WO2024037175A1 - 生物质基多孔碳复合材料及制备与在co2吸附中的应用 - Google Patents

生物质基多孔碳复合材料及制备与在co2吸附中的应用 Download PDF

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WO2024037175A1
WO2024037175A1 PCT/CN2023/101340 CN2023101340W WO2024037175A1 WO 2024037175 A1 WO2024037175 A1 WO 2024037175A1 CN 2023101340 W CN2023101340 W CN 2023101340W WO 2024037175 A1 WO2024037175 A1 WO 2024037175A1
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black liquor
porous carbon
pulping
carbon composite
biomass
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French (fr)
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肖睿
刘超
许佳欢
薛北辰
范宇阳
徐维聪
孔祥琛
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东南大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4837—Lignin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to carbon-based composite materials, in particular to a biomass-based porous carbon composite material and its preparation and application in CO 2 adsorption.
  • Biochar is generally prepared by two methods: pyrolysis carbonization and hydrothermal carbonization.
  • the degree of carbonization of biomass hydrothermal carbon is not as good as that of pyrolysis. Carbon can generally only be used in bottom-end applications such as adsorbents for water pollutants. High-end applications often require secondary pyrolysis and carbonization. Due to the characteristic properties of biomass, it is generally necessary to use a template agent to create pores during the carbonization process, and the resulting carbonized product needs further activation to obtain the performance required for high-end applications.
  • biomass carbonization has problems such as complex process, high energy consumption, many by-products (VOC, organic wastewater, etc.), high cost, and the need for further refinement of the product, which seriously restricts its large-scale production and application.
  • Lignin is one of the three major components of lignocellulosic biomass. Its high carbon content and rich aromatic structure make it easier to prepare high-performance biochar. Using industrial lignin as raw material to prepare biochar can simultaneously realize the recycling of industrial waste. Harmless treatment and high-value utilization are of great significance.
  • lignin-based biochar is mostly made from purified industrial lignin and is prepared by adding template agents and activators (Journal paper ACS Sustainable Chemistry&Engineering 6 (2016) 10454-10462, Journal paper ChemSusChem 8 (2015) 428-432.
  • Dissertation Preparation of lignin-based mesoporous carbon materials by template method and study on electrochemical properties [D], Chinese Academy of Forestry Sciences, 2018”, Dissertation “Preparation, characterization and adsorption of papermaking black liquor lignin activated carbon” Application [D], Shandong University, 2018”, thesis “Preparation and electrochemistry of mesoporous carbon and its composite materials using lignin as carbon source [D], Zhejiang University of Technology, 2015”, patent ZL201210207757.9, Patent ZL201811376052.3, etc.), ignores the source of industrial lignin and avoids the cost of extracting and purifying lignin from pulping and papermaking black liquor and the environmental burden caused by the use of chemicals.
  • the adsorption of CO 2 on the surface of porous carbon benefits from its specific surface area and pore volume, that is, the micropores and mesopores in porous carbon are mainly used for physical adsorption.
  • By regulating the preparation process of porous carbon more micropores and mesopores can be obtained.
  • pore structure thereby increasing the adsorption capacity of CO 2 , but simple physical adsorption has an adsorption bottleneck and is difficult to significantly break through.
  • heteroatoms S, N, P, etc.
  • these additional reagents and materials undoubtedly increase the cost of CO2 adsorption by porous carbon.
  • the present invention provides a biomass-based porous carbon composite material and its preparation and application in CO 2 adsorption.
  • the purpose is to realize the full utilization of pulping and papermaking black liquor and obtain both physical sites for CO 2 adsorption.
  • High-performance porous carbon composite materials with chemical sites avoid the steps and costs of separating, extracting, and purifying lignin from black liquor.
  • the invention provides a biomass-based porous carbon composite material, which is obtained through arc treatment using pulping and papermaking black liquor solids as a precursor, and has a porous carbon structure that can physically adsorb CO 2 and a chemically adsorbed CO 2 Alkaline species, the porous carbon structure uses lignin in the precursor as the carbon source, sodium hydroxide, sodium salt and small molecule carbohydrate degradation products in the precursor as templates and activators, and is heated by arc heat It is obtained after carbonization and self-activation.
  • the alkaline species is obtained by arc thermal decomposition of sodium hydroxide and sodium salt in the precursor.
  • the porous carbon structure can be controlled by changing the carbonization conditions.
  • the invention also provides a method for preparing the biomass-based porous carbon composite material, which includes:
  • the black liquor solid is treated with arc to obtain a solid product
  • the solid product is ground to obtain a biomass-based porous carbon composite material.
  • the arc current is 10-1000A, and the treatment time is 1s-10min.
  • the drying of pulping and papermaking black liquor into black liquor solids includes:
  • the pulping and papermaking black liquor is caustic soda pulping black liquor, caustic soda-anthraquinone pulping black liquor, sulfate pulping black liquor, organic solvent pulping black liquor, chemical mechanical pulping black liquor, paper pulp At least one of the black liquor obtained by washing.
  • the pulping and papermaking black liquor is at least one of laboratory pulping black liquor, pulping plant thin black liquor, and pulping plant thick black liquor.
  • the invention also provides an application of the biomass-based porous carbon composite material in CO 2 adsorption.
  • the present invention utilizes the high-temperature zone generated by the arc to achieve biomass carbonization. Compared with traditional pyrolysis carbonization and hydrothermal carbonization methods, it has the advantages of low energy consumption, high efficiency, extremely rapid carbonization of biomass, etc., and the process is flexible and The operation is simple and the equipment occupies a small area, making it very suitable for large-scale production.
  • the present invention uses all solid components of pulping and papermaking black liquor as raw materials, and obtains high-performance porous carbon composite materials through one-step carbonization. It is different from obtaining lignin from black liquor by separating, extracting and purifying it, and then adding template agents, activators, etc.
  • the traditional method of carbonizing holes has a short process route and simple operation.
  • the present invention utilizes the original sodium hydroxide, sodium salt, oligosaccharide, etc. in the black liquor solids as a template agent and activator for lignin carbonization pore creation and a source of alkaline material for CO 2 adsorption, without the need to add additional template agents and activators. and other alkaline species and alkaline materials, with low cost and high economic benefits.
  • the porous carbon composite material obtained by the present invention has both a porous structure for physical adsorption of CO2 and an alkaline species for chemical adsorption of CO2 . It does not require secondary treatment and can greatly increase the amount of CO2 adsorption. Moreover, porous carbon has a well-developed pore structure, mainly micropores and mesopores, has high specific surface area and pore volume, and is rich in surface oxygen functional groups, providing new ideas for the high-value utilization of pulping and papermaking black liquor, breaking through the traditional Limitations of incineration treatment.
  • the invention rapidly freezes in a uniformly stirred state, which can mix organic matter and inorganic matter evenly, facilitate uniform pore creation during later carbonization, and the ice crystals produced by freezing also serve as templates, making the obtained solids loose and porous, which is more beneficial to terminals. Many Formation of porous carbon structures.
  • Figure 1 is the CO 2 adsorption curve at 0°C of the biomass-based porous carbon composite material obtained in Example 3 of the present invention.
  • Figure 2 is a nitrogen adsorption and desorption curve of the biomass-based porous carbon composite material obtained in Example 3 of the present invention.
  • This application provides a biomass-based porous carbon composite material, which is obtained through arc treatment using pulping and papermaking black liquor solids as a precursor. It has a porous carbon structure that can physically adsorb CO 2 and an alkali that can chemically adsorb CO 2
  • the porous carbon structure uses lignin in the precursor as the carbon source, sodium hydroxide, sodium salt and small molecule carbohydrate degradation products in the precursor as templates and activators, and is carbonized by arc heat. And it is obtained by self-activation.
  • the alkaline species is obtained by arc thermal decomposition of sodium hydroxide and sodium salt in the precursor.
  • the porous carbon structure can be controlled by changing the carbonization conditions, such as carbonization time, arc current, etc.
  • This application also provides a method for preparing biomass-based porous carbon composite materials, including:
  • the black liquor solid is treated with arc to obtain a solid product
  • the solid product is ground to obtain a biomass-based porous carbon composite material.
  • the arc current during arc treatment is 10-1000A, and the treatment time is 1s-10min.
  • drying of pulping and papermaking black liquor into black liquor solids includes:
  • This application also provides the application of a biomass-based porous carbon composite material in CO 2 adsorption.
  • This application uses pulping and papermaking black liquor solids as the precursor and obtains porous carbon composite materials for CO 2 adsorption through one-step arc carbonization, avoiding the steps and costs of separating, extracting, and purifying lignin from the black liquor, and achieving By fully utilizing pulping and papermaking black liquor, the porous carbon composite material obtained has both physical sites and chemical sites for CO 2 adsorption and has excellent performance.
  • the thick black liquor produced by the sulfate pulping method in the pulping plant is used as the raw material, and the black liquor solid is made into a black liquor solid by the freeze-drying method, and then carbonized in a 10A arc zone under a carbon dioxide atmosphere for 10 minutes, and the solid product is ground to form a porous carbon composite Material; the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 11.05mmol/g.
  • the thick black liquor produced by the sulfate pulping method in the pulping plant is used as the raw material, and the black liquor solid is made into a black liquor solid by the freeze-drying method, and then carbonized in a 100A arc zone under a helium atmosphere for 1 minute, and the solid product is ground to form porous carbon.
  • Composite material; the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 13.99mmol/g.
  • the thick black liquor produced by the sulfate pulping method in the pulping plant is used as the raw material, and the black liquor solid is made into the black liquor solid by the vacuum drying method, and then in the neon Carbonize in a 200A arc zone for 30 seconds in an air atmosphere, and grind the solid product to form a porous carbon composite material; the CO 2 adsorption capacity of the porous carbon composite material at 0°C is 15.65mmol/g.
  • the thick black liquor produced by the sulfate pulping method in the pulping plant is used as the raw material, and the black liquor solid is made into a black liquor solid by the vacuum drying method, and then carbonized in the 1000A arc zone under an argon atmosphere for 1 second, and the solid product is ground, that is, porous carbon Composite material; the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 8.63mmol/g.
  • the thick black liquor produced by the pulping plant's caustic soda method is used as the raw material, and the black liquor solid is made into a black liquor solid by a vacuum drying method, and then carbonized in a 200A arc zone for 30 seconds in a carbon dioxide atmosphere, and the solid product is ground to form a porous carbon composite material ;
  • the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 12.98mmol/g.
  • the dilute black liquor produced by the pulping plant's caustic soda-anthraquinone method is used as the raw material, and the black liquor solid is made into a black liquor solid by a vacuum drying method, and then carbonized in a 200A arc zone under a carbon dioxide atmosphere for 30 seconds, and the solid product is ground to become porous.
  • Carbon composite material; the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 12.03mmol/g.
  • the dilute black liquor pulped by the laboratory organic solvent method is used as the raw material, and the black liquor solid is made into a black liquor solid by a vacuum drying method, and then carbonized in a 200A arc zone under a carbon dioxide atmosphere for 30 seconds, and the solid product is ground to form a porous carbon composite material ;
  • the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 5.53mmol/g.
  • the dilute black liquor produced by the chemical mechanical pulping method in the pulping plant is used as raw material, and the black liquor solid is made into a black liquor solid by a vacuum drying method, and then carbonized in a 200A arc zone for 30 seconds in a carbon dioxide atmosphere, and the solid product is ground to form a porous carbon composite Material; the CO 2 adsorption capacity of this porous carbon composite material at 0°C is 9.62mmol/g.
  • the black liquor solid is made into a black liquor solid using a vacuum drying method, and then carbonized in a 200A arc zone under a carbon dioxide atmosphere for 30 seconds, and the solid product is ground to form a porous carbon composite material;
  • the CO2 adsorption capacity of this porous carbon composite material at 0°C is 6.96mmol/g.
  • arc treatment can be implemented using equipment such as an electric arc furnace.
  • the arc area refers to the arc heat radiation area of the electric arc furnace, that is, the area where the solid black liquor is subjected to arc heat treatment.
  • the porous carbon composite material obtained by carbonization in the 100A arc zone for 1 minute under a helium atmosphere can isothermally adsorb 15.65mmol/g CO 2 at 0°C and 1bar pressure, and its porous carbon pore structure is well developed. , mainly micropores and mesopores, and the high specific surface area is as high as 2001.52m 2 /g.

Abstract

一种生物质基多孔碳复合材料及制备与在CO 2吸附中的应用，生物质基多孔碳复合材料以制浆造纸黑液固形物为前驱体，通过电弧处理后得到，具有可物理吸附CO 2的多孔碳结构、以及可化学吸附CO 2的碱性物种，所述多孔碳结构以所述前驱体中的木质素为碳源，以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂，受电弧热炭化并自活化后得到，所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。还涉及一种生物质基多孔碳复合材料在CO 2吸附中的应用。实现了制浆造纸黑液全利用，获得兼具CO 2吸附物理位点和化学位点的高性能多孔碳复合材料，避免从黑液中分离、提取、纯化木质素的步骤及成本。

Description

生物质基多孔碳复合材料及制备与在CO2吸附中的应用 技术领域
本发明涉及碳基复合材料，尤其是一种生物质基多孔碳复合材料及制备与在CO2吸附中的应用。
背景技术
利用可再生的生物质资源制备高品质生物炭是现如今的发展趋势和研究热点，生物炭一般通过热解炭化和水热炭化两种方法制备得到，生物质水热炭的炭化程度不及热解炭，一般只能应用于如水体污染物吸附剂等底端应用场合中，高端应用往往需要二次热解炭化。由于生物质的特征属性，其在炭化过程中一般需要借助模板剂造孔，所得炭化产物还需进一步活化，以获得高端应用所需的性能。总体而言，生物质炭化存在工艺过程复杂、能耗高、副产物多(VOC、有机废水等)、成本高、产品需进一步精制等问题，严重制约了其规模化生产与应用。
木质素是木质纤维类生物质的三大组成之一，其碳含量高，且丰富的芳香结构使得其更易制备高性能生物炭，利用工业木质素为原料制备生物炭能同步实现工业废弃物的无害化处理与高值化利用，意义重大。
现有技术中，木质素基生物炭大多以纯化的工业木质素为原料，通过添加模板剂、活化剂制备得到(期刊论文ACS Sustainable Chemistry&Engineering 6(2018)10454-10462、期刊论文ChemSusChem 8(2015)428-432、学位论文“模板法制备木质素基中孔碳材料及电化学性能研究[D]，中国林业科学研究院，2018”、学位论文“造纸黑液木质素活性炭的制备、表征及吸附应用[D]，山东大学，2018”、学位论文“以木质素为碳源介孔碳及其复合材料制备和电化学中的应用[D]，浙江工业大学，2015”、专利ZL201210207757.9、专利ZL201811376052.3等)，忽视了工业木质素的来源问题，避开了从制浆造纸黑液中提取、纯化木质素的成本及使用化学药剂带来的环境负担。专利CN202010522079.X、专利CN201610697874.6和专利ZL201210207757.9虽然提及了黑液木质素多孔碳，但也只是以制浆造纸黑液为原材料，实质还是先分离得到木质素，再进行后续的多孔碳制备。虽然，木质素是制浆造纸黑液的主要固形物成分，但制浆造纸黑液固形物中还包含其他有机质(碳水化合物降解物)和无机成分，现有的木质素多孔碳制备都忽略了对制浆造纸黑液的全组分直接利用。
CO2在多孔碳表面的吸附得益于其比表面积和孔体积，即主要利用多孔碳中的微孔和介孔进行物理吸附，通过调控多孔碳的制备工艺可以获得更多的微孔和介孔结构，进而提高CO2的吸附量，但单纯的物理吸附存在吸附瓶颈、难以大幅突破。为进一步增加多孔碳对CO2的吸附量，通常在多孔碳中引入杂原子(S、N、P等)创造碱性位点，或与其他碱性材料组合成复合材料，使CO2更易吸附在多孔碳的表面；然而这些额外的试剂和材料无疑增加了多孔碳吸附CO2的成本。
发明内容
针对现有技术的不足，本发明提供一种生物质基多孔碳复合材料及制备与在CO2吸附中的应用，目的是实现制浆造纸黑液全利用，获得兼具CO2吸附物理位点和化学位点的高性能多孔碳复合材料，避免从黑液中分离、提取、纯化木质素的步骤及成本。
本发明采用的技术方案如下：
本发明提供了一种生物质基多孔碳复合材料，以制浆造纸黑液固形物为前驱体，通过电弧处理后得到，具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种，所述多孔碳结构以所述前驱体中的木质素为碳源，以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂，受电弧热炭化并自活化后得到，所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
所述多孔碳结构可通过改变炭化工况进行调控。
本发明还提供了一种所述的生物质基多孔碳复合材料的制备方法，包括：
将制浆造纸黑液干燥成黑液固形物；
在惰性气体保护下，电弧处理所述黑液固形物，得到固体产物；
将所述固体产物研磨，即得生物质基多孔碳复合材料。
电弧处理过程中电弧电流为10-1000A，处理时间为1s-10min。
所述将制浆造纸黑液干燥成黑液固形物，包括：
将制浆造纸黑液搅拌均匀，在搅拌状态下将制浆造纸黑液浸入液氮中，使制浆造纸黑液快速冷冻，然后采用冷冻干燥法进行干燥，获得黑液固形物。
所述制浆造纸黑液为烧碱法制浆黑液、烧碱-蒽醌法制浆黑液、硫酸盐法制浆黑液、有机溶剂法制浆黑液、化学机械法制浆黑液、纸浆洗涤所得黑液中的至少一种。
所述制浆造纸黑液为实验室制浆黑液、制浆厂稀黑液、制浆厂浓黑液中的至少一种。
本发明还提供一种所述的生物质基多孔碳复合材料在CO2吸附中的应用。
本发明的有益效果如下：
本发明利用电弧产生的高温区实现生物质炭化，相比于传统的热解炭化和水热炭化法相比，具有能耗低、效率高、能极快速实现生物质炭化等优势，且工艺灵活、操作简单、设备占地面积小，非常适用于规模化生产。
本发明以制浆造纸黑液固形物全组分为原料，一步炭化即得高性能多孔碳复合材料，区别于从黑液中分离、提取、纯化得到木质素，再添加模板剂、活化剂等实现炭化造孔的传统方法，工艺路线短、操作简单。
本发明利用黑液固形物中原有的氢氧化钠、钠盐、寡糖等作为木质素炭化造孔的模板剂和活化剂及CO2吸附的碱性物质来源，无需额外添加模板剂和活化剂及其他碱性物种和碱性材料，成本低、经济效益高。
本发明所得多孔碳复合材料兼具CO2物理吸附的多孔结构及CO2化学吸附的碱性物种，无需二次处理，能大幅提高CO2吸附量。且多孔碳孔隙结构发达，以微孔和介孔为主，具有高比表面积和孔容，富含表面氧官能团，为制浆造纸黑液的高值化利用提供了新的思路，突破了传统焚烧处理法的局限。
本发明在均匀搅拌状态下快速冷冻，能使有机物和无机物混合均匀，便于后期炭化时均匀造孔，且冷冻产生的冰晶也具有模板的作用，使获得的固形物疏松多孔，更有益于终端多 孔碳结构的形成。
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。
附图说明
图1是本发明实施例3所得生物质基多孔碳复合材料在0℃时的CO2吸附曲线。
图2是本发明实施例3所得生物质基多孔碳复合材料的氮气吸脱附曲线。
具体实施方式
以下结合附图说明本发明的具体实施方式。
本申请提供一种生物质基多孔碳复合材料，以制浆造纸黑液固形物为前驱体，通过电弧处理后得到，具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种，所述多孔碳结构以所述前驱体中的木质素为碳源，以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂，受电弧热炭化并自活化得到，所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
所述多孔碳结构可通过改变炭化工况进行调控，例如炭化时长、电弧电流等。
本申请还提供一种生物质基多孔碳复合材料的制备方法，包括：
将制浆造纸黑液干燥成黑液固形物；
在惰性气体保护下，电弧处理所述黑液固形物，得到固体产物；
将所述固体产物研磨，即得生物质基多孔碳复合材料。
其中，电弧处理过程中电弧电流为10-1000A，处理的时间为1s-10min。
其中，所述将制浆造纸黑液干燥成黑液固形物，包括：
将制浆造纸黑液搅拌均匀，在搅拌状态下将制浆造纸黑液浸入液氮中，使制浆造纸黑液快速冷冻，然后采用冷冻干燥法进行干燥，获得黑液固形物。
本申请还提供一种生物质基多孔碳复合材料在CO2吸附中的应用。
本申请以制浆造纸黑液固形物为前驱体、通过电弧一步炭化获得用于CO2吸附的多孔碳复合材料，避免了从黑液中分离、提取、纯化木质素的步骤及成本，实现了制浆造纸黑液全利用，获得的多孔碳复合材料兼具CO2吸附物理位点和化学位点，性能优异。
以下以具体实施例进一步说明本申请生物质基多孔碳复合材料的制备方法的技术方案。
实施例1：
以制浆厂硫酸盐法制浆浓黑液为原料，采用冷冻干燥法将其制成黑液固形物，而后在二氧化碳氛围下于10A电弧区炭化10min，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为11.05mmol/g。
实施例2：
以制浆厂硫酸盐法制浆浓黑液为原料，采用冷冻干燥法将其制成黑液固形物，而后在氦气氛围下于100A电弧区炭化1min，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为13.99mmol/g。
实施例3：
以制浆厂硫酸盐法制浆浓黑液为原料，采用真空干燥法将其制成黑液固形物，而后在氖 气氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为15.65mmol/g。
实施例4：
以制浆厂硫酸盐法制浆浓黑液为原料，采用真空干燥法将其制成黑液固形物，而后在氩气氛围下于1000A电弧区炭化1s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为8.63mmol/g。
实施例5：
以制浆厂烧碱法制浆浓黑液为原料，采用真空干燥法将其制成黑液固形物，而后在二氧化碳氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为12.98mmol/g。
实施例6：
以制浆厂烧碱-蒽醌法制浆稀黑液为原料，采用真空干燥法将其制成黑液固形物，而后在二氧化碳氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为12.03mmol/g。
实施例7：
以实验室有机溶剂法制浆稀黑液为原料，采用真空干燥法将其制成黑液固形物，而后在二氧化碳氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为5.53mmol/g。
实施例8：
以制浆厂化学机械法制浆稀黑液为原料，采用真空干燥法将其制成黑液固形物，而后在二氧化碳氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为9.62mmol/g。
实施例9：
以制浆厂纸浆洗涤所得稀黑液为原料，采用真空干燥法将其制成黑液固形物，而后在二氧化碳氛围下于200A电弧区炭化30s，将固体产物研磨，即得多孔碳复合材料；该多孔碳复合材料在0℃时的CO2吸附量为6.96mmol/g。
以上各实施例中，电弧处理可采用电弧炉等设备进行具体实施，电弧区即指采用电弧炉的电弧热辐射区域，也即黑液固形物受电弧热处理的区域。
如图1和图2所示，在氦气氛围下于100A电弧区炭化1min所得多孔碳复合材料能在0℃时于1bar压力下等温吸附15.65mmol/g的CO2，其多孔碳孔隙结构发达，以微孔和介孔为主，且高比表面积高达2001.52m2/g。
此外，除非权利要求中明确说明，本发明所述处理元素和序列的顺序、数字字母的使用、或其他名称的使用，并非用于限定本申请流程和方法的顺序；尽管上述披露中通过各种示例讨论了一些目前认为有用的发明实施例，但应当理解的是，该类细节仅起到说明的目的，附加的权利要求并不仅限于披露的实施例，相反，权利要求旨在覆盖所有符合本申请实施例实质和范围的修正和等价组合；例如，虽然以上所描述的系统组件可以通过硬件设备实现，但是也可以只通过软件的解决方案得以实现，如在现有的服务器或移动设备上安装所描述的系统。
最后，应当理解的是，本发明中所述实施例仅用以说明本发明实施例的原则；其他的变 形也可能属于本发明的范围；因此，作为示例而非限制，本发明实施例的替代配置可视为与本发明的教导一致；相应地，本发明的实施例不限于本发明明确介绍和描述的实施例。

Claims (8)

  1. 一种生物质基多孔碳复合材料，其特征在于，以制浆造纸黑液固形物为前驱体，通过电弧处理后得到，具有可物理吸附CO2的多孔碳结构、以及可化学吸附CO2的碱性物种，所述多孔碳结构以所述前驱体中的木质素为碳源，以前驱体中的氢氧化钠、钠盐及小分子碳水化合物降解物为模板剂和活化剂，受电弧热炭化并自活化后得到，所述碱性物种为前驱体中的氢氧化钠、钠盐受电弧热分解后得到。
  2. 根据权利要求1所述的生物质基多孔碳复合材料，其特征在于，所述多孔碳结构可通过改变炭化工况进行调控。
  3. 一种如权利要求1所述的生物质基多孔碳复合材料的制备方法，其特征在于，包括：
    将制浆造纸黑液干燥成黑液固形物；
    在惰性气体保护下，电弧处理所述黑液固形物，得到固体产物；
    将所述固体产物研磨，即得生物质基多孔碳复合材料。
  4. 根据权利要求3所述的生物质基多孔碳复合材料的制备方法，其特征在于，电弧处理过程中电弧电流为10-1000A，处理时间为1s-10min。
  5. 根据权利要求3所述的生物质基多孔碳复合材料的制备方法，其特征在于，所述将制浆造纸黑液干燥成黑液固形物，包括：
    将制浆造纸黑液搅拌均匀，在搅拌状态下将制浆造纸黑液浸入液氮中，使制浆造纸黑液快速冷冻，然后采用冷冻干燥法进行干燥，获得黑液固形物。
  6. 根据权利要求3所述的生物质基多孔碳复合材料的制备方法，其特征在于，所述制浆造纸黑液为烧碱法制浆黑液、烧碱-蒽醌法制浆黑液、硫酸盐法制浆黑液、有机溶剂法制浆黑液、化学机械法制浆黑液、纸浆洗涤所得黑液中的至少一种。
  7. 根据权利要求3所述的生物质基多孔碳复合材料的制备方法，其特征在于，所述制浆造纸黑液为实验室制浆黑液、制浆厂稀黑液、制浆厂浓黑液中的至少一种。
  8. 一种如权利要求1所述的生物质基多孔碳复合材料在CO2吸附中的应用。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1052347A (zh) * 1990-03-27 1991-06-19 核工业西南物理研究院 等离子体处理纸浆废液回收化学物质的新方法
CN101460405A (zh) * 2006-04-05 2009-06-17 弗雷特等离子实验室公司 利用来自电弧的波能处理液体的系统、方法和装置
JP2009299196A (ja) * 2007-06-14 2009-12-24 Hitoshi Murakami 黒液処理方法及び黒液処理装置並びに発電システム
CN106622137A (zh) * 2017-01-03 2017-05-10 南京林业大学 一种烟气脱汞吸附剂的生产方法
WO2020157379A1 (en) * 2019-01-28 2020-08-06 Lappeenrannan-Lahden Teknillinen Yliopisto Lut Method for producing activated carbon
CN113816374A (zh) * 2021-09-29 2021-12-21 海南金海浆纸业有限公司 一种利用制浆黑液制备高吸附性能活性炭的方法
CN115445588A (zh) * 2022-08-15 2022-12-09 东南大学 生物质基多孔碳复合材料及制备与在co2吸附中的应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045535A (zh) * 2006-03-30 2007-10-03 农光再 造纸制浆黑液浓缩炭化生产活性炭
JP5062593B2 (ja) * 2007-12-03 2012-10-31 独立行政法人産業技術総合研究所 リグニンを原料とする炭素微粒子及びその製造方法
CN105633380A (zh) * 2016-03-04 2016-06-01 中国科学院新疆理化技术研究所 一种锂离子电池淀粉基多孔硬炭负极材料的制备方法
CN107452960A (zh) * 2017-07-06 2017-12-08 陕西科技大学 一种造纸黑液转化多孔碳钠离子电池负极材料的制备方法
CN109809428A (zh) * 2017-11-20 2019-05-28 中国科学院大连化学物理研究所 一种无机载体表面负载碳层的复合材料及其制备方法
CN108715446A (zh) * 2018-07-04 2018-10-30 北京林业大学 一种多中孔木质素基活性炭的制备方法
CN110394155A (zh) * 2019-08-29 2019-11-01 浙江理工大学 一种碳纳米管修饰的改性活性炭吸附剂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1052347A (zh) * 1990-03-27 1991-06-19 核工业西南物理研究院 等离子体处理纸浆废液回收化学物质的新方法
CN101460405A (zh) * 2006-04-05 2009-06-17 弗雷特等离子实验室公司 利用来自电弧的波能处理液体的系统、方法和装置
JP2009299196A (ja) * 2007-06-14 2009-12-24 Hitoshi Murakami 黒液処理方法及び黒液処理装置並びに発電システム
CN106622137A (zh) * 2017-01-03 2017-05-10 南京林业大学 一种烟气脱汞吸附剂的生产方法
WO2020157379A1 (en) * 2019-01-28 2020-08-06 Lappeenrannan-Lahden Teknillinen Yliopisto Lut Method for producing activated carbon
CN113816374A (zh) * 2021-09-29 2021-12-21 海南金海浆纸业有限公司 一种利用制浆黑液制备高吸附性能活性炭的方法
CN115445588A (zh) * 2022-08-15 2022-12-09 东南大学 生物质基多孔碳复合材料及制备与在co2吸附中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAOYU MA, LIU TINGTING, CUI SUPING, WANG YALI, GUO, QIN HONGXIA, QIN NAMAN: "Research Progress on Preparation and Resource Utilization of Biomass Materials", JOURNAL OF BEIJING UNIVERSITY OF TECHNOLOGY, vol. 46, no. 10, 10 October 2020 (2020-10-10), pages 1204 - 1212, XP093140064 *

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