WO2023103321A1 - 一种生物质负碳排放发电系统及其工作方法 - Google Patents

一种生物质负碳排放发电系统及其工作方法 Download PDF

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WO2023103321A1
WO2023103321A1 PCT/CN2022/098820 CN2022098820W WO2023103321A1 WO 2023103321 A1 WO2023103321 A1 WO 2023103321A1 CN 2022098820 W CN2022098820 W CN 2022098820W WO 2023103321 A1 WO2023103321 A1 WO 2023103321A1
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power generation
biomass
carbon
carbon nanotube
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PCT/CN2022/098820
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English (en)
French (fr)
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刘蓉
王焕君
郭东方
刘练波
郜时旺
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中国华能集团清洁能源技术研究院有限公司
华能国际电力股份有限公司
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Publication of WO2023103321A1 publication Critical patent/WO2023103321A1/zh

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K13/00—General layout or general methods of operation of complete plants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • the present application relates to the field of chemical technology, in particular to a biomass negative carbon emission power generation system and its working method.
  • biomass has gradually become one of the promising renewable energy sources.
  • the research, development and application of biomass energy and petroleum substitute products is an effective way to ensure energy supply, reduce dependence on fossil energy, and solve future energy problems.
  • biomass energy conversion and utilization technologies are reviewed, mainly including direct combustion technology, biochemical conversion technology (fermentation and anaerobic digestion), thermochemical conversion technology (gasification, pyrolysis), liquefaction technology, compact molding technology, Supercritical fluid conversion technology, etc.; introduces the application of biomass conversion technology, including biomass gasification power generation, gasification hydrogen production, thermal cracking hydrogen production, fermentation to produce fuel ethanol, thermal cracking to produce bio-oil, solidified molding to produce solid fuel , composting and fermenting fertilizers, anaerobic digestion to produce biogas, catalytic cracking to produce biofuels, etc.
  • biomass energy utilization technology including biomass gasification power generation, gasification hydrogen production, thermal cracking hydrogen production, fermentation to produce fuel ethanol, thermal cracking to produce bio-oil, solidified molding to produce solid fuel , composting and fermenting fertilizers, anaerobic digestion to produce biogas, catalytic cracking to produce biofuels, etc.
  • direct combustion power generation is a common way to utilize biomass energy, but because the flue gas produced in the process of direct combustion of biomass contains a large number of polluting particles, which restricts the large-scale application of direct combustion power generation technology, therefore, the development of economic Effective flue gas purification technology can greatly promote the development of direct combustion of biomass.
  • the technical problem to be solved in this application is to overcome the defects in the prior art, thereby providing a biomass negative carbon emission power generation system and its working method, the energy in the process is effectively utilized, energy is saved, and the negative carbon dioxide emission.
  • a biomass negative carbon emission power generation system comprising:
  • the flue gas outlet of the biomass power generation unit is connected with the inlet of the flue gas pretreatment unit, and the outlet of the flue gas pretreatment unit is connected with the CO2 inlet of the carbon dioxide carbon nanotube unit;
  • the waste water outlet of the biomass power generation unit is connected to the inlet of the water pretreatment unit, and the outlet of the water pretreatment unit is connected to the water inlet of the electrolytic hydrogen production unit; the hydrogen outlet of the electrolytic hydrogen production unit is connected to the hydrogen collection unit The inlet is connected, and the outlet of the hydrogen collection unit is connected with the hydrogen inlet of the carbon nanotube production unit.
  • the product outlet of the unit for producing carbon nanotubes from carbon dioxide is connected to a carbon nanotube refining unit.
  • the oxygen outlet of the electrolytic hydrogen production unit is connected to the inlet of the oxygen collection unit, and the outlet of the oxygen collection unit is connected to the oxygen inlet of the biomass unit.
  • the biomass power generation unit is connected with the carbon nanotube unit made of carbon dioxide through a power transmission line.
  • control valves are provided on the connecting pipelines between the carbon dioxide-made carbon nanotube unit, the flue gas pretreatment unit and the hydrogen collection unit.
  • a control valve is provided on the connecting pipeline between the water pretreatment unit, the electrolytic hydrogen production unit and the biomass power generation unit.
  • a control valve is provided on the connecting pipeline between the carbon nanotube refining unit and the carbon nanotube production unit.
  • an air separation unit is also included, and the air separation unit is connected to the oxygen inlet of the biomass power generation unit.
  • the outlet of the water pretreatment unit is connected to the water inlet of the biomass power generation unit.
  • a working method of the biomass negative carbon emission power generation system comprising: a biomass power generation unit performs biomass power generation to generate electric energy;
  • the flue gas produced by the biomass power generation unit enters the flue gas pretreatment unit for treatment and then enters the carbon dioxide production carbon nanotube unit, and the carbon nanotube is prepared by electrochemical method;
  • the wastewater generated by the biomass power generation unit is treated by the water pretreatment unit and then enters the electrolytic hydrogen production unit.
  • the hydrogen generated by the electrolytic hydrogen production unit is collected by the hydrogen collection unit and then enters the carbon dioxide production carbon nanotube unit, and the carbon nanotubes are prepared by electrochemical methods. .
  • the product obtained from the unit for producing carbon nanotubes from carbon dioxide enters the carbon nanotube refining unit for refining.
  • the oxygen generated by the electrolytic hydrogen production unit enters the biomass unit after being collected by an oxygen collection unit.
  • the electrical energy generated by the biomass power generation unit provides electrical energy to the carbon dioxide-made carbon nanotube unit through a power transmission line.
  • the oxygen separated by the air separation unit enters the biomass power generation unit for biomass power generation.
  • the circulating water generated by the water pretreatment unit enters the biomass power generation unit, realizing the recycling of waste water.
  • the oxygen content in the reaction atmosphere in the biomass power generation unit is 0.5v/v%-5v/v%.
  • the raw material gas H 2 : CO 2 molar ratio in the unit for producing carbon nanotubes from carbon dioxide is 2.15 ⁇ 5.27.
  • Biomass includes all plants, microorganisms, animals that feed on plants and microorganisms, and the waste produced by them. Representative biomass is crops, crop waste, wood, wood waste and animal manure.
  • a biomass negative carbon emission power generation system comprising: a biomass power generation unit; the flue gas outlet of the biomass power generation unit is connected to the inlet of the flue gas pretreatment unit, and the flue gas pretreatment unit
  • the outlet of the carbon dioxide is connected with the CO inlet of the carbon nanotube unit
  • the waste water outlet of the biomass power generation unit is connected with the inlet of the water pretreatment unit
  • the outlet of the water pretreatment unit is connected with the water inlet of the electrolytic hydrogen production unit
  • the hydrogen outlet of the electrolytic hydrogen production unit is connected to the inlet of the hydrogen collection unit, and the outlet of the hydrogen collection unit is connected to the hydrogen inlet of the carbon nanotube production unit from carbon dioxide; the application finds that sulfur, nitrogen, etc.
  • the content of non-metals is low, the sulfur compounds and nitrogen oxides produced by combustion are less, and the flue gas produced by biomass power generation can be directly used to prepare carbon nanotubes by electrochemical method after pretreatment without carbon dioxide capture.
  • the applied biomass negative carbon emission power generation system in the system, the flue gas generated by the biomass power generation unit enters the flue gas pretreatment unit for treatment and then enters the carbon dioxide carbon nanotube unit, and the carbon nanotube is prepared by electrochemical method, and the biomass
  • the wastewater from the power generation unit is pretreated and the hydrogen obtained by electrolysis is sent to the carbon nanotube production unit to prepare carbon nanotubes by electrochemical methods.
  • the above system can effectively reduce carbon dioxide emissions and not only improve the utilization of biomass rate, the generated products have high economic value, and realize negative CO 2 emissions.
  • a biomass negative carbon emission power generation system provided by this application, the oxygen outlet of the electrolytic hydrogen production unit is connected to the inlet of the oxygen collection unit, and the outlet of the oxygen collection unit is connected to the oxygen inlet of the biomass unit , to realize the utilization of all components of biomass.
  • control valves are installed on the connecting pipelines between the carbon dioxide-made carbon nanotube unit, the flue gas pretreatment unit and the hydrogen collection unit, which can coordinately control the carbon dioxide-made carbon nanotube unit.
  • the amount of hydrogen and pretreated flue gas in the tube unit and then control the preparation of carbon nanotubes.
  • a working method of the biomass negative carbon emission power generation system comprising: the biomass power generation unit performs biomass power generation to generate electric energy; the flue gas generated by the biomass power generation unit enters the flue gas pretreatment unit for treatment After that, it enters the carbon nanotube production unit of carbon dioxide, and the carbon nanotube is prepared by electrochemical method; the wastewater generated by the biomass power generation unit is treated by the water pretreatment unit and then enters the electrolytic hydrogen production unit, and the hydrogen generated by the electrolytic hydrogen production unit passes through the hydrogen collection unit After being collected, it enters the unit of carbon dioxide to make carbon nanotubes, and electrochemical methods are used to prepare carbon nanotubes; the above-mentioned working method of using biomass negative carbon emission power generation system not only improves the utilization rate of biomass, but also generates products with high economic value , and the negative emission of CO 2 has been realized in biomass power generation, and the degree of automation is high.
  • Fig. 1 is a schematic structural diagram of a biomass negative carbon emission power generation system in Example 1 of the present application.
  • 1-Biomass power generation unit 2-Flue gas pretreatment unit, 3-Carbon nanotube production unit from carbon dioxide, 4-Carbon nanotube refining unit, 5-Water pretreatment unit, 6-Electrolytic hydrogen production unit, 7-Hydrogen collection unit, 8-oxygen collection unit, 9-air separation unit.
  • This embodiment provides a biomass negative carbon emission power generation system, as shown in Figure 1, including:
  • Biomass power generation unit 1
  • the flue gas outlet of the biomass power generation unit 1 is connected with the inlet of the flue gas pretreatment unit 2, and the outlet of the flue gas pretreatment unit 2 is connected with the CO inlet of the carbon nanotube unit 3 made of carbon dioxide;
  • the waste water outlet of the biomass power generation unit 1 is connected to the inlet of the water pretreatment unit 5, and the outlet of the water pretreatment unit 5 is connected to the water inlet of the electrolytic hydrogen production unit 6; the hydrogen outlet of the electrolytic hydrogen production unit 6 It is connected with the inlet of the hydrogen gas collection unit 7, and the outlet of the hydrogen gas collection unit 7 is connected with the hydrogen gas inlet of the carbon nanotube made of carbon dioxide unit 3.
  • the flue gas generated by generating electricity in the biomass power generation unit 1 enters the flue gas pretreatment unit 2, and passes through the flue gas pretreatment unit 2 to filter and pretreat impurities such as dust in the flue gas Directly enter carbon dioxide carbon nanotube unit 3 for the electrochemical method to prepare carbon nanotubes, and generate waste water generated in biomass power generation unit 1.
  • the waste water is pretreated by water pretreatment unit 5, and water treatment unit 5 adopts flocculation reaction
  • the precipitation process removes suspended solids, colloids and other impurities in the raw water to make it meet the technical requirements of water electrolysis hydrogen production.
  • the water treated by water treatment unit 5 should meet the technical requirements of water electrolysis hydrogen production system GB/T 19774-2005, which meets the requirements
  • the hydrogen produced by entering the electrolytic hydrogen production unit 6 enters the carbon dioxide production carbon nanotube unit 3 for the electrochemical method to prepare carbon nanotubes.
  • the above system can effectively reduce the emission of carbon dioxide, which not only improves the utilization rate of biomass,
  • the generated products have high economic value, and realize negative emission of CO 2 .
  • the product outlet of the carbon nanotube production unit 3 is connected to the carbon nanotube refining unit 4 to further refine the prepared carbon nanotubes.
  • the oxygen outlet of the electrolytic hydrogen production unit 6 is connected to the inlet of the oxygen collection unit 8, and the outlet of the oxygen collection unit 8 is connected to the oxygen inlet of the biomass unit 1, so as to realize the whole group of biomass points of use.
  • the biomass power generation unit 1 is connected to the carbon nanotube unit 3 made of carbon dioxide through a power transmission line, so as to provide electric energy to the carbon nanotube unit 3 made of carbon dioxide in the system to prepare carbon nanotubes electrochemically.
  • control valves are provided on the connecting pipelines between the carbon dioxide-made carbon nanotube unit 3 and the flue gas pretreatment unit 2 and the hydrogen gas collection unit 7.
  • the amount of carbon dioxide and hydrogen in unit 3 realizes the control of carbon nanotube preparation.
  • a control valve is provided on the connecting pipeline between the water pretreatment unit 5, the electrolytic hydrogen production unit 6 and the biomass power generation unit 1. Due to the setting of the control valve, the water pretreatment unit 5 can be coordinated and regulated. Two water paths with the electrolytic hydrogen production unit 6 and the water pretreatment unit 5 and the biomass power generation unit 1.
  • a control valve is provided on the connecting pipeline between the carbon nanotube refining unit 4 and the carbon nanotube producing unit 3 to control the amount of carbon nanotube refining unit 4 refining.
  • an air separation unit 9 is also included, and the air separation unit 9 is connected to the oxygen inlet of the biomass power generation unit 1.
  • the oxygen of the biomass power generation unit 1 comes from air passing through Air separation unit 9 is obtained.
  • the outlet of the water pretreatment unit 5 is connected to the water inlet in the biomass power generation unit 1, and most of the circulating water processed by the water pretreatment unit 5 returns to the biomass power generation unit 1 for recycling, and a small part
  • the water is sent to the electrolytic hydrogen production unit 6 for electrolytic hydrogen production to realize full utilization of resources.
  • This embodiment provides a working method utilizing the biomass negative carbon emission power generation system of Embodiment 1, including:
  • Biomass power generation is performed by the biomass power generation unit 1 to generate electric energy.
  • the flue gas and waste water generated by the biomass power generation unit 1 are processed and utilized through the following two routes:
  • the flue gas produced by the biomass power generation unit 1 enters the flue gas pretreatment unit 2 for treatment and then enters the carbon dioxide carbon nanotube unit 3, and the carbon nanotubes are prepared by electrochemical methods;
  • the waste water produced by the biomass power generation unit 1 enters the electrolytic hydrogen production unit 6 after being treated by the water pretreatment unit 5, and the hydrogen gas generated by the electrolytic hydrogen production unit 6 is collected by the hydrogen gas collection unit 7 and enters the carbon nanotube production unit 3 from carbon dioxide. Chemically prepared carbon nanotubes.
  • the flue gas and waste water produced by the above-mentioned biomass power generation unit 1 are processed and utilized through two routes, which can effectively reduce the emission of carbon dioxide in biomass power generation, not only improve the utilization rate of biomass, but also generate products with high economic value , and achieve negative CO 2 emissions, and a high degree of automation.
  • the product obtained in the carbon nanotube production unit 3 enters the carbon nanotube refining unit 4 for refining.
  • the oxygen generated by the electrolytic hydrogen production unit 6 is collected by the oxygen collection unit 8 and then enters the biomass unit 1, making full use of waste water resources generated by biomass power generation.
  • the electrical energy generated by the biomass power generation unit 1 provides electrical energy to the carbon nanotube unit 3 made of carbon dioxide through a power transmission line.
  • the air separation unit 9 separates and obtains pure nitrogen and oxygen, and mixes them according to requirements, and then enters the biomass power generation unit 1 for biomass power generation.
  • the water produced by the water pretreatment unit 5 enters the biomass power generation unit 1, and most of the circulating water treated by the water pretreatment unit 5 returns to the biomass power generation unit 1 for recycling, and a small part of the water is sent into the biomass power generation unit 1.
  • the electrolytic hydrogen production unit 6 performs electrolytic hydrogen production to realize full utilization of resources
  • the oxygen content in the reaction atmosphere in the biomass power generation unit 1 is 0.5v/v%-5v/v%, and 3v/v% is selected in this embodiment.
  • the H 2 :CO 2 molar ratio of the raw material gas in the carbon nanotube production unit is 2.15-5.27, and the H 2 :CO 2 molar ratio is selected to be 3.5 in this embodiment.
  • straw is fed into the biomass power generation unit 1 to generate electricity, and the flue gas generated in the biomass power generation unit 1 enters the flue gas pretreatment unit 2 for treatment, and the flue gas pretreatment unit 2 removes the dust in the flue gas, etc.
  • the impurities are filtered and pretreated and directly enter the carbon nanotube production unit 3 from carbon dioxide, and the carbon nanotubes are prepared by electrochemical methods; the waste water generated by the biomass power generation unit 1 is treated by the water pretreatment unit 5, and the water treatment unit 5 adopts the flocculation reaction precipitation process Remove suspended solids, colloids and other impurities in the raw water to meet the technical requirements of water electrolysis for hydrogen production, and then enter the electrolysis hydrogen production unit 6.
  • the hydrogen generated by the electrolysis hydrogen production unit 6 is collected by the hydrogen collection unit 7 and enters carbon dioxide to produce carbon nanotubes In unit 3, carbon nanotubes were prepared by electrochemical methods.
  • the electric energy of the carbon nanotube unit 3 made of carbon dioxide is provided by the electric energy generated by the biomass power generation unit 1 through the transmission line.
  • the control valve provided on the connecting pipeline between the carbon dioxide carbon nanotube unit 3, the flue gas pretreatment unit 2 and the hydrogen collection unit 7, the raw material gas H2 : CO2 molar ratio in the carbon dioxide carbon nanotube unit is adjusted to be 2.15 ⁇ 5.27, the molar ratio of H 2 :CO 2 is chosen to be 3.5 in this embodiment.
  • the product obtained from the carbon nanotube production unit 3 enters the carbon nanotube refining unit 4 for refining.
  • the oxygen content in the reaction atmosphere of the biomass power generation unit 1 to be 0.5v/v%-5v/v%, in this embodiment select 3v/v%, a part of the oxygen-containing reaction atmosphere of the biomass power generation unit 1 It is separated from the air separation unit 9, and a part comes from the oxygen produced by the electrolytic hydrogen production unit 6.
  • the oxygen produced by the electrolytic hydrogen production unit 6 enters the biomass unit 1 after being collected by the oxygen collection unit 8, and the reaction atmosphere is regulated by the above two parts. of oxygen content.
  • most of the circulating water treated by the water pretreatment unit 5 returns to the biomass power generation unit 1 for recycling. After testing, when the straw feeding rate is 200t/h, the entire biomass power generation system has achieved negative carbon emissions, and the output of carbon nanotubes per hour is 43.1t/h.

Abstract

本申请提供了一种生物质负碳排放发电系统及其工作方法。该系统包括：生物质发电单元；所述生物质发电单元的烟气出口与烟气预处理单元的入口连接，所述烟气预处理单元的出口与二氧化碳制碳纳米管单元的CO 2入口连接；所述生物质发电单元的废水出口与水预处理单元的入口连接，所述水预处理单元的出口与电解制氢单元的水入口连接；所述电解制氢单元的氢气出口与氢气收集单元的入口连接，所述氢气收集单元的出口与所述二氧化碳制碳纳米管单元的氢气入口连接。该系统可有效地减少二氧化碳的排放，不仅提高了生物质利用率，生成的产品有较高的经济价值，而且实现了CO 2负排放。

Description

一种生物质负碳排放发电系统及其工作方法
相关申请的交叉引用
本申请要求在2021年12月9日提交中国专利局、申请号为202111500675.9、发明名称为“一种生物质负碳排放发电系统及其工作方法”的中国专利申请的优先权，其全部内容通过引用的方式并入本文中。
技术领域
本申请涉及化工技术领域，具体涉及一种生物质负碳排放发电系统及其工作方法。
背景技术
近年来，随着化石能源的日益枯竭以及环境污染的日益加剧，生物质逐渐成为具有前景的可再生能源之一。生物质能源和石油替代产品的研究、开发和应用，是保障能源供应、减少对化石能源的依赖、解决未来能源问题的有效途径。综述了目前国内外生物质能的转化利用技术，主要包括直接燃烧技术、生化转化技术(发酵和厌氧性消化)、热化学转化技术(气化、热解)、液化技术、致密成型技术、超临界流体转化技术等；介绍了生物质转化技术的应用，包括生物质气化发电、气化制氢、热裂解制氢、发酵法生产燃料乙醇、热裂解制生物油、固化成型制固态燃料、堆肥发酵制肥料、厌氧性消化生产沼气、催化裂解生产生物燃料等。对未来的生物质能利用技术的发展进行了展望。其中，直燃发电是利用生物质能源常见的一种方 式，但由于生物质直燃过程中产生的烟气含有大量的污染性颗粒，制约了直燃发电技术的大规模应用，因此，开发经济有效的烟气净化技术可极大的促进生物质直燃利用的发展。
发明内容
因此，本申请要解决的技术问题在于克服现有技术中的缺陷，从而提供一种生物质负碳排放发电系统及其工作方法，过程中的能源有效利用，节约了能源，实现了二氧化碳的负排放。
为此，本申请提供了如下的技术方案：
一种生物质负碳排放发电系统，包括：
生物质发电单元；
所述生物质发电单元的烟气出口与烟气预处理单元的入口连接，所述烟气预处理单元的出口与二氧化碳制碳纳米管单元的CO 2入口连接；
所述生物质发电单元的废水出口与水预处理单元的入口连接，所述水预处理单元的出口与电解制氢单元的水入口连接；所述电解制氢单元的氢气出口与氢气收集单元的入口连接，所述氢气收集单元的出口与所述二氧化碳制碳纳米管单元的氢气入口连接。
可选的，所述二氧化碳制碳纳米管单元的产物出口与碳纳米管精制单元连接。
可选的，所述电解制氢单元的氧气出口与氧气收集单元的入口连接，所述氧气收集单元的出口与所述生物质单元的氧气入口连接。
可选的，所述生物质发电单元通过输电线路与二氧化碳制碳纳米管单 元连接。
可选的，所述二氧化碳制碳纳米管单元与所述烟气预处理单元和所述氢气收集单元的连接管路上均设有控制阀。
可选的，所述水预处理单元与所述电解制氢单元和所述生物质发电单元之间的连接管路上设有控制阀。
可选的，所述碳纳米管精制单元与所述二氧化碳制碳纳米管单元的连接管路上设有控制阀。
可选的，还包括空气分离单元，所述空气分离单元与所述生物质发电单元的氧气入口连接。
可选的，水预处理单元的出口与生物质发电单元中的水入口连接。
一种所述的生物质负碳排放发电系统的工作方法，包括：生物质发电单元进行生物质发电产生电能；
生物质发电单元产生的烟气进入烟气预处理单元处理后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管；
生物质发电单元产生的废水经过水预处理单元处理后进入电解制氢单元，电解制氢单元产生的氢气经过氢气收集单元收集后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管。
可选的，所述二氧化碳制碳纳米管单元得到的产物进入碳纳米管精制单元进行精制。
可选的，所述电解制氢单元产生的氧气经过氧气收集单元收集后进入所述生物质单元。
可选的，所述生物质发电单元产生的电能通过输电线路向二氧化碳制 碳纳米管单元提供电能。
可选的，空气分离单元分离得到的氧气进入所述生物质发电单元中进行生物质发电。
可选的，水预处理单元产生的循环水进入生物质发电单元中，实现了废水的循环利用。
可选的，所述生物质发电单元中反应气氛中的含氧量为0.5v/v％-5v/v％。
可选的，所述二氧化碳制碳纳米管单元中原料气H 2：CO 2摩尔比为2.15～5.27。
本申请中生物质广义概念：生物质包括所有的植物、微生物以及以植物、微生物为食物的动物及其生产的废弃物。有代表性的生物质如农作物、农作物废弃物、木材、木材废弃物和动物粪便。狭义概念：生物质主要是指农林业生产过程中除粮食、果实以外的秸秆、树木等木质纤维素(简称木质素)、农产品加工业下脚料、农林废弃物及畜牧业生产过程中的禽畜粪便和废弃物等物质。
本申请技术方案，具有如下优点：
1.本申请提供的一种生物质负碳排放发电系统，包括：生物质发电单元；所述生物质发电单元的烟气出口与烟气预处理单元的入口连接，所述烟气预处理单元的出口与二氧化碳制碳纳米管单元的CO 2入口连接；所述生物质发电单元的废水出口与水预处理单元的入口连接，所述水预处理单元的出口与电解制氢单元的水入口连接；所述电解制氢单元的氢气出口与氢气收集单元的入口连接，所述氢气收集单元的出口与所述二氧化碳制碳 纳米管单元的氢气入口连接；本申请发现生物质中的硫、氮等非金属含量低，燃烧产生的含硫化合物、氮氧化物较少，生物质发电产生的烟气经预处理后可以直接用于电化学法制备碳纳米管，无需二氧化碳捕集，从而提出了本申请的生物质负碳排放发电系统，在系统中，生物质发电单元产生的烟气进入烟气预处理单元处理后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管，生物质发电单元的废水经预处理后进行电解制氢得到的氢气送入二氧化碳制碳纳米管单元中采用电化学方法制备碳纳米管，上述系统中可有效地减少二氧化碳的排放，不仅提高了生物质利用率，生成的产品有较高的经济价值，而且实现了CO 2负排放。
2.本申请提供的一种生物质负碳排放发电系统，所述电解制氢单元的氧气出口与氧气收集单元的入口连接，所述氧气收集单元的出口与所述生物质单元的氧气入口连接，实现生物质的全组分利用。
3.本申请提供的一种生物质负碳排放发电系统，二氧化碳制碳纳米管单元与烟气预处理单元和氢气收集单元的连接管路上均设有控制阀，能够协同控制进入二氧化碳制碳纳米管单元的氢气和预处理的烟气的量，进而控制碳纳米管的制备。
4.本申请提供的一种所述的生物质负碳排放发电系统的工作方法，包括：生物质发电单元进行生物质发电产生电能；生物质发电单元产生的烟气进入烟气预处理单元处理后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管；生物质发电单元产生的废水经过水预处理单元处理后进入电解制氢单元，电解制氢单元产生的氢气经过氢气收集单元收集后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管；上述利 用生物质负碳排放发电系统的工作方法，不仅提高了生物质利用率，生成的产品有较高的经济价值，而且生物质发电中实现了CO 2负排放，且自动化程度高。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请实施例1中生物质负碳排放发电系统结构示意图。
附图标记：
1-生物质发电单元，2-烟气预处理单元，3-二氧化碳制碳纳米管单元，4-碳纳米管精制单元，5-水预处理单元，6-电解制氢单元，7-氢气收集单元，8-氧气收集单元，9-空气分离单元。
具体实施方式
提供下述实施例是为了更好地进一步理解本申请，并不局限于所述最佳实施方式，不对本申请的内容和保护范围构成限制，任何人在本申请的启示下或是将本申请与其他现有技术的特征进行组合而得出的任何与本申请相同或相近似的产品，均落在本申请的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的 常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
实施例1
本实施例提供了一种生物质负碳排放发电系统，如图1所示，包括：
生物质发电单元1；
所述生物质发电单元1的烟气出口与烟气预处理单元2的入口连接，所述烟气预处理单元2的出口与二氧化碳制碳纳米管单元3的CO 2入口连接；
所述生物质发电单元1的废水出口与水预处理单元5的入口连接，所述水预处理单元5的出口与电解制氢单元6的水入口连接；所述电解制氢单元6的氢气出口与氢气收集单元7的入口连接，所述氢气收集单元7的出口与所述二氧化碳制碳纳米管单元3的氢气入口连接。
在上述系统中，生物质发电单元1中进行发电产生的烟气，该烟气进入烟气预处理单元2，并经过烟气预处理单元2将烟气中的粉尘等杂质进行过滤预处理后直接进入二氧化碳制碳纳米管单元3中用于电化学法制备碳纳米管，生物质发电单元1中进行发电产生的废水，该废水经过水预处理单元5预处理，水处理单元5采用絮凝反应沉淀工艺除去原水中的悬浮物、胶体等杂质，使其符合水电解制氢的技术要求，水处理单元5处理后的水应符合水电解制氢系统技术要求GB/T 19774-2005，符合要求的水进入电解制氢单元6制得的氢气进入二氧化碳制碳纳米管单元3中用于电化学法制备碳纳米管，上述系统中可有效地减少二氧化碳的排放，不仅提高 了生物质利用率，生成的产品有较高的经济价值，而且实现了CO 2负排放。
作为优化的实施方式，所述二氧化碳制碳纳米管单元3的产物出口与碳纳米管精制单元4连接，对制备的碳纳米管进行进一步精制。
作为优化的实施方式，所述电解制氢单元6的氧气出口与氧气收集单元8的入口连接，所述氧气收集单元8的出口与所述生物质单元1的氧气入口连接，实现生物质全组分的利用。
作为可替换的实施方式，所述生物质发电单元1通过输电线路与二氧化碳制碳纳米管单元3连接，实现系统内向二氧化碳制碳纳米管单元3提供电能进行电化学方法制备碳纳米管。
作为优化的实施方式，所述二氧化碳制碳纳米管单元3与烟气预处理单元2和氢气收集单元7的连接管路上均设有控制阀，通过设置控制阀，协同调控进入二氧化碳制碳纳米管单元3中二氧化碳和氢气的量，实现碳纳米管制备的控制。
作为优化的实施方式，所述水预处理单元5与电解制氢单元6和生物质发电单元1之间的连接管路上设有控制阀，由于控制阀的设置，可以协同调控水预处理单元5与电解制氢单元6以及水预处理单元5与生物质发电单元1的两条水路。
作为优化的实施方式，所述碳纳米管精制单元4与二氧化碳制碳纳米管单元3的连接管路上设有控制阀，控制碳纳米管精制单元4精制的量。
作为可替换的实施方式，还包括空气分离单元9，所述空气分离单元9与所述生物质发电单元1的氧气入口连接，在本实施方式中，生物质发电 单元1的氧气来源于空气经过空气分离单元9获得的。
作为优化的实施方式，水预处理单元5的出口与生物质发电单元1中的水入口连接，水预处理单元5处理后的循环水大部分回到生物质发电单元1进行循环利用，少部分水送入电解制氢单元6进行电解制氢，实现资源充分利用。
实施例2
本实施例提供了一种利用实施例1的生物质负碳排放发电系统的工作方法，包括：
由生物质发电单元1进行生物质发电产生电能，在发电过程中，生物质发电单元1产生的烟气和废水经过如下两条路线进行处理和利用：
生物质发电单元1产生的烟气进入烟气预处理单元2处理后进入二氧化碳制碳纳米管单元3中，采用电化学方法制备碳纳米管；
生物质发电单元1产生的废水经过水预处理单元5处理后进入电解制氢单元6，电解制氢单元6产生的氢气经过氢气收集单元7收集后进入二氧化碳制碳纳米管单元3中，采用电化学方法制备碳纳米管。
上述生物质发电单元1产生的烟气和废水经过两条路线进行处理和利用，可有效地减少生物质发电中二氧化碳的排放，不仅提高了生物质利用率，生成的产品有较高的经济价值，而且实现了CO 2负排放，且自动化程度高。
作为优化的实施方式，所述二氧化碳制碳纳米管单元3得到的产物进入碳纳米管精制单元4进行精制。
作为优化的实施方式，所述电解制氢单元6产生的氧气经过氧气收集单元8收集后进入所述生物质单元1，充分利用了生物质发电产生的废水资源。
作为可替换的实施方式，所述生物质发电单元1产生的电能通过输电线路向二氧化碳制碳纳米管单元3提供电能。
作为优化的实施方式，空气分离单元9分离得到纯的氮气和氧气，按要求配比，然后进入所述生物质发电单元1中进行生物质发电。
作为优化的实施方式，水预处理单元5产生的水进入生物质发电单元1中，水预处理单元5处理后的循环水大部分回到生物质发电单元1进行循环利用，少部分水送入电解制氢单元6进行电解制氢，实现资源充分利用
作为优化的实施方式，所述生物质发电单元1中反应气氛中的含氧量为0.5v/v％-5v/v％，在本实施例中选择3v/v％。
作为优化的实施方式，所述二氧化碳制碳纳米管单元中原料气H 2：CO 2摩尔比为2.15～5.27，在本实施例中选择H 2：CO 2摩尔比为3.5。
如图1所示，向生物质发电单元1中投料秸秆进行发电，生物质发电单元1中产生的烟气进入烟气预处理单元2处理，烟气预处理单元2将烟气中的粉尘等杂质进行过滤预处理后直接进入二氧化碳制碳纳米管单元3，采用电化学方法制备碳纳米管；生物质发电单元1产生的废水经过水预处理单元5处理，水处理单元5采用絮凝反应沉淀工艺除去原水中的悬浮物、胶体等杂质，使其符合水电解制氢的技术要求后进入电解制氢单元6，电解制氢单元6产生的氢气经过氢气收集单元7收集后进入二氧化碳制碳纳米管单元3中，采用电化学方法制备碳纳米管。所述二氧化碳制碳纳米管单元3的电能由生物质发电单元1产生的电能通过输电线路提供。通过控制 二氧化碳制碳纳米管单元3与烟气预处理单元2和氢气收集单元7的连接管路上设有的控制阀，调控二氧化碳制碳纳米管单元中原料气H 2：CO 2摩尔比为2.15～5.27，在本实施例中选择H 2：CO 2摩尔比为3.5。二氧化碳制碳纳米管单元3得到的产物进入碳纳米管精制单元4进行精制。调控所述生物质发电单元1中反应气氛中的含氧量为0.5v/v％-5v/v％，在本实施例中选择3v/v％，生物质发电单元1的含氧反应气氛一部分来自空气分离单元9分离获得，一部分来自电解制氢单元6产生的氧气，电解制氢单元6产生的氧气经过氧气收集单元8收集后进入所述生物质单元1，通过上述两部分调控反应气氛中的含氧量。为节约资源，水预处理单元5处理后的循环水大部分回到生物质发电单元1进行循环利用。经检测，当秸秆投料量为200t/h，整个生物质发电系统的实现了负碳排放，每小时碳纳米管产量为43.1t/h。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种生物质负碳排放发电系统，其特征在于，包括：
    生物质发电单元；
    所述生物质发电单元的烟气出口与烟气预处理单元的入口连接，所述烟气预处理单元的出口与二氧化碳制碳纳米管单元的CO 2入口连接；
    所述生物质发电单元的废水出口与水预处理单元的入口连接，所述水预处理单元的出口与电解制氢单元的水入口连接；所述电解制氢单元的氢气出口与氢气收集单元的入口连接，所述氢气收集单元的出口与所述二氧化碳制碳纳米管单元的氢气入口连接。
  2. 根据权利要求1所述的生物质负碳排放发电系统，其特征在于，所述二氧化碳制碳纳米管单元的产物出口与碳纳米管精制单元连接。
  3. 根据权利要求1或2所述的生物质负碳排放发电系统，其特征在于，所述电解制氢单元的氧气出口与氧气收集单元的入口连接，所述氧气收集单元的出口与所述生物质单元的氧气入口连接。
  4. 根据权利要求1或2所述的生物质负碳排放发电系统，其特征在于，所述生物质发电单元通过输电线路与二氧化碳制碳纳米管单元连接。
  5. 根据权利要求1或2所述的生物质负碳排放发电系统，其特征在于，所述二氧化碳制碳纳米管单元与所述烟气预处理单元和所述氢气收集单元的连接管路上均设有控制阀。
  6. 根据权利要求1或2所述的生物质负碳排放发电系统，其特征在于，所述水预处理单元与所述电解制氢单元和所述生物质发电单元之间的连接管路上设有控制阀。
  7. 根据权利要求2所述的生物质负碳排放发电系统，其特征在于，所述碳纳米管精制单元与所述二氧化碳制碳纳米管单元的连接管路上设有控制阀。
  8. 一种如权利要求1-7中任一项所述的生物质负碳排放发电系统的工作方法，其特征在于，包括：生物质发电单元进行生物质发电产生电能；
    生物质发电单元产生的烟气进入烟气预处理单元处理后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管；
    生物质发电单元产生的废水经过水预处理单元处理后进入电解制氢单元，电解制氢单元产生的氢气经过氢气收集单元收集后进入二氧化碳制碳纳米管单元中，采用电化学方法制备碳纳米管。
  9. 根据权利要求8所述的生物质负碳排放发电系统的工作方法，其特征在于，所述二氧化碳制碳纳米管单元得到的产物进入碳纳米管精制单元 进行精制。
  10. 根据权利要求8或9所述的生物质负碳排放发电系统的工作方法，其特征在于，所述电解制氢单元产生的氧气经过氧气收集单元收集后进入所述生物质单元；
    可选的，所述生物质发电单元产生的电能通过输电线路向二氧化碳制碳纳米管单元提供电能；
    可选的，所述生物质发电单元中反应气氛中的含氧量为0.5v/v％-5v/v％；
    可选的，所述二氧化碳制碳纳米管单元中原料气H 2：CO 2摩尔比为2.15～5.27。
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