100 DEG C of water-baths, is put into 120 in baking oven DEG C drying 12 hours；Finally it is calcined 8 hours in 550 DEG C and air atmosphere using Muffle furnace, is wrapped The mixed oxide catalyst presoma of nickeliferous, iron, cerium, magnesium and aluminium；The complex catalyst precursor that will be prepared again Body and field fine powder binding agent (Kosé treasured company, model BP60) carry out mixed grinding and obtain mixed-powder, Wherein binding agent accounts for the 15wt% of total mixed-powder quality, by after above-mentioned mixed-powder compressing tablet in temperature 120 Dried 12 hours under conditions of DEG C, sieving obtains the nickel-base catalyst microparticle that particle diameter is 60~80 mesh, close Envelope is saved backup.
According to raw material dosage and preparation process, the content to each component in above-mentioned catalyst precursor is carried out Calculate, as a result for：NiO 22.7wt%, Fe2O310.3wt%, CeO27.0wt%, MgO 5.3wt%, Al2O354.7wt%.
Embodiment 4
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock for using is Anhui Province's biomass clean National Renewable Energy Laboratory production The quick hot tearing bio oil (patent of rice husk：CN200910116098.6), bio oil by oxygen-bearing organic matter and Water is constituted, and wherein water content is about 30.3wt%, the essential element group of oxygen-bearing organic matter in the bio oil As 39.92wt%C, 8.15wt%H and 51.29wt%O.
In the present embodiment, catalyzing and reforming biologic oil reactor used is one with external heat and insulation The tubular fixed bed catalytic reactor of layer, bio-oil feedstock and carrier gas (vapor) are connected with its two ends Be passed through pipeline and product output channel, bio oil holding vessel and liquid addition device (liquid injection pump) It is connected, carrier gas channel is passed through pipeline connection with reactant, and is respectively equipped with gas control valve and reaction stream Amount controller, be passed through pipeline outer wall be provided with for preheat external heating device；In product efferent duct It is connected with turn on road including double-condenser, liquid product collection device and gas collection of products tank.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in reactor first Heart flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2 Volume content is 10% H2/ Ar gaseous mixtures are used as also Primordial Qi, use quality flow controller coutroi velocity It is 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is carried out Reduction 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens vapor carrier gas Valve, switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, is purged at room temperature Reactor purges 60min.In question response device after also Primordial Qi is discharged, then by adjusting reactor external heat The power of stove, makes the temperature of flat-temperature zone in reactor inner chamber at 300 DEG C, and the feed pipe for passing through reactor Feed pipe is preheating to 180 DEG C by the external heating device of upper setting.After temperature stabilization in reactor, open The valve of the feeder on bio-oil feedstock holding vessel outlet, bio oil inlet amount is 100g per hour, Bio oil and carrier gas are through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber 3：1.Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture passes through Gaseous product collecting tank is collected.
Embodiment 5
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 350 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 6
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 400 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 7
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 450 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 8
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 500 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 9
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 550 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 10
The present embodiment is intended to the quick hot tearing bio oil of explanation rice husk and individually uses catalytic reforming reaction process for making hydrogen Hydrogen manufacturing effect.
In the present embodiment, the bio-oil feedstock and catalyzing and reforming biologic oil reactor and the phase of embodiment 4 for using Together.
In the present embodiment, nickel-base catalyst obtained in 10g embodiments 1 is filled in the center of reactor first Flat-temperature zone.Before reaction, catalyst purges 60min with nitrogen at room temperature first, then switches to H2Volume Content is 10% H2Used as also Primordial Qi, use quality flow controller coutroi velocity is /Ar gaseous mixtures 100ml/min, then catalytic bed is heated to 650 DEG C with 10 DEG C/min heating rates, catalyst is reduced 5 hours.After catalyst process reduction terminates, reactor is down to room temperature, opens the valve of vapor carrier gas, Switching also Primordial Qi is vapor carrier gas, and the flow for adjusting carrier gas is 100ml/min, at room temperature purge Purging 60min.In question response device after also Primordial Qi is discharged, then by adjusting the work(of reactor externally heated oven Rate, makes the temperature of flat-temperature zone in reactor inner chamber at 600 DEG C, and is set on the feed pipe for passing through reactor External heating device feed pipe is preheating to 180 DEG C.After temperature stabilization in reactor, bio oil is opened The valve of the feeder on raw material storage tanks outlet, bio oil inlet amount is 100g, bio oil per hour With carrier gas through being passed through pipeline into catalytic reactor inner chamber, the water-oil factor for controlling reactor inner chamber is 3：1. Bio oil reacts the hydrogeneous gaseous mixture of generation in the presence of catalyst, and the hydrogeneous gaseous mixture is produced by gas Thing collecting tank is collected.
Embodiment 11
After catalyzing and reforming biologic oil reaction carries out 1h, hydrogeneous gaseous mixture obtained in embodiment 4~10 is carried out into Analysis, and calculate bio oil conversion ratio and hydrogen yield.Wherein, the conversion ratio of bio oil is by actually disappearing The biological oil carbon molal quantity of consumption and the radiometer for being input into the carbon molal quantity of bio oil in fixed bed catalytic reactor Calculate, hydrogen yield is by the hydrogen quality of actual acquisition and the matter of bio oil in input fixed bed catalytic reactor The ratio calculation of amount.Result is as shown in table 1：
Table 1 individually uses hydrogen manufacturing effect during catalyzing and reforming biologic oil reaction process
It can be seen from Table 1 that, the catalyst provided using the embodiment of the present invention 1 can be 300~600 Bio oil is catalytically conveted to hydrogen under the conditions of DEG C, bio oil conversion ratio reaches as high as 92.9%, hydrogen yield Reach as high as 11.5g/ (100g bio oils).
Embodiment 12
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill and the hydrogen manufacturing effect of water-gas shift reaction technique coupling.
In the present embodiment, the bio-oil feedstock for using is Anhui Province's biomass clean National Renewable Energy Laboratory production The quick hot tearing bio oil of wood chip, bio oil is made up of oxygen-bearing organic matter and water, and wherein water content is about 27.7 Wt%, in the bio oil oxygen-bearing organic matter essential element composition be 41.71wt%C, 7.71wt%H and 50.30wt%O.
In the present embodiment, catalyzing and reforming biologic oil reactor used is one with external heat and insulation The tubular fixed bed catalytic reactor of layer, bio-oil feedstock and carrier gas (vapor) are connected with its two ends Be passed through pipeline and product output channel, bio oil holding vessel and liquid addition device (liquid injection pump) It is connected, carrier gas channel is passed through pipeline connection with reactant, and is respectively equipped with gas control valve and reaction stream Amount controller, be passed through pipeline outer wall be provided with for preheat external heating device.
In the present embodiment, water-gas shift reactor used is one with external heat and heat-insulation layer Tubular fixed bed catalytic reactor, raw material and product output channel are connected with its two ends, are passed through water The raw material of gas shift reactor is the hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained, bio oil catalysis weight The output channel of whole reactor is connected with the pipeline that is passed through of water-gas shift reactor, carrier gas channel with reaction Thing is passed through pipeline connection, and is respectively equipped with gas control valve and reaction stream amount controller, is passed through outside pipeline Wall is provided with the external heating device for preheating；It is connected with turn including double on product output channel Condenser, liquid product collection device and gas collection of products tank.
In the present embodiment, nickel-base catalyst obtained in embodiment 2 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.The operating procedure of catalyzing and reforming biologic oil reaction and implementation The step of being carried out in example 4 is identical, and the reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil is urged It is 650 DEG C to change reforming reaction temperature, and bio oil inlet amount is 100g per hour, in water oil in reactor cavity Than being 3:1.After catalyzing and reforming biologic oil reactor reaches and stabilization is pre-conditioned more than, life is opened The output channel and the valve being passed through between pipeline of water-gas shift reactor of thing oil catalytic reforming reactor Door, the hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained is passed directly into water-gas shift reactor, then By adjusting the power of water-gas shift reactor externally heated oven, make perseverance in water-gas shift reactor inner chamber The temperature of warm area is at 150 DEG C.The hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained enters in the presence of catalyst Row water-gas shift reaction, obtains hydrogen-rich gaseous mixture, and the hydrogen-rich gaseous mixture passes through water-gas shift reaction The gaseous product collecting tank of device is collected.
Embodiment 13
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill and the hydrogen manufacturing effect of water-gas shift reaction technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor and the water-gas shift for using Reactor is identical with embodiment 12.
In the present embodiment, nickel-base catalyst obtained in embodiment 2 is filled in catalyzing and reforming biologic oil first anti- The center flat-temperature zone answered, catalyst amount is 10g, then by for the copper zinc catalyst of water-gas shift reaction (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) be filled in water-gas shift reactor Heart flat-temperature zone, catalyst amount is 10g.In the operating procedure and embodiment 4 of catalyzing and reforming biologic oil reaction The step of carrying out is identical, and the reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Catalyzing and reforming biologic oil Reaction temperature is 650 DEG C, and it in 100g per hour, reactor cavity in water-oil factor is 3 that bio oil inlet amount is:1. After catalyzing and reforming biologic oil reactor reaches and stabilization is pre-conditioned more than, bio oil catalysis is opened The output channel of reforming reactor and the valve being passed through between pipeline of water-gas shift reactor, by biology The hydrogeneous gaseous mixture that oily catalytic reforming is obtained is passed directly into water-gas shift reactor, then by adjusting water The power of gas shift reactor externally heated oven, makes the temperature of flat-temperature zone in water-gas shift reactor inner chamber At 200 DEG C.The hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained carries out water-gas in the presence of catalyst and turns Reaction is changed, hydrogen-rich gaseous mixture is obtained, the hydrogen-rich gaseous mixture is produced by the gas of water-gas shift reactor Thing collecting tank is collected.
Embodiment 14
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill and the hydrogen manufacturing effect of water-gas shift reaction technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor and the water-gas shift for using Reactor is identical with embodiment 12.
In the present embodiment, nickel-base catalyst obtained in embodiment 2 is filled in catalyzing and reforming biologic oil first anti- The center flat-temperature zone answered, catalyst amount is 10g, then by for the copper zinc catalyst of water-gas shift reaction (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) be filled in water-gas shift reactor Heart flat-temperature zone, catalyst amount is 10g.In the operating procedure and embodiment 4 of catalyzing and reforming biologic oil reaction The step of carrying out is identical, and the reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Catalyzing and reforming biologic oil Reaction temperature is 650 DEG C, and it in 100g per hour, reactor cavity in water-oil factor is 3 that bio oil inlet amount is:1. After catalyzing and reforming biologic oil reactor reaches and stabilization is pre-conditioned more than, bio oil catalysis is opened The output channel of reforming reactor and the valve being passed through between pipeline of water-gas shift reactor, by biology The hydrogeneous gaseous mixture that oily catalytic reforming is obtained is passed directly into water-gas shift reactor, then by adjusting water The power of gas shift reactor externally heated oven, makes the temperature of flat-temperature zone in water-gas shift reactor inner chamber At 250 DEG C.The hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained carries out water-gas in the presence of catalyst and turns Reaction is changed, hydrogen-rich gaseous mixture is obtained, the hydrogen-rich gaseous mixture is produced by the gas of water-gas shift reactor Thing collecting tank is collected.
Embodiment 15
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill and the hydrogen manufacturing effect of water-gas shift reaction technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor and the water-gas shift for using Reactor is identical with embodiment 12.
In the present embodiment, nickel-base catalyst obtained in embodiment 2 is filled in catalyzing and reforming biologic oil first anti- The center flat-temperature zone answered, catalyst amount is 10g, then by for the copper zinc catalyst of water-gas shift reaction (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) be filled in water-gas shift reactor Heart flat-temperature zone, catalyst amount is 10g.In the operating procedure and embodiment 4 of catalyzing and reforming biologic oil reaction The step of carrying out is identical, and the reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Catalyzing and reforming biologic oil Reaction temperature is 650 DEG C, and it in 100g per hour, reactor cavity in water-oil factor is 3 that bio oil inlet amount is:1. After catalyzing and reforming biologic oil reactor reaches and stabilization is pre-conditioned more than, bio oil catalysis is opened The output channel of reforming reactor and the valve being passed through between pipeline of water-gas shift reactor, by biology The hydrogeneous gaseous mixture that oily catalytic reforming is obtained is passed directly into water-gas shift reactor, then by adjusting water The power of gas shift reactor externally heated oven, makes the temperature of flat-temperature zone in water-gas shift reactor inner chamber At 300 DEG C.The hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained carries out water-gas in the presence of catalyst and turns Reaction is changed, hydrogen-rich gaseous mixture is obtained, the hydrogen-rich gaseous mixture is produced by the gas of water-gas shift reactor Thing collecting tank is collected.
Embodiment 16
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill and the hydrogen manufacturing effect of water-gas shift reaction technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor and the water-gas shift for using Reactor is identical with embodiment 12.
In the present embodiment, nickel-base catalyst obtained in embodiment 2 is filled in catalyzing and reforming biologic oil first anti- The center flat-temperature zone answered, catalyst amount is 10g, then by for the copper zinc catalyst of water-gas shift reaction (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) be filled in water-gas shift reactor Heart flat-temperature zone, catalyst amount is 10g.In the operating procedure and embodiment 4 of catalyzing and reforming biologic oil reaction The step of carrying out is identical, and the reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Catalyzing and reforming biologic oil Reaction temperature is 650 DEG C, and it in 100g per hour, reactor cavity in water-oil factor is 3 that bio oil inlet amount is:1. After catalyzing and reforming biologic oil reactor reaches and stabilization is pre-conditioned more than, bio oil catalysis is opened The output channel of reforming reactor and the valve being passed through between pipeline of water-gas shift reactor, by biology The hydrogeneous gaseous mixture that oily catalytic reforming is obtained is passed directly into water-gas shift reactor, then by adjusting water The power of gas shift reactor externally heated oven, makes the temperature of flat-temperature zone in water-gas shift reactor inner chamber At 350 DEG C.The hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained carries out water-gas in the presence of catalyst and turns Reaction is changed, hydrogen-rich gaseous mixture is obtained, the hydrogen-rich gaseous mixture is produced by the gas of water-gas shift reactor Thing collecting tank is collected.
Embodiment 17
After catalyzing and reforming biologic oil reaction carries out 1h, hydrogeneous gaseous mixture obtained in embodiment 12~16 is carried out into Analysis, and calculate bio oil conversion ratio and hydrogen yield.Wherein, the conversion ratio of bio oil is by actually disappearing The biological oil carbon molal quantity of consumption and the radiometer for being input into the carbon molal quantity of bio oil in fixed bed catalytic reactor Calculate, hydrogen yield is by the hydrogen quality of actual acquisition and the matter of bio oil in input fixed bed catalytic reactor The ratio calculation of amount.Result is as shown in table 2：
Table 2 is using catalyzing and reforming biologic oil reaction process and the effect of water-gas shift reaction technique coupled hydrogen making
It can be seen from Table 2 that, the catalyst provided using the embodiment of the present invention 2 can be in reforming reaction temperature Spend for 650 DEG C and water-gas shift reaction temperature are to be catalytically conveted to bio oil under the conditions of 150~350 DEG C Hydrogen, bio oil conversion ratio reaches as high as 95.9%, and hydrogen yield reaches as high as 12.9g/ (100g bio oils). By table 2 it can also be seen that catalyzing and reforming biologic oil react the CO to be formed can be several by water gas shift reaction It is fully converted to CO2And hydrogen, reacted by biological oil reforming and water gas reaction coupling process not only disappears Except CO impurity components, it is easy to the purification of hydrogen product, while improve bio-oil hydrogen making yield.
Embodiment 18
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2The hydrogen manufacturing effect of technique coupling.
In the present embodiment, the bio-oil feedstock for using is Anhui Province's biomass clean National Renewable Energy Laboratory production The quick hot tearing bio oil of wood chip, bio oil is made up of oxygen-bearing organic matter and water, and wherein water content is about 27.7 Wt%, in the bio oil oxygen-bearing organic matter essential element composition be 41.71wt%C, 7.71wt%H and 50.30wt%O.
In the present embodiment, catalyzing and reforming biologic oil reactor used is one with external heat and insulation The tubular fixed bed catalytic reactor of layer, bio-oil feedstock and carrier gas (vapor) are connected with its two ends Be passed through pipeline and product output channel, bio oil holding vessel and liquid addition device (liquid injection pump) It is connected, carrier gas channel is passed through pipeline connection with reactant, and is respectively equipped with gas control valve and reaction stream Amount controller, be passed through pipeline outer wall be provided with for preheat external heating device.
In the present embodiment, water-gas shift reactor used is one with external heat and heat-insulation layer Tubular fixed bed catalytic reactor, raw material and product output channel are connected with its two ends, are passed through water The raw material of gas shift reactor is the hydrogeneous gaseous mixture that catalyzing and reforming biologic oil is obtained, bio oil catalysis weight The output channel of whole reactor is connected with the pipeline that is passed through of water-gas shift reactor, carrier gas channel with reaction Thing is passed through pipeline connection, and is respectively equipped with gas control valve and reaction stream amount controller, is passed through outside pipeline Wall is provided with the external heating device for preheating.
In the present embodiment, CO used2Absorbing reaction device is that a tubular with outer loop water cooling is anti- Device is answered, pipeline and product output channel are passed through what its two ends was connected with raw material, be passed through CO2Absorb anti- The raw material for answering device is the hydrogen-rich gaseous mixture by being produced after biological oil reforming reaction and water-gas shift reaction, The output channel and CO of water-gas shift reaction2The pipeline that is passed through of absorbing reaction device is connected, and is respectively equipped with gas Body controls valve and reaction stream amount controller；It is connected with turn on product output channel including double cold Condenser and gas collection of products tank.
In the present embodiment, nickel-base catalyst obtained in embodiment 3 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.CO2It is molten that absorbing reaction device loads 4 liters of 20wt%CaO Liquid.
The operating procedure of catalyzing and reforming biologic oil reaction is same as Example 4, the behaviour of water-gas shift reaction Make step identical with embodiment 12.The reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil Catalytic reforming reaction temperature is 600 DEG C, and bio oil inlet amount is in water in 100g per hour, reactor cavity Oil is than being 3.5:1；It is 250 that the reaction condition of water-gas shift reaction is fixed on water-gas shift reaction temperature ℃.When catalyzing and reforming biologic oil reactor and water-gas shift reactor reach and stable default more than After condition, CO is opened2The outer loop water cooling of absorbing reaction device, is then turned on water-gas shift reactor Output channel and CO2The valve being passed through between pipeline of absorbing reaction device, catalyzing and reforming biologic oil is anti- CO should be passed through with the hydrogen-rich gaseous mixture of generation after water-gas shift reaction2In absorbing reaction device.Hydrogen-rich mixes Carbon dioxide in gas is in CO2It is removed in the presence of absorbing liquid, obtains high-purity hydrogen, it is described high-purity Hydrogen passes through CO2The gaseous product collecting tank of absorbing reaction device is collected.
Embodiment 19
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2The hydrogen manufacturing effect of technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor, the water-gas shift for using Reactor and CO2Absorbing reaction device is identical with embodiment 18.
In the present embodiment, nickel-base catalyst obtained in embodiment 3 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.CO2Absorbing reaction device loads 4 liters of 20wt%Ca (OH)2 Solution.
The operating procedure of catalyzing and reforming biologic oil reaction is same as Example 4, the operation of water-gas shift reaction Step is identical with embodiment 12.The reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil is urged It is 600 DEG C to change reforming reaction temperature, and bio oil inlet amount is 100g per hour, in water-oil factor in reactor cavity It is 3.5:1；The reaction condition of water-gas shift reaction is fixed on water-gas shift reaction temperature for 250 DEG C.When Catalyzing and reforming biologic oil reactor and water-gas shift reactor reach and stabilization is pre-conditioned more than Afterwards, CO is opened2The outer loop water cooling of absorbing reaction device, is then turned on the output of water-gas shift reactor Pipeline and CO2The valve being passed through between pipeline of absorbing reaction device, by catalyzing and reforming biologic oil reaction and water coal The hydrogen-rich gaseous mixture produced after gas shift reaction is passed through CO2In absorbing reaction device.Dioxy in hydrogen-rich gaseous mixture Change carbon in CO2It is removed in the presence of absorbing liquid, obtains high-purity hydrogen, the high-purity hydrogen passes through CO2 The gaseous product collecting tank of absorbing reaction device is collected.
Embodiment 20
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2The hydrogen manufacturing effect of technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor, the water-gas shift for using Reactor and CO2Absorbing reaction device is identical with embodiment 18.
In the present embodiment, nickel-base catalyst obtained in embodiment 3 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.CO2It is molten that absorbing reaction device loads 4 liters of 10wt%NaOH Liquid.
The operating procedure of catalyzing and reforming biologic oil reaction is same as Example 4, the operation of water-gas shift reaction Step is identical with embodiment 12.The reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil is urged It is 600 DEG C to change reforming reaction temperature, and bio oil inlet amount is 100g per hour, in water-oil factor in reactor cavity It is 3.5:1；The reaction condition of water-gas shift reaction is fixed on water-gas shift reaction temperature for 250 DEG C.When Catalyzing and reforming biologic oil reactor and water-gas shift reactor reach and stabilization is pre-conditioned more than Afterwards, CO is opened2The outer loop water cooling of absorbing reaction device, is then turned on the output of water-gas shift reactor Pipeline and CO2The valve being passed through between pipeline of absorbing reaction device, by catalyzing and reforming biologic oil reaction and water coal The hydrogen-rich gaseous mixture produced after gas shift reaction is passed through CO2In absorbing reaction device.Dioxy in hydrogen-rich gaseous mixture Change carbon in CO2It is removed in the presence of absorbing liquid, obtains high-purity hydrogen, the high-purity hydrogen passes through CO2 The gaseous product collecting tank of absorbing reaction device is collected.
Embodiment 21
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2The hydrogen manufacturing effect of technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor, the water-gas shift for using Reactor and CO2Absorbing reaction device is identical with embodiment 18.
In the present embodiment, nickel-base catalyst obtained in embodiment 3 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.CO2It is molten that absorbing reaction device loads 4 liters of 20wt%NaOH Liquid.
The operating procedure of catalyzing and reforming biologic oil reaction is same as Example 4, the operation of water-gas shift reaction Step is identical with embodiment 12.The reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil is urged It is 600 DEG C to change reforming reaction temperature, and bio oil inlet amount is 100g per hour, in water-oil factor in reactor cavity It is 3.5:1；The reaction condition of water-gas shift reaction is fixed on water-gas shift reaction temperature for 250 DEG C.When Catalyzing and reforming biologic oil reactor and water-gas shift reactor reach and stabilization is pre-conditioned more than Afterwards, CO is opened2The outer loop water cooling of absorbing reaction device, is then turned on the output of water-gas shift reactor Pipeline and CO2The valve being passed through between pipeline of absorbing reaction device, by catalyzing and reforming biologic oil reaction and water coal The hydrogen-rich gaseous mixture produced after gas shift reaction is passed through CO2In absorbing reaction device.Dioxy in hydrogen-rich gaseous mixture Change carbon in CO2It is removed in the presence of absorbing liquid, obtains high-purity hydrogen, the high-purity hydrogen passes through CO2 The gaseous product collecting tank of absorbing reaction device is collected.
Embodiment 22
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2The hydrogen manufacturing effect of technique coupling.
In the present embodiment, bio-oil feedstock, catalyzing and reforming biologic oil reactor, the water-gas shift for using Reactor and CO2Absorbing reaction device is identical with embodiment 18.
In the present embodiment, nickel-base catalyst obtained in embodiment 3 is filled in catalyzing and reforming biologic oil first The center flat-temperature zone of reaction, catalyst amount is 10g, then will be urged for the copper zinc of water-gas shift reaction Agent (33.2wt%CuO/12.8wt%ZnO/54.0wt%Al2O3) it is filled in water-gas shift reactor Center flat-temperature zone, catalyst amount is 10g.CO2Absorbing reaction device loads 4 liters of absorbing liquids, the suction Receive liquid and contain 15wt%CaO and 15wt%Na2CO3。
The operating procedure of catalyzing and reforming biologic oil reaction is same as Example 4, the operation of water-gas shift reaction Step is identical with embodiment 12.The reaction condition of catalyzing and reforming biologic oil reaction is fixed as：Bio oil is urged It is 600 DEG C to change reforming reaction temperature, and bio oil inlet amount is 100g per hour, in water-oil factor in reactor cavity It is 3.5:1；The reaction condition of water-gas shift reaction is fixed on water-gas shift reaction temperature for 250 DEG C.When Catalyzing and reforming biologic oil reactor and water-gas shift reactor reach and stabilization is pre-conditioned more than Afterwards, CO is opened2The outer loop water cooling of absorbing reaction device, is then turned on the output of water-gas shift reactor Pipeline and CO2The valve being passed through between pipeline of absorbing reaction device, by catalyzing and reforming biologic oil reaction and water coal The hydrogen-rich gaseous mixture produced after gas shift reaction is passed through CO2In absorbing reaction device.Dioxy in hydrogen-rich gaseous mixture Change carbon in CO2It is removed in the presence of absorbing liquid, obtains high-purity hydrogen, the high-purity hydrogen passes through CO2 The gaseous product collecting tank of absorbing reaction device is collected.
Embodiment 23
After catalyzing and reforming biologic oil reaction carries out 1h, composition is carried out to high-purity hydrogen obtained in embodiment 18~22 Analysis, and calculate bio oil conversion ratio and hydrogen yield.Wherein, the conversion ratio of bio oil presses actual consumption Biological oil carbon molal quantity with input fixed bed catalytic reactor in bio oil carbon molal quantity radiometer Calculate, hydrogen yield is by the hydrogen quality of actual acquisition and the matter of bio oil in input fixed bed catalytic reactor The ratio calculation of amount.Result is as shown in table 3：
Table 3 is using catalyzing and reforming biologic oil reaction process, water-gas shift reaction technique CO is removed with hydrogen-rich gaseous mixture2The effect of technique coupled hydrogen making
It can be seen from Table 3 that, the catalyst provided using the embodiment of the present invention 3 can be in reforming reaction Temperature is that 600 DEG C and water-gas shift reaction temperature are that bio oil is catalytically conveted into hydrogen under the conditions of 250 DEG C Gas, bio oil conversion ratio reaches as high as 95.4%, and hydrogen yield reaches as high as 12.9g/ (100g bio oils), The purity of hydrogen gas product reaches as high as 99.98vol%.
By table 3 it can also be seen that catalyzing and reforming biologic oil reacts and formation during water gas reaction CO2CO is removed by hydrogen-rich gaseous mixture2Process can be removed almost completely, and anti-by the reformation of bio oil Answer, water gas reaction and hydrogen-rich gaseous mixture remove CO2Coupling process can prepare high-purity hydrogen.
Embodiment 24
The present embodiment is intended to the quick hot tearing bio oil of explanation wood chip and reacts hydrogen manufacturing work using catalyzing and reforming biologic oil Skill, water-gas shift reaction technique and hydrogen-rich gaseous mixture remove CO2Catalyst is steady in the hydrogen production process of technique coupling Qualitative and recycling utilization.
In the present embodiment, the original that bio-oil feedstock, catalyst and the reactor and embodiment 18 for using are used Material, catalyst and reactor, the CO for using2Absorbing liquid is containing 15wt%CaO and 15wt%NaCO3's Blend absorbent.Nickel-base catalyst is filled in the center flat-temperature zone of catalyzing and reforming biologic oil reaction first, Catalyst amount is 10g, then is turned water-gas is filled in for the copper zinc catalyst of water-gas shift reaction The center flat-temperature zone of reactor is changed, catalyst amount is 10g.CO2Absorbing reaction device loads 4 liters and contains 15wt%CaO and 15wt%NaCO3Blend absorbent.
In the present embodiment, catalyzing and reforming biologic oil reaction, water-gas shift reaction and hydrogen-rich gaseous mixture remove CO2 Operating procedure it is identical with the step of being carried out in embodiment 18.The reaction condition of catalyzing and reforming biologic oil reaction It is fixed as：Catalyzing and reforming biologic oil reaction temperature is 650 DEG C, and bio oil inlet amount is 50g per hour, instead Answer in device chamber water-oil factor be 4:1；The reaction condition of water-gas shift reaction is fixed as：Water-gas shift is anti- It is 250 DEG C to answer temperature；CO2The reaction condition of absorbing reaction is fixed as：25 DEG C of room temperature.Work as bio-oil hydrogen making Reaction time reaches 30 hours, stops injection bio-oil feedstock and vapor carrier gas.
After bio-oil hydrogen making reacts to be stopped, regeneration treatment is carried out to nickel-base catalyst：Catalyst is used first The nitrogen purging 30min of 100ml/min flow velocitys, then switch to oxygen as oxidant, at 650 DEG C and Bio oil catalytic reforming reaction catalyst is carried out at coke-burning regeneration under the Oxygen Condition of 100ml/min flow velocitys Reason 3 hours；Then switch to 10%H2/ Ar also Primordial Qi, use quality flow controller coutroi velocity is 100ml/min, carries out reduction 3 hours under the conditions of 650 DEG C to bio oil catalytic reforming reaction catalyst. Meanwhile, extract CO2Lime deposit in absorbing reaction device, is put into baking oven 120 DEG C of dryings 4 hours, Again in Muffle furnace 800 DEG C sinter 6 hours, the sintered product for obtaining regeneration treatment is dissolved in solution and again It is secondary to use.After regeneration is disposed, the test of next round bio-oil hydrogen making is carried out continuously.
When the catalyzing and reforming biologic oil reaction of every wheel test carries out 1h and 30h to CO2The gas of absorbing reaction device The high-purity hydrogen collected in body collection of products tank carries out constituent analysis, and calculates bio oil conversion ratio and hydrogen Yield.Wherein, the conversion ratio of bio oil is urged by the biological oil carbon molal quantity of actual consumption with input fixed bed Change the ratio calculation of the carbon molal quantity of bio oil in reactor, hydrogen yield is by the actual hydrogen quality for obtaining With the ratio calculation of the quality of bio oil in input fixed bed catalytic reactor.Result is as shown in table 4：
The bio oil of table 4 prepares the stability and regeneration effect of catalyst during high-purity hydrogen
It can be seen from Table 4 that, when reacted between be 1 hour, by the reforming reaction of bio oil, water Coal gas conversion reaction and hydrogen-rich gaseous mixture remove CO2After coupling process, the conversion ratio of bio oil is up to 95.3 %, hydrogen yield is highest 12.8g hydrogen/(100g bio oil), and the hydrogen product purity for obtaining is up to 99.98vol%.It it is 30 hours between when reacted, the conversion ratio of bio oil is up to 77.4%, hydrogen is produced Rate is up to 10.5g hydrogen/(100g bio oil), the hydrogen product purity up to 98.72vol% for obtaining. By table 4 it can also be seen that to the catalyst and CO of inactivation2Absorbing liquid carries out regeneration and processes and enter Row retest, catalyst and CO after being processed using regeneration2Bio-oil hydrogen making effect connects during absorbing liquid Closely use fresh catalyst and CO2The bio-oil hydrogen making effect of absorbing liquid.Therefore, by inactivation Catalyst and CO2Absorbing liquid carries out regeneration treatment and can realize catalyst and CO2Absorbing liquid is recycled.
The above is only the preferred embodiment of the present invention, it is noted that general for the art For logical technical staff, under the premise without departing from the principles of the invention, some improvement and profit can also be made Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims (8)

1. a kind of nickel-base catalyst, in terms of parts by weight, including：
2. catalyst according to claim 1, it is characterised in that in terms of parts by weight, including：
3. a kind of method that utilization bio oil prepares hydrogen, comprises the following steps：
A), bio oil and water are carried out instead in the presence of the nickel-base catalyst described in any one of claim 1~2 Should, obtain hydrogeneous gaseous mixture；
B), the hydrogeneous gaseous mixture is reacted in the presence of copper zinc catalyst, obtains hydrogen.
4. method according to claim 3, it is characterised in that in step a), the bio oil It it is 300~650 DEG C with the temperature that water reacts.
5. method according to claim 3, it is characterised in that in step a), the bio oil It is 1 with the mass ratio of water：(3~4).
6. method according to claim 3, it is characterised in that in step b), it is described hydrogeneous mixed The temperature that conjunction gas is reacted is 150~350 DEG C.
7. method according to claim 3, it is characterised in that the hydrogeneous gaseous mixture is reacted Also include afterwards：
The hydrogen-rich gaseous mixture and CO of the hydrogeneous mixing solid/liquid/gas reactions generation2Absorbing liquid hybrid reaction, obtains hydrogen Gas.
8. method according to claim 7, it is characterised in that the CO2Absorbing liquid includes oxidation One kind or many in the calcium aqueous solution, calcium hydroxide aqueous solution, aqueous sodium carbonate and sodium hydrate aqueous solution Kind.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108187683A (en) * 2018-01-12 2018-06-22 安徽理工大学 Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application
CN109513443A (en) * 2017-09-19 2019-03-26 侯飞燕 A kind of support type bio-oil reforming hydrogen-production catalyst and preparation method thereof
CN112473680A (en) * 2020-12-10 2021-03-12 华中科技大学 Difunctional calcium-based catalyst and preparation method and application thereof
CN113318745A (en) * 2021-06-24 2021-08-31 南京林业大学 Preparation method of hydrogen-rich catalyst for biomass pyrolysis
CN113950370A (en) * 2019-04-22 2022-01-18 马来西亚国立大学 Catalyst composition for pure hydrogen production and method for preparing the same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172232A (en) * 2007-10-10 2008-05-07 大连理工大学 Palygorskite load nickel base biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof
CN101177239A (en) * 2007-10-15 2008-05-14 中国科学技术大学 Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil
CN101306370A (en) * 2008-06-03 2008-11-19 中国科学技术大学 Mixed oxide catalyst and use thereof in steam reforming bio-oil hydrogen making
CN101348234A (en) * 2008-09-05 2009-01-21 华东理工大学 Method for preparing hydrogen from biomass
CN101439844A (en) * 2008-12-16 2009-05-27 中国科学院广州能源研究所 Chemical link coupling catalytic reforming hydrogen making method and device
CN101444740A (en) * 2008-12-16 2009-06-03 中国科学院广州能源研究所 Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof
CN101530801A (en) * 2009-04-15 2009-09-16 中国科学技术大学 Carbon nano tube supported nickel catalyst as well as preparation method and application thereof
CN101584995A (en) * 2009-06-19 2009-11-25 华东理工大学 Catalyst carrier and catalyst as well as preparation method thereof
CN102974362A (en) * 2012-11-30 2013-03-20 安徽理工大学 Catalyst for hydrogen production by catalytic reforming with biological oil and preparation method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172232A (en) * 2007-10-10 2008-05-07 大连理工大学 Palygorskite load nickel base biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof
CN101177239A (en) * 2007-10-15 2008-05-14 中国科学技术大学 Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil
CN101306370A (en) * 2008-06-03 2008-11-19 中国科学技术大学 Mixed oxide catalyst and use thereof in steam reforming bio-oil hydrogen making
CN101348234A (en) * 2008-09-05 2009-01-21 华东理工大学 Method for preparing hydrogen from biomass
CN101439844A (en) * 2008-12-16 2009-05-27 中国科学院广州能源研究所 Chemical link coupling catalytic reforming hydrogen making method and device
CN101444740A (en) * 2008-12-16 2009-06-03 中国科学院广州能源研究所 Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof
CN101530801A (en) * 2009-04-15 2009-09-16 中国科学技术大学 Carbon nano tube supported nickel catalyst as well as preparation method and application thereof
CN101584995A (en) * 2009-06-19 2009-11-25 华东理工大学 Catalyst carrier and catalyst as well as preparation method thereof
CN102974362A (en) * 2012-11-30 2013-03-20 安徽理工大学 Catalyst for hydrogen production by catalytic reforming with biological oil and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
马世昌: "《化学物质辞典》", 30 April 1999 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109513443A (en) * 2017-09-19 2019-03-26 侯飞燕 A kind of support type bio-oil reforming hydrogen-production catalyst and preparation method thereof
CN108187683A (en) * 2018-01-12 2018-06-22 安徽理工大学 Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application
CN113950370A (en) * 2019-04-22 2022-01-18 马来西亚国立大学 Catalyst composition for pure hydrogen production and method for preparing the same
CN112473680A (en) * 2020-12-10 2021-03-12 华中科技大学 Difunctional calcium-based catalyst and preparation method and application thereof
CN112473680B (en) * 2020-12-10 2021-10-08 华中科技大学 Difunctional calcium-based catalyst and preparation method and application thereof
CN113318745A (en) * 2021-06-24 2021-08-31 南京林业大学 Preparation method of hydrogen-rich catalyst for biomass pyrolysis

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