CN104194834A - Device for biomass pyrolysis and chemical-looping hydrogen production by utilizing biomass pyrolysis gas - Google Patents
Device for biomass pyrolysis and chemical-looping hydrogen production by utilizing biomass pyrolysis gas Download PDFInfo
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- CN104194834A CN104194834A CN201410332169.7A CN201410332169A CN104194834A CN 104194834 A CN104194834 A CN 104194834A CN 201410332169 A CN201410332169 A CN 201410332169A CN 104194834 A CN104194834 A CN 104194834A
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Abstract
The invention provides a device for biomass pyrolysis and chemical-looping hydrogen production by utilizing biomass pyrolysis gas. The device mainly comprises a biomass pyrolysis gasification device and a chemical-looping hydrogen production reaction device, wherein in the chemical-looping hydrogen production reaction device, a NiFe2O4 oxygen carrier with a spinel structure is mainly utilized to alternatively react with the biomass pyrolysis gas and water vapor, so that pure hydrogen is prepared. The chemical-looping hydrogen production reaction device is provided with multiple zones of different section diameters, which are used for regulating the gas circulation speed, so that the rate and completeness of the reaction are controlled. The device disclosed by the invention has the advantages that the device is easy to operate and low in energy consumption, tar subjected to biomass treatment is low in content, biochar materials can be simultaneously produced in the hydrogen production process and the like, and the aim of efficiently and cleanly converting the biomass is achieved.
Description
Technical field
The present invention relates to Biological resources and re-use to produce the technical field of clean energy, particularly relate to a kind of biomass pyrolytic 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 environmental pollution.
Utilizing biomass-making is to have one of scientific research project of Research Prospects at present most for hydrogen.Biomass are reproducible environmental protection resources, and source is abundant.Utilize biomass hydrogen preparation can greatly reduce the secondary pollution that current biomass irrational utilization brings, realize CO
2near zero release, be conducive to improve problem of environmental pollution, conservation of nature environment, promotes human kind sustainable development.
The more biomass pyrogenation gasification hydrogen producing technology of current research is that biomass produce hydrogeneous fuel gas through gasification under gasifying medium participates in as air, water vapour, pure oxygen etc., through reformation, purification, separated, purification hydrogen making, gasifying reactor is generally fixed bed and fluidized-bed reactor again.Although this, first producing hydrogen purifies again, the technique of separating-purifying and technological line can be realized biomass pyrolytic hydrogen manufacturing, as turn S of Hawaii, America university etc. studies biomass fluid bed steam gasification hydrogen manufacturing under excess oxygen, obtain hydrogen output 128g/kg biomass, deduction rare gas element hydrogen is the highest consists of 57.4%, domestic Chinese Academy of Sciences Guangzhou Energy Research Institute, Chinese University of Science and Technology, the units such as Southeast China University are also from theoretical and experimentally this operational path is studied, confirmed its feasibility, but this technical scheme adds reformation because of need, purify, the links such as separating-purifying make complex process, energy consumption is higher, greatly raised hydrogen manufacturing cost, and hydrogen making purity is lower, tar content is relative also higher, a kind of good biomass-making hydrogen production device can not only be realized biomass reforming hydrogen producing technology route, also should be taken into account the energy consumption of device, hydrogen manufacturing cost, hydrogen manufacturing purity, tar content and device 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, a kind of reaction unit of novel biomass pyrogenation gasification hydrogen manufacturing is provided, the hydrogen purity of producing approaches 100%, and does not need complicated purification separating 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: by biomass pyrolytic generate pyrolysis gas of biomass biomass pyrogenation gasification device, utilize the pyrolysis gas of biomass and the water vapour that in described biomass pyrogenation gasification device, generate alternately to prepare the hydrogen production of chemical chain reaction unit of hydrogen with oxygen carrier generation redox reaction; Described biomass pyrogenation gasification device is connected by pyrolysis gas transfer lime 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 between the first section and the 3rd section, and the diameter of section of the first section and the 3rd section is all greater than the second section; Described the first section is pyrolysis gas distributing section, and described the first section is provided with reaction gas inlet, and biomass pyrogenation gasification device is communicated with described reaction gas inlet by pyrolysis gas transfer lime; Described the second section is redox reaction generation section, and oxygen carrier is located in described 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, and described pyrolysis gas of biomass is introduced to oxygen carrier generation redox reaction in hydrogen production of chemical chain reaction unit and wherein, and oxygen carrier is reduced; Then stop passing into pyrolysis gas of biomass, reactant gases is switched to water vapour, the oxygen carrier under reduced state and the high-temperature vapor generation hydrogen that reacts; Tail gas in hydrogen production of chemical chain reaction unit obtain pure hydrogen after cooling.
In actually operating, pyrolysis gas of biomass and water vapour are all incorporated into hydrogen production of chemical chain reaction unit from the first section, and the reaction gas inlet of described the first section is also communicated with external source gas inlet pipe.Mixed in order to there is not string between pyrolysis gas of biomass and two kinds of reactant gasess of water vapour, after pyrolysis gas of biomass stops passing into, first pass into rare gas element, then pass into water vapour, described rare gas element and water vapour all can pass through by external source gas inlet pipe.
Preferably, described oxygen carrier is the NiFe with spinel structure
2o
4.
Preferably, the working temperature of described hydrogen production of chemical chain reaction unit is 800～1000 ℃.
Preferably, in described the first section, be also provided with cloth wind discharge device; Described cloth wind discharge device comprises: the drainage conduit and the high-temperature ball valve that are arranged on the air distribution plate in the first section and are arranged on air distribution plate bottom.
Preferably, described biomass pyrogenation gasification device comprises: biomass pyrogenation gasification reactor, be arranged on opening for feed and safety valve on biomass pyrogenation gasification reactor, be placed in biomass pyrogenation gasification reactor cavity and biomass pyrogenation gasification reactor is separated into the middle traverse baffle of two chambers, the ash exhauster that is arranged on biomass pyrogenation gasification reactor bottom and ash bucket, is opened on the pyrolysis gas outlet of biomass pyrogenation gasification reactor; Described pyrolysis gas outlet is connected with the first section of hydrogen production of chemical chain reaction unit through pyrolysis gas output tube.Preferably, the working temperature of described biomass pyrogenation gasification reactor is 800～850 ℃.
Preferably, the opening for feed of biomass pyrogenation gasification device is provided with screw type thruster.
Preferably, described hydrogen production of chemical chain reaction unit is connected with and will in described hydrogen production of chemical chain reaction unit, generates the gas gas-solid separating device separated with solid impurity.Described gas-solid separating device is cyclonic separator, and described cyclonic separator is connected with the gas delivery port of hydrogen production of chemical chain reaction unit through connecting tube.
Conventionally under stronger air-flow, tail gas in described hydrogen production of chemical chain reaction unit can be mingled with short grained oxygen carrier, gas-solid separating device, for tail gas is separated with the small-particle oxygen carrier being mingled with, return to isolated oxygen carrier in hydrogen production of chemical chain reaction unit and utilizes.
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 biomass transforms.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention;
Reference numeral: 1-opening for feed; 2-safety valve; 3-biomass pyrogenation gasification reactor; Traverse baffle in the middle of 4-; 5-ash exhauster; 6-ash bucket; 7-pyrolysis gas outlet; 8-screw type thruster; 9-pyrolysis gas transfer lime; 10-external source gas inlet pipe; 11-gas sampling mouth; 12-reaction gas inlet; 13-the first section; 14-the second section; 15-the 3rd section; 16-gas delivery port; 17-cyclonic separator; 18-generates gas output tube; 19-air distribution plate; 20-drainage conduit; 21-high-temperature ball valve.
Embodiment
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 biomass pyrogenation gasification 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 opening for feed 1 and safety valve 2 on biomass pyrogenation gasification reactor 3, be placed in biomass pyrogenation gasification reactor 3 chambeies and biomass pyrogenation gasification reactor 3 is separated into the middle traverse baffle 4 of two chambers, the ash exhauster 5 that is arranged on biomass pyrogenation gasification reactor 3 bottoms and ash bucket 6, is opened on the pyrolysis gas outlet 7 of biomass pyrogenation gasification reactor 3.Near opening for feed 1, be provided with screw type thruster 8.In the outlet 7 of venting one's spleen, be provided with gas sampling mouth 11.
Hydrogen production of chemical chain reaction unit includes the first section 13, the second section 14 and the 3rd section 15.The first section 13 is pyrolysis gas distributing section, and the first section 13 is provided with reaction gas inlet 12; The second section 14 is redox reaction generation section, in the second section 14, is provided with the NiFe with spinel structure
2o
4oxygen carrier; The 3rd section 15 is air-flow buffer section, and the 3rd section 15 is provided with gas delivery port 16.Wherein the second section 14 is placed between the first section 13 and the 3rd section 15, and 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: the drainage conduit 20 and the high-temperature ball valve 21 that are arranged on the cone shaped distributor 19 in the first section and are arranged on cone shaped distributor bottom.
Biomass pyrogenation gasification device and hydrogen production of chemical chain reaction unit are realized ventilation by the pyrolysis gas transfer lime 9 being communicated between pyrolysis gas outlet 7 and reaction gas inlet 12.On reaction gas inlet 12, be also connected with external source gas inlet pipe 10, for the gases such as water vapour are incorporated into hydrogen production of chemical chain reaction unit.Pyrolysis gas transfer lime 9, external source gas inlet pipe 10 and reaction gas inlet 12 are connected by T-valve.
Gas-solid separating device mainly comprises cyclonic separator 17.Cyclonic separator 17 is connected with the gas delivery port 16 of hydrogen production of chemical chain reaction unit through connecting tube.Cyclonic separator 17 is also provided with the generation gas output tube 18 being connected with gas quench system.
In above-mentioned reaction unit, the working temperature of hydrogen production of chemical chain reaction unit is 800～1000 ℃; The working temperature of biomass pyrogenation gasification reactor 3 is 800～850 ℃.
Embodiment 2:
Choose spinel type NiFe
2o
4for oxygen carrier material, after processing, make particle diameter 40-80 order oxygen carrier particle, put into hydrogen production of chemical chain reactive system 14 (add-on 150-300g), during operation, open reactor external heat system, set two reactor reaction temperature, biomass pyrolysis reactor 3 working temperatures are 800 ℃, hydrogen production of chemical chain reactor 14 working temperatures are 800 ℃, two reactor operating pressure are pressure-fired, open and connect two pipe reactor ball valves 10, open two reactor inert carrier gases 11, start to replace two reactor air.Unit temp all reaches after set(ting)value, open feed bin Balance Air (20ml/min), start charging, biomass enter biomass pyrogenation gasification system 3 and carry out pyrolytic gasification (installing raw materials used can be the biomass materials such as stalk, wood chip, rice husk, bagasse under feeding screw 1 promotes, the pine powder of take in the embodiment of the present invention is tested as representative, feeding rate, 200g/h), generates H
2, CO, CH
4, CO
2deng gas, pyrolysis reactor is provided with gas sampling mouth 7, and about 5min once sampling, carries out composition analysis by gas-chromatography, the biological flue gas generating is through connecting tube 7, 9 are introduced into hydrogen production of chemical chain reactor 14 carries out redox reaction with oxygen carrier wherein, oxygen carrier is reduced into as FeO, Ni or Fe, generate tail gas emptying after cyclone 16 separation, separated oxygen carrier enters lower seal chamber, return to afterwards hydrogen generating system, after oxygen carrier is reduced completely (approximately 40～60min), stop biomass charging 1, close biological fuel gas ball valve 10, open the inert carrier gas 10 of hydrogen production of chemical chain reactor, displacement hydrogen generating system 14 in not the biological flue gas of complete reaction (flow is 60ml/min, about 10～20min), after being replaced, steam 10 (water vapour flow 50ml/min fetches boiling water, 120 ℃), oxygen carrier in reduced state is oxidized by high-temperature vapor, steam cracking produces H
2, after separating and condensing, approximately 3～5min once sampling, analyzes by gas-chromatography, H
2purity surpasses 99%, CO concentration and is less than 0.05%, CO
2concentration is less than 0.5%, CH4 concentration is less than 0.01%, tar in gas, do not detected, after oxygen carrier complete reaction (about 20min), close water vapour 10, open rare gas element valve 10 metathesis reactor entrap bubble (60ml/min, about 10～20min), after being replaced, passing into air 10 (60ml/min) oxygen carrier in hydrogen generating system is further oxidized, oxidization time is about 10min, treat that oxygen carrier oxidation is complete, tested once circulation, so alternately passed into biomass, rare gas element, water vapour, 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 technical process of executing example 2, by the implementation condition of table 2, prepare hydrogen, and analyze generating gas by gas-chromatography, 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 technical process of executing example 2, by the implementation condition of table 3, prepare hydrogen, and analyze generating gas by gas-chromatography, 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 (10)
1. biomass pyrolytic and biomass pyrogenation gasification are learned a device for chain hydrogen manufacturing, it is characterized in that comprising: by biomass pyrolytic generate pyrolysis gas of biomass biomass pyrogenation gasification device, utilize the pyrolysis gas of biomass and the water vapour that in described biomass pyrogenation gasification device, generate alternately to prepare the hydrogen production of chemical chain reaction unit of hydrogen with oxygen carrier generation redox reaction; Described biomass pyrogenation gasification device is connected by pyrolysis gas transfer lime 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 between the first section and the 3rd section, and the diameter of section of the first section and the 3rd section is all greater than the second section; Described the first section is pyrolysis gas distributing section, and described the first section is provided with reaction gas inlet, and biomass pyrogenation gasification device is communicated with described reaction gas inlet by pyrolysis gas transfer lime; Described the second section is redox reaction generation section, and oxygen carrier is located in described the second section; Described the 3rd section is air-flow buffer section, is provided with gas delivery port.
2. device according to claim 1, is characterized in that, described oxygen carrier is the NiFe with spinel structure
2o
4.
3. device according to claim 1, is characterized in that, the working temperature of described hydrogen production of chemical chain reaction unit is 800～1000 ℃.
4. device according to claim 1, is characterized in that, described reaction gas inlet is also communicated with external source gas inlet pipe, is also provided with cloth wind discharge device in described the first section.
5. device according to claim 4, is characterized in that, described cloth wind discharge device comprises: the drainage conduit and the high-temperature ball valve that are arranged on the air distribution plate in the first section and are arranged on air distribution plate bottom.
6. device according to claim 1, it is characterized in that, described biomass pyrogenation gasification device comprises: biomass pyrogenation gasification reactor, be arranged on opening for feed and safety valve on biomass pyrogenation gasification reactor, be placed in biomass pyrogenation gasification reactor cavity and biomass pyrogenation gasification reactor is separated into the middle traverse baffle of two chambers, the ash exhauster that is arranged on biomass pyrogenation gasification reactor bottom and ash bucket, is opened on the pyrolysis gas outlet of biomass pyrogenation gasification reactor; Described pyrolysis gas outlet is connected with the first section of hydrogen production of chemical chain reaction unit through pyrolysis gas output tube.
7. device according to claim 6, is characterized in that, the working temperature of described biomass pyrogenation gasification reactor is 800～850 ℃.
8. device according to claim 6, is characterized in that, the opening for feed of described biomass pyrogenation gasification device is provided with screw type thruster.
9. device according to claim 1, is characterized in that, described hydrogen production of chemical chain reaction unit is also connected with and will in described hydrogen production of chemical chain reaction unit, generates the gas gas-solid separating device separated with solid impurity.
10. device according to claim 9, is characterized in that, described gas-solid separating device is cyclonic separator, and described cyclonic separator is connected with the gas delivery port of hydrogen production of chemical chain reaction unit through connecting tube.
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| CN109282279A (en) * | 2018-09-05 | 2019-01-29 | 东南大学 | A kind of regenerated burning chemistry chains air reactor of reinforcing oxygen carrier oxidating |
| 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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