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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- 239000002028 Biomass Substances 0.000 title claims abstract description 105
- 239000001257 hydrogen Substances 0.000 title claims abstract description 88
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 71
- 238000002309 gasification Methods 0.000 title claims abstract description 51
- 238000000197 pyrolysis Methods 0.000 claims abstract description 111
- 239000007789 gas Substances 0.000 claims abstract description 85
- 239000000126 substance Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 5
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- 239000012495 reaction gas Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000006479 redox reaction Methods 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
本发明提供一种生物质热解及利用生物质热解气制氢的装置，该装置主要包括生物质热解气化装置和化学链制氢反应装置，所述化学链制氢反应装置主要利用具有尖晶石结构的NiFe2O4氧载体与生物质热解气好水蒸气交替反应，从而制备纯净的氢气。化学链制氢反应装置设置有多个不同截面直径的区段，用于调节气体流通速度，从而控制反应的速率和完全性。本发明的装置具有操作简单、能耗低，生物质处理的焦油含量低、制氢过程还可以同时生产生物碳材料等优势，实现了生物质的高效清洁转化的目的。
The invention provides a device for pyrolysis of biomass and hydrogen production using biomass pyrolysis gas. The device mainly includes a biomass pyrolysis gasification device and a chemical chain hydrogen production reaction device. The chemical chain hydrogen production reaction device mainly uses NiFe 2 O 4 oxygen carrier with spinel structure alternately reacts with biomass pyrolysis gas and water vapor to produce pure hydrogen. The chemical chain hydrogen production reaction device is provided with multiple sections with different cross-sectional diameters, which are used to adjust the gas flow rate, thereby controlling the rate and completeness of the reaction. The device of the present invention has the advantages of simple operation, low energy consumption, low tar content in biomass treatment, and simultaneous production of bio-carbon materials in the hydrogen production process, thereby achieving the purpose of efficient and clean conversion of biomass.
Description
技术领域technical field
本发明涉及生物资源重新利用生产清洁能源的技术领域，特别是涉及一种生物质热解及利用生物质热解气制氢的装置。The invention relates to the technical field of reusing biological resources to produce clean energy, in particular to a device for pyrolyzing biomass and utilizing biomass pyrolysis gas to produce hydrogen.
背景技术Background technique
氢是一种清洁高效，环境友好的理想能源，氢在全球范围内的使用正在不断扩大。传统氢的来源主要是从石化燃料中制备，生产过程会产生粉尘、氮硫气体等，造成环境污染。Hydrogen is an ideal energy source that is clean, efficient, and environmentally friendly. The use of hydrogen is expanding worldwide. The traditional source of hydrogen is mainly prepared from fossil fuels, and the production process will produce dust, nitrogen and sulfur gases, etc., causing environmental pollution.
利用生物质制备氢是目前最有研究前景的科研项目之一。生物质是可再生的环保资源，来源丰富。利用生物质制氢可以大大减少目前生物质不合理利用带来的二次污染，实现CO2的近零排放，有利于改善环境污染问题，保护自然环境，促进人类可持续发展。The production of hydrogen from biomass is one of the most promising research projects at present. Biomass is a renewable and environmentally friendly resource with abundant sources. The use of biomass to produce hydrogen can greatly reduce the secondary pollution caused by the current irrational use of biomass, and achieve near-zero emissions of CO2 , which is conducive to improving environmental pollution problems, protecting the natural environment, and promoting sustainable human development.
当前研究较多的生物质热解气化制氢技术是生物质在气化介质如空气、水蒸气、纯氧等参与下经气化产生含氢的燃料气，再经重整、净化、分离、提纯制取氢气，气化反应器一般为固定床和流化床反应器。虽然这种先产生氢气再净化、分离提纯的工艺和技术路线可以实现生物质热解制氢，如美国夏威夷大学turnS等在富氧条件下研究生物质流化床水蒸气气化制氢，获得氢气产量128g/kg生物质，扣除惰性气体氢气最高组成为57.4％，国内中科院广州能源研究所，中国科技大学、东南大学等单位也从理论和实验上对该工艺路线进行了研究，证实了其可行性，但该技术方案因需加重整、净化、分离提纯等环节使得工艺复杂，能耗较高，极大地推高了制氢成本，并且制取氢气纯度较低，焦油含量相对也较高，一种良好的生物质制氢装置不仅能实现生物质重整制氢技术路线，还应考虑到装置的能耗、制氢成本、制氢纯度、焦油含量及装置操作性等。The currently researched biomass pyrolysis gasification hydrogen production technology is that biomass is gasified with the participation of gasification media such as air, water vapor, pure oxygen, etc. to produce hydrogen-containing fuel gas, which is then reformed, purified, and separated. , Purify and produce hydrogen, the gasification reactors are generally fixed bed and fluidized bed reactors. Although this process and technical route of generating hydrogen first and then purifying, separating and purifying can realize hydrogen production by pyrolysis of biomass, such as turnS of the University of Hawaii in the United States, studied the production of hydrogen by steam gasification of material fluidized bed under oxygen-enriched conditions to obtain hydrogen The output is 128g/kg biomass, and the maximum composition of hydrogen after deducting the inert gas is 57.4%. The domestic Guangzhou Institute of Energy Research, Chinese Academy of Sciences, University of Science and Technology of China, Southeast University and other units have also carried out theoretical and experimental research on this process route, confirming its feasibility However, due to the need to increase the steps of reforming, purification, separation and purification, this technical solution makes the process complex and consumes high energy consumption, which greatly increases the cost of hydrogen production, and the purity of hydrogen produced is relatively low, and the tar content is relatively high , a good biomass hydrogen production device can not only realize the technical route of biomass reforming hydrogen production, but also consider the energy consumption of the device, the cost of hydrogen production, the purity of hydrogen production, the tar content and the operability of the device.
发明内容Contents of the invention
本发明的目的在于克服现有生物质热解气化制氢装置中存在的缺点，提供一种新型的生物质热解气化制氢的反应装置，制取的氢气纯度接近100％，且不需要复杂的提纯分离工艺。The purpose of the present invention is to overcome the shortcomings existing in the existing biomass pyrolysis gasification hydrogen production device, to provide a new type of reaction device for biomass pyrolysis gasification hydrogen production, the purity of the produced hydrogen is close to 100%, and there is no Complex purification and separation processes are required.
为了达到上述目的，本发明采用以下技术方案予以实现：In order to achieve the above object, the present invention adopts the following technical solutions to achieve:
一种生物质热解及利用生物质热解气制氢的装置，包括：将生物质热解生成生物质热解气的生物质热解气化装置、利用所述生物质热解气化装置中生成的生物质热解气和水蒸气交替与氧载体发生氧化还原反应制备氢气的化学链制氢反应装置；所述生物质热解气化装置与化学链制氢反应装置通过热解气输送管相连通；A device for pyrolyzing biomass and utilizing biomass pyrolysis gas to produce hydrogen, comprising: a biomass pyrolysis gasification device that generates biomass pyrolysis gas by pyrolysis of biomass, and a biomass pyrolysis gasification device that utilizes the biomass pyrolysis gasification device Biomass pyrolysis gas and water vapor generated in the chemical chain hydrogen production reaction device alternately undergo redox reactions with oxygen carriers to prepare hydrogen; the biomass pyrolysis gasification device and chemical chain hydrogen production reaction device are transported through the pyrolysis gas pipe connected;
所述化学链制氢反应装置包括第一区段、第二区段和第三区段，第二区段置于第一区段与第三区段之间，第一区段与第三区段的截面直径均大于第二区段；所述第一区段为热解气布送区段，所述第一区段设有反应气体入口，生物质热解气化装置通过热解气输送管连通所述反应气体入口；所述第二区段为氧化还原反应发生区段，氧载体设于所述第二区段内；所述第三区段为气流缓冲区段，设有气体输出口。The chemical chain hydrogen production reaction device includes a first section, a second section and a third section, the second section is placed between the first section and the third section, and the first section and the third section The cross-sectional diameter of each section is larger than that of the second section; the first section is a pyrolysis gas distribution section, and the first section is provided with a reaction gas inlet, and the biomass pyrolysis gasification device is transported through the pyrolysis gas The pipe is connected to the reaction gas inlet; the second section is a redox reaction generation section, and the oxygen carrier is arranged in the second section; the third section is a gas flow buffer section, and a gas output is provided. mouth.
本发明利用生物质热解气化装置将生物质热解气化生成生物质热解气，将所述的生物质热解气引入化学链制氢反应装置中与其中的氧载体发生氧化还原反应，氧载体被还原；然后停止通入生物质热解气，将反应气体切换到水蒸气，处于还原状态下的氧载体与高温水蒸气发生反应生成氢气；化学链制氢反应装置中的尾气经冷却后即得纯净的氢气。The present invention uses a biomass pyrolysis gasification device to generate biomass pyrolysis gas by pyrolysis and gasification of biomass, and introduces the biomass pyrolysis gas into a chemical chain hydrogen production reaction device to undergo oxidation-reduction reaction with the oxygen carrier therein , the oxygen carrier is reduced; then stop feeding the biomass pyrolysis gas, switch the reaction gas to water vapor, and the oxygen carrier in the reduced state reacts with high-temperature water vapor to generate hydrogen; the tail gas in the chemical loop hydrogen production reaction device passes through After cooling, pure hydrogen is obtained.
在实际操作中，生物质热解气和水蒸气均从第一区段引入到化学链制氢反应装置中，所述第一区段的反应气体入口还与外源气体输入管连通。为了生物质热解气和水蒸气两种反应气体之间不会发生串混，在生物质热解气停止通入后，先通入惰性气体，再通入水蒸气，所述惰性气体和水蒸气均可通过外源气体输入管通过。In actual operation, both biomass pyrolysis gas and water vapor are introduced into the chemical loop hydrogen production reaction device from the first section, and the reaction gas inlet of the first section is also communicated with an external gas input pipe. In order to prevent cross-mixing between the two reaction gases of biomass pyrolysis gas and water vapor, after the feed of biomass pyrolysis gas is stopped, the inert gas is first introduced, and then water vapor is introduced. The inert gas and water vapor All can pass through the external source gas input tube.
较佳地，所述氧载体为具有尖晶石结构的NiFe2O4。Preferably, the oxygen carrier is NiFe 2 O 4 with a spinel structure.
较佳地，所述化学链制氢反应装置的工作温度为800～1000℃。Preferably, the operating temperature of the chemical looping hydrogen production reaction device is 800-1000°C.
较佳地，所述第一区段内还设有布风排料装置；所述布风排料装置包括：设置在第一区段内的布风板以及设置在布风板底部的排料管和高温球阀。Preferably, an air distribution and discharge device is also provided in the first section; the air distribution and discharge device includes: an air distribution plate arranged in the first section and a discharge material arranged at the bottom of the air distribution plate pipe and high temperature ball valve.
较佳地，所述生物质热解气化装置包括：生物质热解气化反应器、设置在生物质热解气化反应器上的进料口和安全阀、置于生物质热解气化反应器腔内并将生物质热解气化反应器分隔成两个腔室的中间折流板、设置在生物质热解气化反应器底部的排灰装置和灰斗、开口于生物质热解气化反应器的热解气出口；所述热解气出口经热解气输出管与化学链制氢反应装置的第一区段相连通。较佳地，所述生物质热解气化反应器的工作温度为800～850℃。Preferably, the biomass pyrolysis gasification device includes: a biomass pyrolysis gasification reactor, a feed port and a safety valve arranged on the biomass pyrolysis gasification reactor, a biomass pyrolysis gasification The intermediate baffle plate in the chamber of the biomass pyrolysis gasification reactor and divides the biomass pyrolysis gasification reactor into two chambers, the ash discharge device and the ash hopper at the bottom of the biomass pyrolysis gasification reactor, and the opening to the biomass The pyrolysis gas outlet of the pyrolysis gasification reactor; the pyrolysis gas outlet communicates with the first section of the chemical chain hydrogen production reaction device through the pyrolysis gas output pipe. Preferably, the operating temperature of the biomass pyrolysis gasification reactor is 800-850°C.
较佳地，生物质热解气化装置的进料口设有螺杆型推进器。Preferably, the feed port of the biomass pyrolysis gasification device is provided with a screw type propeller.
较佳地，所述化学链制氢反应装置连接有将所述化学链制氢反应装置中生成气体与固体杂质分离的气固分离装置。所述气固分离装置为旋风分离器，所述旋风分离器经连接管道与化学链制氢反应装置的气体输出口相连接。Preferably, the chemical looping hydrogen production reaction device is connected with a gas-solid separation device for separating the gas generated in the chemical looping hydrogen production reaction device from solid impurities. The gas-solid separation device is a cyclone separator, and the cyclone separator is connected to the gas output port of the chemical chain hydrogen production reaction device through a connecting pipeline.
通常在较强的气流下，所述化学链制氢反应装置中的尾气会夹杂小颗粒的氧载体，气固分离装置用于将尾气与夹杂的小颗粒氧载体分离，将分离出的氧载体重新返回到化学链制氢反应装置中利用。Usually under strong air flow, the tail gas in the chemical looping hydrogen production reaction device will be mixed with small particles of oxygen carriers, and the gas-solid separation device is used to separate the tail gas from the mixed small particles of oxygen carriers, and the separated oxygen carriers It is returned to the chemical chain hydrogen production reaction device for utilization.
本发明的装置具有操作简单、能耗低，生物质处理的焦油含量低、制氢过程还可以同时生产生物碳材料等优势，实现了生物质的高效清洁转化的目的。The device of the invention has the advantages of simple operation, low energy consumption, low tar content in biomass treatment, and simultaneous production of bio-carbon materials in the hydrogen production process, thereby realizing the purpose of efficient and clean conversion of biomass.
附图说明Description of drawings
图1为本发明实施例的结构示意图；Fig. 1 is the structural representation of the embodiment of the present invention;
附图标记：1-进料口；2-安全阀；3-生物质热解气化反应器；4-中间折流板；5-排灰装置；6-灰斗；7-热解气出口；8-螺杆型推进器；9-热解气输送管；10-外源气体输入管；11-气体取样口；12-反应气体入口；13-第一区段；14-第二区段；15-第三区段；16-气体输出口；17-旋风分离器；18-生成气输出管；19-布风板；20-排料管；21-高温球阀。Reference signs: 1-feed inlet; 2-safety valve; 3-biomass pyrolysis gasification reactor; 4-intermediate baffle; 5-ash discharge device; 6-ash hopper; 7-pyrolysis gas outlet ; 8-screw type propeller; 9-pyrolysis gas delivery pipe; 10-external gas input pipe; 11-gas sampling port; 12-reaction gas inlet; 13-first section; 14-second section; 15-the third section; 16-gas output port; 17-cyclone separator; 18-generated gas output pipe; 19-air distribution plate; 20-discharge pipe; 21-high temperature ball valve.
具体实施方式detailed description
以下结合附图和实施例对本发明做进一步描述，但本发明不限于以下实施例：The present invention will be further described below in conjunction with accompanying drawing and embodiment, but the present invention is not limited to following embodiment:
实施例1Example 1
如图1所示，一种生物质热解及利用生物质热解气制氢的装置，包括生物质热解气化装置、化学链制氢反应装置和气固分离装置。As shown in Figure 1, a device for biomass pyrolysis and hydrogen production using biomass pyrolysis gas includes a biomass pyrolysis gasification device, a chemical loop hydrogen production reaction device, and a gas-solid separation device.
生物质热解气化装置包括：生物质热解气化反应器3、设置在生物质热解气化反应器3上的进料口1和安全阀2、置于生物质热解气化反应器3腔内并将生物质热解气化反应器3分隔成两个腔室的中间折流板4、设置在生物质热解气化反应器3底部的排灰装置5和灰斗6、开口于生物质热解气化反应器3的热解气出口7。在进料口1附近设有螺杆型推进器8。在解气出口7上设有气体取样口11。The biomass pyrolysis gasification device includes: a biomass pyrolysis gasification reactor 3, a feed port 1 and a safety valve 2 arranged on the biomass pyrolysis gasification reactor 3, and a biomass pyrolysis gasification reaction The intermediate baffle plate 4 that separates the biomass pyrolysis gasification reactor 3 into two chambers, the ash discharge device 5 and the ash hopper 6 arranged at the bottom of the biomass pyrolysis gasification reactor 3, Open to the pyrolysis gas outlet 7 of the biomass pyrolysis gasification reactor 3 . A screw type propeller 8 is provided near the feed port 1 . A gas sampling port 11 is provided on the degassing outlet 7 .
化学链制氢反应装置包括有第一区段13、第二区段14和第三区段15。第一区段13为热解气布送区段，第一区段13设有反应气体入口12；第二区段14为氧化还原反应发生区段，第二区段14内设有具有尖晶石结构的NiFe2O4氧载体；第三区段15为气流缓冲区段，第三区段15上设有气体输出口16。其中第二区段14置于第一区段13与第三区段15之间，第一区段13与第三区段15的截面直径均大于第二区段14。The chemical chain hydrogen production reaction device includes a first section 13 , a second section 14 and a third section 15 . The first section 13 is the pyrolysis gas distribution section, and the first section 13 is provided with the reaction gas inlet 12; the second section 14 is the section where the oxidation-reduction reaction occurs, and the second section 14 is provided with a NiFe 2 O 4 oxygen carrier with stone structure; the third section 15 is a gas flow buffer section, and the third section 15 is provided with a gas output port 16 . Wherein the second section 14 is placed between the first section 13 and the third section 15 , the cross-sectional diameters of the first section 13 and the third section 15 are larger than the second section 14 .
其中，在第一区段13内还设有布风排料装置。所述布风排料装置包括：设置在第一区段内的锥形布风板19以及设置在锥形布风板底部的排料管20和高温球阀21。Wherein, an air distribution and discharge device is also provided in the first section 13 . The air distribution and discharge device includes: a conical air distribution plate 19 arranged in the first section, a discharge pipe 20 and a high temperature ball valve 21 arranged at the bottom of the conical air distribution plate.
生物质热解气化装置和化学链制氢反应装置通过连通于热解气出口7和反应气体入口12之间的热解气输送管9实现通气。在反应气体入口12上还连接有外源气体输入管10，用于将水蒸气等气体引入到化学链制氢反应装置中。热解气输送管9、外源气体输入管10和反应气体入口12通过三通阀连接。The biomass pyrolysis gasification device and the chemical chain hydrogen production reaction device are ventilated through the pyrolysis gas delivery pipe 9 connected between the pyrolysis gas outlet 7 and the reaction gas inlet 12 . An external gas input pipe 10 is also connected to the reaction gas inlet 12 for introducing gas such as water vapor into the chemical loop hydrogen production reaction device. The pyrolysis gas delivery pipe 9, the external source gas input pipe 10 and the reaction gas inlet 12 are connected through a three-way valve.
气固分离装置主要包括旋风分离器17。旋风分离器17经连接管道与化学链制氢反应装置的气体输出口16相连接。旋风分离器17还设有与气体冷却装置连接的生成气输出管18。The gas-solid separation device mainly includes a cyclone separator 17 . The cyclone separator 17 is connected to the gas outlet 16 of the chemical loop hydrogen production reaction device through a connecting pipeline. The cyclone separator 17 is also provided with a produced gas output pipe 18 connected to the gas cooling device.
上述反应装置中，化学链制氢反应装置的工作温度为800～1000℃；生物质热解气化反应器3的工作温度为800～850℃。Among the above reaction devices, the working temperature of the chemical looping hydrogen production reaction device is 800-1000°C; the working temperature of the biomass pyrolysis gasification reactor 3 is 800-850°C.
实施例2：Example 2:
选取尖晶石型NiFe2O4为氧载体材料，经加工后制成粒径40-80目氧载体颗粒，放入化学链制氢反应系统14中(加入量150-300g)，运行时，开启反应器外加热系统，设定两反应器反应温度，生物质热解反应器3工作温度为800℃，化学链制氢反应器14工作温度为800℃，两反应器工作压力为微正压，打开连接两反应器管道球阀10，打开两反应器惰性载气11，开始置换两反应器空气。装置温度都达到设定值后，打开料仓平衡气(20ml/min)，开始进料，生物质在螺旋进料器1推动下进入生物质热解气化系统3进行热解气化(装置所用原料可以为秸秆、木屑、稻壳、甘蔗渣等生物质原料，本发明实施例中以松木粉为代表进行实验，进料速率，200g/h)，生成H2、CO、CH4、CO2等气体，热解反应器设有气体采样口7，约5min采样一次，通过气相色谱进行成分分析；所生成的生物燃气经连接管道7、9被引入化学链制氢反应器14与其中的氧载体进行氧化还原反应，氧载体被还原成为FeO、Ni或Fe，生成尾气经旋风器16分离后排空，分离的氧载体进入下部密封室，之后返回制氢系统，待载氧体被完全还原后(约40～60min)，停止生物质进料1，关闭生物质燃气球阀10，打开化学链制氢反应器的惰性载气10，置换制氢系统14中未完全反应的生物燃气(流量为60ml/min，约10～20min)，置换完毕后，打开水蒸气10(水蒸气流量50ml/min，120℃)，处于还原状态的载氧体被高温水蒸气氧化，水蒸气裂解产生出H2，经分离冷凝后，约3～5min采样一次，通过气相色谱进行分析，H2纯度超过99％，CO浓度小于0.05％，CO2浓度小于0.5％，CH4浓度小于0.01％，气体中没有检测到焦油，待氧载体完全反应后(约20min)，关闭水蒸气10，打开惰性气体阀门10置换反应器残留气体(60ml/min，约10～20min)，置换完毕后，通入空气10(60ml/min)对制氢系统中氧载体进行进一步氧化，氧化时间约为10min，待氧载体氧化完毕，实验完成一次循环，如此交替通入生物质、惰性气体、水蒸气，反应持续循环进行。实施结果如下：Choose spinel type NiFe 2 O 4 is the oxygen carrier material, after processing, make the oxygen carrier particles with a particle size of 40-80 mesh, put it into the chemical chain hydrogen production reaction system 14 (addition amount 150-300g), during operation, Turn on the external heating system of the reactor, set the reaction temperature of the two reactors, the operating temperature of the biomass pyrolysis reactor 3 is 800°C, the operating temperature of the chemical looping hydrogen production reactor 14 is 800°C, and the operating pressure of the two reactors is slightly positive pressure , open the pipe ball valve 10 connecting the two reactors, open the inert carrier gas 11 of the two reactors, and begin to replace the air in the two reactors. After the temperature of the device reaches the set value, the balance gas (20ml/min) of the silo is opened to start feeding, and the biomass enters the biomass pyrolysis gasification system 3 under the push of the screw feeder 1 for pyrolysis gasification (device The raw materials used can be biomass raw materials such as straw, sawdust, rice husk, bagasse, etc. In the embodiment of the present invention, pine wood powder is used as a representative to carry out experiments, the feed rate is 200g/h), and H 2 , CO, CH 4 , CO are generated 2 and other gases, the pyrolysis reactor is equipped with a gas sampling port 7, which is sampled once every 5 minutes and analyzed by gas chromatography; the generated biogas is introduced into the chemical loop hydrogen production reactor 14 and the The oxygen carrier undergoes oxidation-reduction reaction, the oxygen carrier is reduced to FeO, Ni or Fe, the generated tail gas is separated by the cyclone 16 and then emptied, the separated oxygen carrier enters the lower sealed chamber, and then returns to the hydrogen production system, until the oxygen carrier is completely After reduction (about 40-60min), stop the biomass feed 1, close the biomass gas ball valve 10, open the inert carrier gas 10 of the chemical chain hydrogen production reactor, and replace the incompletely reacted biogas in the hydrogen production system 14 (flow rate 60ml/min, about 10-20min), after the replacement, turn on the water vapor 10 (water vapor flow rate 50ml/min, 120°C), the oxygen carrier in the reduced state is oxidized by high-temperature water vapor, and the water vapor cracks to produce H 2. After separation and condensation, take a sample every 3 to 5 minutes and analyze it by gas chromatography. The purity of H2 exceeds 99%, the concentration of CO is less than 0.05%, the concentration of CO2 is less than 0.5%, and the concentration of CH4 is less than 0.01%. There is no detection in the gas To the tar, after the oxygen carrier has completely reacted (about 20min), turn off the water vapor 10, open the inert gas valve 10 to replace the residual gas in the reactor (60ml/min, about 10-20min), after the replacement, feed air 10 (60ml /min) to further oxidize the oxygen carrier in the hydrogen production system. The oxidation time is about 10 minutes. After the oxidation of the oxygen carrier is completed, the experiment completes a cycle. In this way, biomass, inert gas, and water vapor are alternately introduced, and the reaction continues to cycle. The implementation results are as follows:
表1利用物质热解及热解气化学链制氢装置制备氢气的条件及结果Table 1 Conditions and results of hydrogen production by material pyrolysis and pyrolysis gas chemical loop hydrogen production device
实施例3：Example 3:
利用实施例1的设备，按照施例2的工艺流程，按表2的实施条件制备氢气，并通过气相色谱对生成气体进行分析，结果如下：Utilize the equipment of embodiment 1, according to the technological process of embodiment 2, prepare hydrogen by the implementation condition of table 2, and generate gas is analyzed by gas chromatography, the results are as follows:
表2利用物质热解及热解气化学链制氢装置制备氢气的条件及结果Table 2 Conditions and results of hydrogen production by material pyrolysis and pyrolysis gas chemical loop hydrogen production device
实施例4：Example 4:
利用实施例1的设备，按照施例2的工艺流程，按表3的实施条件制备氢气，并通过气相色谱对生成气体进行分析，结果如下：Utilize the equipment of embodiment 1, according to the technological process of embodiment 2, prepare hydrogen by the implementation condition of table 3, and generate gas is analyzed by gas chromatography, the results are as follows:
表3利用物质热解及热解气化学链制氢装置制备氢气的条件及结果Table 3 Conditions and results of hydrogen production by material pyrolysis and pyrolysis gas chemical loop hydrogen production device
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