CN101098022A - Biomass hydrogen energy electric generation method - Google Patents
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Abstract
A biomass hydrogen energy generating method is characterized in that using biomass thermal chemical hydrogen generating method to convert biomass into clean high-temperature hydrogen-abundant fuel gas, which can be directly used in fusion carbonate fuel battery without purification to generate electricity.
Description
Technical field
The present invention relates to a kind of method of biomass hydrogen energy electric generation.
Background technology
Along with the growing tension of fossil fuel shortage, energy supply situation, the exploitation of biomass energy attracts great attention.Biomass energy has aboundresources, the huge and reproducible characteristics of reserves.The biomass fermentation power technology utilizes abandoned biomass resource production green electric power supplies such as stalk, for alleviating power supply shortage, ensureing that energy security is significant.The biomass fermentation power technology of development mainly contains direct combustion power generation of biomass and gasifying electricity generation at present.Directly combustion power generation as boiler oil, is produced superheated steam with biomass, realizes electrical production by steam turbine, gas turbine; Gasifying electricity generation is converted into middle fuel gas with low heat value by the gasifier of forms such as fluid bed, fixed bed with biomass material, is converted into electric power then in internal combustion engine, gas turbine.The method of the plant straw and stalk generating of a kind of 80%-90% of utilization is disclosed as patent " method of utilizing plant straw and stalk to generate electricity " (01129656.9), at first biological substance is carried out cracking reaction at 200-500 ℃, produce mixed pyrolysis gas, then this mixed pyrolysis gas is purified, after the decoking wet goods is handled, again its IC engine supply is generated electricity, or described mixed pyrolysis gas directly delivered to 800-1000 ℃ of combustion zone, produce combustion gas, drive gas turbine by this combustion gas and drive generator for electricity generation, or described mixed pyrolysis gas directly delivered to the thermo-power station boiler combustion, replace coal, fry dried food ingredients.Directly combustion power generation and gasifying electricity generation technology have all had commercial Application, but wherein ubiquitous technology energy transformation ratio is low and the scale utilization in biomass material collect carrying cost and still can not be ignored than problems such as height.The biomass fermentation power technology is combined with Hydrogen Technology, utilize the intermediary of Hydrogen Energy,, will realize that the clean and effective of biomass to electric power transforms in conjunction with the efficient and flexibility of fuel cell as biomass power generation.Fuel cell system is not subjected to the restriction of the second law of thermodynamics, and generating efficiency will be far above the thermal power generation of present routine, internal combustion engine generating etc.Thereby the biomass hydrogen energy electric generation technology has broad application prospects.Patent of invention " is utilized crops biomass hydrogen preparation and hydrogen power generation device " (200410005733.0), disclose a kind of biomass such as agricultural crop straw of utilizing and produced hydrogen, and be converted into electric energy by biomass decomposition, ferment for hydrogen production, reactant liquor reprocessing, water seal, gas wash-out, gas drying, Chu Qing and fuel-cell device by the microbe decomposition method.Microbial conversion process utilizes the decomposition microbe that various agricultural stalks and starchy material are decomposed into glucide, utilizes the microbial fermentation glucide to produce hydrogen; The microbial conversion cycle is longer, and the microbial conversion process generally only can utilize and contain saccharic composition in the raw material, causes the biomass material utilance low, produces the restriction that the hydrogen process is subjected to raw material; Need purify to hydrogen, pure then hydrogen is used for the proton membrane fuel battery generating of low temperature.
Summary of the invention
The purpose of this invention is to provide a kind of method that possesses the biomass hydrogen energy electric generation of higher raw material availability and higher-energy transformation efficiency.The biomass hydrogen energy electric generation method that the present invention proposes, biomass thermal chemistry hydrogen producing technology by the advanced person, biomass are converted into the hydrogen-rich combustion gas of cleaning, the rich, high temperature Hydrogen fuel need not purified can be directly used in molten carbonate fuel cell, realize electrical production, can obtain higher energy conversion efficiency, also greatly expansion of the adaptability of raw material simultaneously.
The solution of the present invention realizes by following steps: a kind of biomass hydrogen energy electric generation method, it is characterized in that by biomass thermal chemistry hydrogen production process biomass being converted into the rich, high temperature Hydrogen fuel of cleaning, the rich, high temperature Hydrogen fuel need not purified and be directly applied to molten carbonate fuel cell and realize electrical production.
Concrete characteristics of the present invention also have, and described biomass thermal chemistry hydrogen production process is for to make biomass material pyrolysis under 550-650 ℃ of temperature be converted into gas-phase product and carbon residue under the secluding air condition; Shift out reaction system after carbon residue separated from gas-phase product, obtain the energy loss that heat is used for the biomass hydrogen energy electric generation process by burning; The gas-phase product that produces after the pyrolysis is carried out cracking under 800-950 ℃ of condition, and realize the cracking of gas-phase product in conjunction with the effect of dolomite catalyst and steam, reform, the heavy hydrocarbons component coke tar cracking that molecular weight is bigger, be restructured as hydrogen, methane and other light hydrocarbons, eliminate tar and reduce hydrocarbon content such as methane, improve the content and the output of hydrogen in the gaseous product, preparation hydrogen volume content reaches the gaseous product of 30%-55%, be cooled to 300 ℃, carry out hot filtration and desulfurization, after removing impurity gaseous product is sent into the carbon monodixe conversion reactor, under carbon monoxide transformation catalyst and steam effect, carbon monoxide further is converted into hydrogen, the hydrogen-rich combustion gas that obtains directly applies in the molten carbonate fuel cell, by the electrochemical process generation electric power of fuel cell system inside.
Described biomass thermal chemistry hydrogen production process is for quantitatively to send the biomass materials such as stalk of water content 10%-20% into pyrolysis reactor after fragmentation; Biomass material in pyrolysis reactor inside by helix transporting device when carry at the pyrolysis reactor rear portion by indirect, biomass pyrolytic under the secluding air condition takes place in the course of conveying, the pyrolytic reaction actuator temperature is regulated by outside flue gas heating and control device, pyrolysis temperature 550-650 ℃, the pyrolytic reaction time was at least 5 minutes, the composition volatile matter that accounts for biomass material weight 60-75% separated out becomes gas-phase product, comprises hydrogen in this gas-phase product, carbon monoxide, carbon dioxide, be condensed into the macromolecular compound of liquid under the normal temperature such as methane under the normal temperature such as incoagulable gas and tar;
The pyrolysis reactor rear portion, the biomass pyrolytic solid product separates with gas-phase product; Gas-phase product enters deduster, and the granule foreign in the gas-phase product is removed; Solid product enters the carbon residue collecting box, and sends into the carbon residue burner by conveying mechanism, realizes good combustion by adjusting air-supply, obtains high-temperature flue gas, is used to keep pyrolytic reaction, cracking reaction portion temperature level and produces overheated steam institute energy requirement;
Pyrolysis gas-phase product after the dedusting enters cracking reactor, filling dolomite catalyst in the cracking reactor, and feed overheated steam (140 ℃), and the make a living 10-30% of material mass of the addition of steam, and adjust according to the biomass material characteristic; The temperature of utilizing flue gas heating and control device to regulate cracker, under temperature 800-950 ℃ condition, carry out cracking, reaction time was at least 3 seconds, and the heavy hydrocarbons component (tar) that molecular weight is bigger is cracked into hydrogen, methane and other light hydrocarbons, and in conjunction with the steam reformation of pyrolysis product, realize the conversion of hydro carbons such as methane, improve hydrogen output, eliminate tar, increase the hydrogen content of gas yield and gas, obtain hydrogen-rich combustion gas, reduce the carbon distribution inactivation of analysing carbon and avoiding catalyst simultaneously.
Beneficial effect of the present invention is: 1, to adopt biomass resource such as stalk be raw material for method of the present invention, be converted into hydrogen-rich combustion gas by pyrolysis in conjunction with cleavage method, and in conjunction with high-temperature fuel cell realization generating, the energy conversion efficiency of fuel gas generation part possesses higher energy conversion efficiency more than 50% than traditional biomass combustion gasifying electricity generation mode.2, pyrolysis is produced the method for hydrogen-rich combustion gas in conjunction with cracking, can use multiple agriculture and forestry organic waste materials such as rice husk, corn stalk, rice straw, straw, and raw material accommodation is wide, and conversion process only produces a small amount of biomass ash, still can be used as also field of fertilizer, the raw material availability height.3, hydrogen content is higher in the hydrogen-rich combustion gas, is directly used in the high-temperature fuel cell generating, has avoided expensive hydrogen purification process; The rich, high temperature Hydrogen fuel that hydrogen manufacturing workshop section produces is directly used in fuel cell, does not cool off, and has improved energy and has utilized economy.4, the biomass hydrogen energy electric generation system is convenient, flexible, be convenient to be arranged in around the user, raw material is collected the expensive of accumulating aspect in having avoided that biomass resource is extensive and utilizing, be suitable for setting up distributed energy resource system, be suitable for vast rural area, forest zone, outlying mountain area, pastoral area, island and some away from electrical network and the energy development of enriching the biomass resource area arranged.
Embodiment
The biomass materials such as stalk of water content 10-20% are carried out quantitatively sending into pyrolysis reactor after the broken preliminary treatment.Pyrolytic reaction under the secluding air condition takes place in biomass material in the course of conveying in pyrolysis apparatus, pyrolysis temperature 550-650 ℃, the pyrolytic reaction time was at least 5 minutes, also correspondingly regulated the regulation and control of the load realization pyrolysis reaction temperature of Smoke-heating device by monitor temperature.After the pyrolysis, biomass material is converted into gas phase and solid product, comprises the macromolecule hydrocarbon that is condensed into liquid under the normal temperature such as hydrogen, carbon monoxide, carbon dioxide, methane under the normal temperature such as incoagulable gas and tar in the vapour-phase pyrolysis product.The pyrolysis fundamental reaction is:
The pyrolysis apparatus rear portion, the pyrolysis solid product separates with gas-phase product.Gas-phase product enters deduster, and the granule foreign in the gas-phase product is removed.Solid product enters the carbon residue collecting box, and sends into the carbon residue burner by conveying mechanism, realizes good combustion by adjusting air-supply, obtains the high-temperature flue gas about 1000 ℃, sends into energy consumption equipments such as pyrolysis apparatus, cracker, CO converter.The carbon residue combustion process only produces the biomass ash that accounts for biomass material quality 5-15%, can be used as also field of fertilizer.
Pyrolysis gas-phase product after the dedusting enters cracker, cracking reaction takes place under dolomite catalyst and overheated steam (more than 140 ℃) effect, the heavy hydrocarbons component (tar) that molecular weight is bigger is cracked into lighter products, and in conjunction with the steam reformation of pyrolysis product, realize the conversion of hydro carbons such as methane, eliminate the heavy hydrocarbons component, increase hydrogen content in gas yield and the gas.800-950 ℃ of cracking reaction temperature, reaction time was at least 3 seconds, by temperature monitoring and corresponding regulate the regulation and control that the Smoke-heating device load is realized the cracking reaction temperature, the make a living 10-30% of material mass of the addition of steam, and adjust according to the biomass material characteristic.The key reaction that cracking process takes place is:
CO+H
2O0 H
2+ CO
3The carbon monodixe conversion reaction
CH
4+ H
2O 3H
2+ CO methane reforming reaction
C+H
2O H
2+ CO water gas reaction
The product gas that comes out from cracker passes through the water-cooled heat reclaim unit, and gas flow temperature is reduced to about 300 ℃, and to satisfy the temperature required level of high temperature filtration and desulfurization, heat? recovery gained hot water can be sent into superheated steam generator.
Product gas about 300 ℃ enters high-temperature filter, and the issuable granule foreign of course of reaction is filtered.Gaseous product after filtering enters devulcanizer, removes the Determination of Trace Sulfur that may contain in the air-flow under 250-350 ℃ of left and right sides temperature and Zinc oxide desulfurizer effect.
Gaseous product after the desulfurization enters the carbon monodixe conversion reactor, adopt water-gas shift reaction catalyst, reaction temperature 300-400 ℃, feed overheated steam more than 140 ℃, and according to gas componant adjustment steam addition, carbon monoxide in the air-flow is converted into hydrogen and carbon dioxide, reduce carbon monoxide content and improve hydrogen output, obtain hydrogen volume content more than 60%, the carbon monoxide volume content is below 3%, the hydrogen-rich combustion gas of methane volume content below 2% can satisfy the needs that molten carbonate fuel cell reacts.The key reaction of this process is: C+H
2O H
2+ CO water gas reaction
300-400 ℃ hydrogen-rich combustion gas is sent into the anode of molten carbonate fuel cell, air and carbon dioxide mix pneumatic transmission are gone into fuel battery negative pole, about 600-650 ℃, with the fused carbonate is electrolyte, electrochemical process by fuel cell system inside produces electric power, externally exports electric energy.The energy conversion efficiency of fuel gas generation part is more than 50%, and far away surpassing in burning, the gasifying electricity generation utilizes internal combustion engine, steam turbine, gas turbine generally to be no more than 40% generating efficiency.The key reaction of this process is:
Negative electrode: O
2+ 2CO
2+ 4e
-→ 2CO
3 3
Anode: 2H
2+ 2CO
3 2-→ 2CO
2+ 2H
2O+4e
-
Overall reaction: O
2+ 2H
2→ 2H
2O
The high-temperature tail gas of fuel cell (more than 500 ℃) can be by discharging behind the water-cooled waste-heat recovery device recovery section heat energy, and the hot water of generation can be sent into superheated steam generator to produce superheated steam, perhaps provides part hot water to realize the heat supply purposes.
Description of drawings
Fig. 1 is the biomass hydrogen energy electric generation method FB(flow block).
Claims (6)
1, a kind of biomass hydrogen energy electric generation method is characterized in that by biomass thermal chemistry hydrogen production process biomass being converted into the rich, high temperature Hydrogen fuel of cleaning, and the rich, high temperature Hydrogen fuel need not purified and be directly applied to molten carbonate fuel cell and realize electrical production.
2, biomass hydrogen energy electric generation method according to claim 1 is characterized in that described biomass thermal chemistry hydrogen production process is to make biomass material pyrolysis under 550-650 ℃ of temperature be converted into gas-phase product and carbon residue under the secluding air condition; Shift out reaction system after carbon residue separated from gas-phase product, obtain the energy loss that heat is used for the biomass hydrogen energy electric generation process by burning; The gas-phase product that produces after the pyrolysis is carried out cracking under 800-950 ℃ of condition, and realize the cracking of gas-phase product in conjunction with the effect of dolomite catalyst and steam, reform, the heavy hydrocarbons component cracking that molecular weight is bigger, be restructured as hydrogen, methane and other light hydrocarbons, eliminate tar and reduce hydrocarbon content such as methane, improve the content and the output of hydrogen in the gaseous product, preparation hydrogen volume content reaches the hydrogen-rich gaseous product of 30%-55%, be cooled to 300 ℃, carry out hot filtration and desulfurization, after removing impurity gaseous product is sent into the carbon monodixe conversion reactor, under carbon monoxide transformation catalyst and steam effect, carbon monoxide further is converted into the rich, high temperature Hydrogen fuel.
3, biomass hydrogen energy electric generation method according to claim 2 is characterized in that described biomass thermal chemistry hydrogen production process is that the biomass material of water content 10%-20% is quantitatively sent into pyrolysis reactor after fragmentation; Biomass material in pyrolysis reactor inside by helix transporting device when carry at the pyrolysis reactor rear portion by indirect, biomass pyrolytic under the secluding air condition takes place in the course of conveying, the pyrolytic reaction actuator temperature is regulated by outside flue gas heating and control device, pyrolysis temperature 550-650 ℃, the pyrolytic reaction time was at least 5 minutes, the composition volatile matter that accounts for biomass material weight 60-75% separated out becomes gas-phase product, comprises hydrogen in this gas-phase product, carbon monoxide, carbon dioxide, be condensed into the macromolecular compound of liquid under the normal temperature such as methane under the normal temperature such as incoagulable gas and tar;
The pyrolysis reactor rear portion, the biomass pyrolytic solid product separates with gas-phase product; Gas-phase product enters deduster, and the granule foreign in the gas-phase product is removed; Solid product enters the carbon residue collecting box, and sends into the carbon residue burner by conveying mechanism, realizes good combustion by adjusting air-supply, obtains high-temperature flue gas, is used to keep pyrolytic reaction, cracking reaction portion temperature level and produces overheated steam institute energy requirement;
Pyrolysis gas-phase product after the dedusting enters cracking reactor, filling dolomite catalyst in the cracking reactor, and feed 140 ℃ overheated steam, and the make a living 10-30% of material mass of the addition of steam, and adjust according to the biomass material characteristic; The temperature of utilizing flue gas heating and control device to regulate cracker, under temperature 800-950 ℃ condition, carry out cracking, reaction time was at least 3 seconds, the heavy hydrocarbons component coke tar cracking that molecular weight is bigger is hydrogen, methane and other light hydrocarbons, and in conjunction with the steam reformation of pyrolysis product, realizes the conversion of hydro carbons such as methane, improve hydrogen output, eliminate tar, increase the hydrogen content of gas yield and gas, obtain hydrogen-rich gaseous product.
4, biomass hydrogen energy electric generation method according to claim 3 is characterized in that described pyrolysis temperature is 600-650 ℃, and cracking temperature is 850-900 ℃.
5, biomass hydrogen energy electric generation method according to claim 3 is characterized in that the described pyrolytic reaction time is 6-8 minute, and the cracking reaction time is 3-6 second.
6, biomass hydrogen energy electric generation method according to claim 3, it is characterized in that the described hydrogen-rich combustion gas temperature of molten carbonate fuel cell that enters is at 300-400 ℃, hydrogen volume content is more than 60% in the combustion gas, and the carbon monoxide volume content is below 3%, and the methane volume content is below 2%.
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