CN104194834B - A kind of biomass pyrolytic and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing - Google Patents
A kind of biomass pyrolytic and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing Download PDFInfo
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- CN104194834B CN104194834B CN201410332169.7A CN201410332169A CN104194834B CN 104194834 B CN104194834 B CN 104194834B CN 201410332169 A CN201410332169 A CN 201410332169A CN 104194834 B CN104194834 B CN 104194834B
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Abstract
The invention provides a kind of biomass pyrolytic and utilize the device of pyrolysis gas of biomass hydrogen manufacturing, this device mainly comprises biomass pyrogenation gasification device and hydrogen production of chemical chain reaction unit, and described hydrogen production of chemical chain reaction unit mainly utilizes the NiFe with spinel structure2O4The good steam alternation response of the carrier of oxygen and pyrolysis gas of biomass, thus prepare pure hydrogen. Hydrogen production of chemical chain reaction unit is provided with the section of multiple different cross section diameters, for adjustments of gas velocity of liquid assets, thereby controls speed and the completeness of reacting. That device of the present invention has is simple to operate, energy consumption is low, and the advantages such as the tar content of biomass processes is low, hydrogen production process production biological carbon simultaneously material have realized the object that the high-efficiency cleaning of living beings transforms.
Description
Technical field
The present invention relates to living resources and re-use the technical field of producing clean energy resource, particularly relate to a kind of biomass thermalSeparate and utilize the device of pyrolysis gas of biomass hydrogen manufacturing.
Background technology
Hydrogen is a kind of clean and effective, the eco-friendly desirable energy, and hydrogen use in the world constantly expands.The source of tradition hydrogen is mainly to prepare from fossil fuel, and production process can produce dust, nitrogen sulphur gas etc., causes environmentPollute.
Utilizing biomass-making is to have one of scientific research project of Research Prospects at present most for hydrogen. Living beings are reproducible environmental protection moneySource, source is abundant. Utilize biomass hydrogen preparation can greatly reduce the secondary pollution that current living beings irrational utilization brings,Realize CO2Near-zero release, be conducive to improve problem of environmental pollution, conservation of nature environment, promotes mankind sustainable developmentExhibition.
The more biomass pyrogenation gasification hydrogen producing technology of current research be living beings at gasifying medium as air, steam, pureUnder participating in, oxygen etc. produce hydrogeneous fuel gas through gasification, then through reformation, purification, separation, purification hydrogen making, gasified reverseAnswer device to be generally fixed bed and fluidized-bed reactor. First produce although this that hydrogen purifies again, the technique of separating-purifying and skillArt route can be realized biomass pyrolytic hydrogen manufacturing, as postgraduate's material under excess oxygen such as turnS of Hawaii, America universityThe hydrogen manufacturing of fluid bed steam gasification, obtains hydrogen output 128g/kg living beings, the highest the consisting of of deduction inert gas hydrogen57.4%, domestic Chinese Academy of Sciences Guangzhou Energy Research Institute, the units such as Chinese University of Science and Technology, Southeast China University are also from theoretical and experimentUpper this process route is studied, has confirmed its feasibility, but this technical scheme adds reformations, purification, separation because of needThe links such as purification make complex process, and energy consumption is higher, have greatly raised hydrogen manufacturing cost, and hydrogen making purity is lower,Tar content is relative also higher, and a kind of good biomass-making hydrogen production device can not only be realized living beings reforming hydrogen producing technology roadLine, also should be taken into account energy consumption, hydrogen manufacturing cost, hydrogen manufacturing purity, the tar content of device and installs operability etc.
Summary of the invention
The object of the invention is to overcome the shortcoming existing in existing biomass pyrogenation gasification device for producing hydrogen, provide a kind of novelThe reaction unit of biomass pyrogenation gasification hydrogen manufacturing, the hydrogen purity of producing approaches 100%, and does not need complicated purificationSeparating technology.
In order to achieve the above object, the present invention is achieved by the following technical solutions:
Biomass pyrolytic and utilize the device of pyrolysis gas of biomass hydrogen manufacturing, comprising: biomass pyrolytic is generated to living beingsThe biomass pyrogenation gasification device of pyrolysis gas, utilize the pyrolysis gas of biomass that generates in described biomass pyrogenation gasification device andSteam is alternately prepared the hydrogen production of chemical chain reaction unit of hydrogen with carrier of oxygen generation redox reaction; Described biomass thermalSeparating gasification installation is connected by pyrolysis gas carrier pipe with hydrogen production of chemical chain reaction unit;
Described hydrogen production of chemical chain reaction unit comprises the first section, the second section and the 3rd section, and the second section is placed in firstBetween section and the 3rd section, the diameter of section of the first section and the 3rd section is all greater than the second section; Described the first sectionFor pyrolysis gas distributing section, described the first section is provided with reaction gas inlet, and biomass pyrogenation gasification device passes through pyrolysis gasCarrier pipe is communicated with described reaction gas inlet; Described the second section is redox reaction generation section, and the carrier of oxygen is located at instituteState in the second section; Described the 3rd section is air-flow buffer section, is provided with gas delivery port.
The present invention utilizes biomass pyrogenation gasification device that biomass pyrogenation gasification is generated to pyrolysis gas of biomass, by described lifeMaterial pyrolysis gas is introduced carrier of oxygen generation redox reaction in hydrogen production of chemical chain reaction unit and wherein, and the carrier of oxygen is gone backFormer; Then stop passing into pyrolysis gas of biomass, reacting gas is switched to steam, the carrier of oxygen under reducing conditionWith the high-temperature vapor generation hydrogen that reacts; Tail gas in hydrogen production of chemical chain reaction unit obtain pure hydrogen after coolingGas.
In practical operation, pyrolysis gas of biomass and steam are all incorporated into hydrogen production of chemical chain reaction unit from the first sectionIn, the reaction gas inlet of described the first section is also communicated with external source gas inlet pipe. For pyrolysis gas of biomass and water steamingBetween two kinds of reacting gas of gas, can there is not string mixed, after pyrolysis gas of biomass stops passing into, first pass into inert gas, thenPass into steam, described inert gas and steam all can pass through by external source gas inlet pipe.
Preferably, the described carrier of oxygen is the NiFe with spinel structure2O4。
Preferably, the operating temperature of described hydrogen production of chemical chain reaction unit is 800～1000 DEG C.
Preferably, in described the first section, be also provided with cloth wind discharge device; Described cloth wind discharge device comprises: be arranged onAir distribution plate in one section and be arranged on drainage conduit and the high-temperature ball valve of air distribution plate bottom.
Preferably, described biomass pyrogenation gasification device comprises: biomass pyrogenation gasification reactor, be arranged on biomass thermalSeparate charging aperture and safety valve on gasification reactor, be placed in biomass pyrogenation gasification reactor cavity and by pyrolysis gas of biomassChange middle deflection plate that reactor is separated into two chambers, be arranged on the ash exhauster of biomass pyrogenation gasification reactor bottomWith ash bucket, be opened on the pyrolysis gas outlet of biomass pyrogenation gasification reactor; Described pyrolysis gas outlet is through pyrolysis gas efferent ductBe connected with the first section of hydrogen production of chemical chain reaction unit. Preferably, the work of described biomass pyrogenation gasification reactorTemperature is 800～850 DEG C.
Preferably, the charging aperture of biomass pyrogenation gasification device is provided with screw type propeller.
Preferably, described hydrogen production of chemical chain reaction unit be connected with by described hydrogen production of chemical chain reaction unit, generate gas withThe gas-solid separating device that solid impurity separates. Described gas-solid separating device is cyclone separator, and described cyclone separator is through connectingTaking over road is connected with the gas delivery port of hydrogen production of chemical chain reaction unit.
Conventionally under stronger air-flow, the tail gas in described hydrogen production of chemical chain reaction unit can be mingled with the short grained carrier of oxygen,Gas-solid separating device is for separating tail gas, by isolated returning to of the carrier of oxygen with the granule carrier of oxygen being mingled withLearn in chain hydrogen making reaction device and utilize.
That device of the present invention has is simple to operate, energy consumption is low, and the tar content of biomass processes is low, hydrogen production process is all rightThe advantages such as the material of production biological carbon simultaneously, realized living beings high-efficiency cleaning transform object.
Brief description of the drawings
Fig. 1 is the structural representation of the embodiment of the present invention;
Reference numeral: 1-charging aperture; 2-safety valve; 3-biomass pyrogenation gasification reactor; Deflection plate in the middle of 4-; 5-rowApparatus for ash; 6-ash bucket; 7-pyrolysis gas outlet; 8-screw type propeller; 9-pyrolysis gas carrier pipe; The input of 10-external source gasPipe; 11-gas sample mouth; 12-reaction gas inlet; 13-the first section; 14-the second section; 15-the 3rd section; 16-Gas delivery port; 17-cyclone separator; 18-generates gas efferent duct; 19-air distribution plate; 20-drainage conduit; 21-high-temperature ball valve.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described further, but the invention is not restricted to following examples:
Embodiment 1
As shown in Figure 1, a kind of biomass pyrolytic and utilize the device of pyrolysis gas of biomass hydrogen manufacturing, comprises pyrolysis gas of biomassGasifying device, hydrogen production of chemical chain reaction unit and gas-solid separating device.
Biomass pyrogenation gasification device comprises: biomass pyrogenation gasification reactor 3, be arranged on biomass pyrogenation gasification reactionCharging aperture 1 on device 3 and safety valve 2, be placed in biomass pyrogenation gasification reactor 3 chambeies and by biomass pyrogenation gasificationReactor 3 be separated into two chambers middle deflection plate 4, be arranged on the ash discharge of biomass pyrogenation gasification reactor 3 bottomsDevice 5 and ash bucket 6, be opened on the pyrolysis gas outlet 7 of biomass pyrogenation gasification reactor 3. Near charging aperture 1, establishThere is screw type propeller 8. Venting one's spleen, outlet is provided with gas sample mouth 11 on 7.
Hydrogen production of chemical chain reaction unit includes the first section 13, the second section 14 and the 3rd section 15. The first section13 is pyrolysis gas distributing section, and the first section 13 is provided with reaction gas inlet 12; The second section 14 is that redox is anti-Should there is section, in the second section 14, be provided with the NiFe with spinel structure2O4The carrier of oxygen; The 3rd section 15 is gasStreambuf section, the 3rd section 15 is provided with gas delivery port 16. Wherein the second section 14 be placed in the first section 13 withBetween the 3rd section 15, the diameter of section of the first section 13 and the 3rd section 15 is all greater than the second section 14.
Wherein, in the first section 13, be also provided with cloth wind discharge device. Described cloth wind discharge device comprises: be arranged onCone shaped distributor 19 in one section and be arranged on drainage conduit 20 and the high-temperature ball valve 21 of cone shaped distributor bottom.
Biomass pyrogenation gasification device and hydrogen production of chemical chain reaction unit are by being communicated in pyrolysis gas outlet 7 and reacting gasPyrolysis gas carrier pipe 9 between entrance 12 is realized ventilation. On reaction gas inlet 12, be also connected with the input of external source gasPipe 10, for being incorporated into hydrogen production of chemical chain reaction unit by gases such as steam. Pyrolysis gas carrier pipe 9, external source gasInput pipe 10 is connected by triple valve with reaction gas inlet 12.
Gas-solid separating device mainly comprises cyclone separator 17. Cyclone separator 17 is anti-through connecting pipe and hydrogen production of chemical chainThe gas delivery port 16 that should install is connected. It is defeated that cyclone separator 17 is also provided with the generation gas being connected with gas quench systemGo out pipe 18.
In above-mentioned reaction unit, the operating temperature of hydrogen production of chemical chain reaction unit is 800～1000 DEG C; Pyrolysis gas of biomassThe operating temperature of changing reactor 3 is 800～850 DEG C.
Embodiment 2:
Choose spinel-type NiFe2O4For carrier of oxygen material, after processing, make particle diameter 40-80 order carrier of oxygen particle, putEnter (addition 150-300g) in hydrogen production of chemical chain reaction system 14, when operation, open reactor external heat system,Set two reactor reaction temperature, biomass pyrolysis reactor 3 operating temperatures are 800 DEG C, hydrogen production of chemical chain reactor 14Operating temperature is 800 DEG C, and two reactor operating pressures are pressure-fired, opens and connects two pipe reactor ball valves 10, opensTwo reactor inert carrier gases 11, start to replace two reactor air. Unit temp all reaches after setting value, opens feed binBalance Air (20ml/min), starts charging, and living beings enter biomass pyrogenation gasification system under feeding screw 1 promotes3 carry out pyrolytic gasification (installing raw materials used can be the biomass materials such as stalk, wood chip, rice husk, bagasse, thisIn bright embodiment, test feed rate, 200g/h taking pine powder as representative), generate H2、CO、CH4、CO2Deng gas, pyrolysis reactor is provided with gas sampling mouth 7, and sampling should be carried out for about 5min, carries out composition divide by gas-chromatographyAnalyse; The biological flue gas generating is introduced into hydrogen production of chemical chain reactor 14 through connecting pipe 7,9 and enters with the carrier of oxygen whereinRow redox reaction, the carrier of oxygen is reduced into as FeO, Ni or Fe, generates tail gas emptying after cyclone 16 separates,The carrier of oxygen separating enters lower seal chamber, returns to afterwards hydrogen generating system, after oxygen carrier is reduced completely (approximately 40～60min), stop living beings charging 1, close biological fuel gas ball valve 10, open the inertia of hydrogen production of chemical chain reactorCarrier gas 10, the biological flue gas of complete reaction (flow is 60ml/min, approximately 10～20min) not in displacement hydrogen generating system 14,After being replaced, the steam 10 of fetching boiling water (steam flow 50ml/min, 120 DEG C), in the oxygen carrier of reducing conditionBe oxidized by high-temperature vapor, steam pyrolysis produces H2, after separating and condensing, approximately sampling should be carried out for 3～5min, logicalCross gas-chromatography analysis, H2Purity exceedes 99%, CO concentration and is less than 0.05%, CO2Concentration is less than 0.5%,CH4 concentration is less than 0.01%, tar do not detected in gas, after carrier of oxygen complete reaction (about 20min), closesClose steam 10, open inert gas valve 10 metathesis reactor residual gas (60ml/min, approximately 10～20min),After being replaced, passing into air 10 (60ml/min) carrier of oxygen in hydrogen generating system is further oxidized, when oxidationBetween be about 10min, treat that carrier of oxygen oxidation is complete, test once and has circulated, so alternately pass into living beings, indifferent gasBody, steam, reaction continues to loop. Result of implementation is as follows:
Table 1 utilizes material pyrolysis and pyrolysis gas chemistry chain device for producing hydrogen to prepare condition and the result of hydrogen
Embodiment 3:
Utilize the equipment of embodiment 1, according to the technological process of executing example 2, prepare hydrogen by the implementation condition of table 2, and logicalCross gas-chromatography and analyze generating gas, result is as follows:
Table 2 utilizes material pyrolysis and pyrolysis gas chemistry chain device for producing hydrogen to prepare condition and the result of hydrogen
Embodiment 4:
Utilize the equipment of embodiment 1, according to the technological process of executing example 2, prepare hydrogen by the implementation condition of table 3, and logicalCross gas-chromatography and analyze generating gas, result is as follows:
Table 3 utilizes material pyrolysis and pyrolysis gas chemistry chain device for producing hydrogen to prepare condition and the result of hydrogen
Claims (9)
1. biomass pyrolytic and biomass pyrogenation gasification are learned a device for chain hydrogen manufacturing, it is characterized in that comprising: by biologyMatter pyrolysis generate pyrolysis gas of biomass biomass pyrogenation gasification device, utilize in described biomass pyrogenation gasification device and generatePyrolysis gas of biomass and the steam hydrogen production of chemical chain of alternately preparing hydrogen with carrier of oxygen generation redox reaction reactDevice; Described biomass pyrogenation gasification device is connected by pyrolysis gas carrier pipe with hydrogen production of chemical chain reaction unit;
Described hydrogen production of chemical chain reaction unit comprises the first section, the second section and the 3rd section, and the second section is placed in firstBetween section and the 3rd section, the diameter of section of the first section and the 3rd section is all greater than the second section; Described the first sectionFor pyrolysis gas distributing section, described the first section is provided with reaction gas inlet, and biomass pyrogenation gasification device passes through pyrolysis gasCarrier pipe is communicated with described reaction gas inlet; Described the second section is redox reaction generation section, and the carrier of oxygen is located at instituteState in the second section; Described the 3rd section is air-flow buffer section, is provided with gas delivery port;
Described biomass pyrogenation gasification device comprises: biomass pyrogenation gasification reactor, to be arranged on biomass pyrogenation gasification anti-Answer charging aperture and safety valve on device, be placed in biomass pyrogenation gasification reactor cavity and by biomass pyrogenation gasification reactorBe separated into the middle deflection plate of two chambers, the ash exhauster that is arranged on biomass pyrogenation gasification reactor bottom and ash bucket,Be opened on the pyrolysis gas outlet of biomass pyrogenation gasification reactor; Described pyrolysis gas outlet is through pyrolysis gas efferent duct and chemical chainThe first section of hydrogen making reaction device is connected.
2. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, the described carrier of oxygen is the NiFe with spinel structure2O4。
3. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, the operating temperature of described hydrogen production of chemical chain reaction unit is 800～1000 DEG C.
4. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, described reaction gas inlet is also communicated with external source gas inlet pipe, is also provided with cloth wind row in described the first sectionMaterials device.
5. a kind of biomass pyrolytic according to claim 4 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, described cloth wind discharge device comprises: be arranged on the air distribution plate in the first section and be arranged on air distribution plate bottomDrainage conduit and high-temperature ball valve.
6. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, the operating temperature of described biomass pyrogenation gasification reactor is 800～850 DEG C.
7. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, the charging aperture of described biomass pyrogenation gasification device is provided with screw type propeller.
8. a kind of biomass pyrolytic according to claim 1 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, described hydrogen production of chemical chain reaction unit be also connected with by described hydrogen production of chemical chain reaction unit, generate gas withThe gas-solid separating device that solid impurity separates.
9. a kind of biomass pyrolytic according to claim 8 and biomass pyrogenation gasification are learned the device of chain hydrogen manufacturing, itsBe characterised in that, described gas-solid separating device is cyclone separator, and described cyclone separator is through connecting pipe and hydrogen production of chemical chainThe gas delivery port of reaction unit is connected.
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| CN112827494A (en) * | 2020-12-31 | 2021-05-25 | 华中科技大学 | Nickel-iron composite oxygen carrier and preparation method and application thereof |
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