CN115976866A - Method for separating components of lignocellulose biomass by pretreatment of lignocellulose with organic solvent - Google Patents
Method for separating components of lignocellulose biomass by pretreatment of lignocellulose with organic solvent Download PDFInfo
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- CN115976866A CN115976866A CN202211467403.8A CN202211467403A CN115976866A CN 115976866 A CN115976866 A CN 115976866A CN 202211467403 A CN202211467403 A CN 202211467403A CN 115976866 A CN115976866 A CN 115976866A
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- lignin
- triethylene glycol
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- hemicellulose
- filter residue
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 12
- 239000003960 organic solvent Substances 0.000 title claims abstract description 7
- 229920005610 lignin Polymers 0.000 claims abstract description 52
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- 229920002678 cellulose Polymers 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 13
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 9
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229920001221 xylan Polymers 0.000 claims abstract description 9
- 150000004823 xylans Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002154 agricultural waste Substances 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 2
- 239000012296 anti-solvent Substances 0.000 claims 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000000605 extraction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 241000609240 Ambelania acida Species 0.000 description 5
- 239000010905 bagasse Substances 0.000 description 5
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 241000209046 Pennisetum Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
技术领域：Technical field:
本发明涉及生物质能源转化利用技术领域，具体涉及一种有机溶剂预处理木质纤维素类生物质组分分离的方法。The invention relates to the technical field of biomass energy conversion and utilization, in particular to a method for separating components of lignocellulosic biomass by organic solvent pretreatment.
背景技术：Background technique:
木质纤维素类生物质是公认的可通过生物炼制过程转化为燃料、材料和化学品的可再生资源。然而，组成木质纤维素类生物质的纤维素、半纤维素和木质素组分之间相互联接，形成致密和复杂的空间三维结构，各组分难以有效的直接转化利用，往往先需要通过预处理手段将组分分离，以利于各组分后续的转化利用，提高生物质三大组分的利用效率，进而实现木质纤维素类生物质的生物炼制过程。Lignocellulosic biomass is a recognized renewable resource that can be converted into fuels, materials, and chemicals through biorefinery processes. However, the cellulose, hemicellulose, and lignin components that make up lignocellulosic biomass are interconnected to form a dense and complex three-dimensional structure. It is difficult to effectively transform and utilize each component directly, and often requires pre-treatment. The treatment method separates the components to facilitate the subsequent conversion and utilization of each component, improve the utilization efficiency of the three major components of biomass, and then realize the biorefinery process of lignocellulosic biomass.
近年来，有机溶剂预处理是实现木质纤维素类生物质组分分离的主要方法之一。专利CN106674538A公开了一种从竹材中分离提取纤维素、半纤维素降解糖和木质素的方法，提供了在酸作用下，γ-戊内酯水溶液为溶剂的木质纤维素组分分离工艺；专利ZL201510813243.1公开了一种木质纤维素组分分离的绿色工艺，通过辐照预处理生物质，耦合四氢呋喃或γ-戊内酯反应，实现了木质纤维素组分的分离；专利ZL201410006095.8公开了一种以高沸醇为溶剂常压超声波辅助制备纤维素和木质素的方法，在130℃～140℃的高沸醇溶液中蒸煮分离生物质中的纤维素和木质素；专利ZL202010101379.0公开了一种离子液体-高沸醇复合体系高效分离木质纤维素并酶解的方法，通过多步复合预处理的方式，进一步提高生物质的组分分离效率。虽然通过有机溶剂组分分离的方法可有效打破木质纤维素结构，实现组分的部分或全部分离，但高效的组分分离技术往往需要较高的反应温度(>150℃)，多步预处理方法带来溶剂循环，半纤维素和木质素分离等过程复杂的工艺步骤，在实际应用过程中易产生高耗能和高环境压力的问题。In recent years, organic solvent pretreatment is one of the main methods to realize the separation of lignocellulosic biomass components. Patent CN106674538A discloses a method for separating and extracting cellulose and hemicellulose from bamboo to degrade sugar and lignin, and provides a lignocellulose component separation process under the action of acid with γ-valerolactone aqueous solution as a solvent; patent ZL201510813243.1 discloses a green process for the separation of lignocellulosic components, which realizes the separation of lignocellulose components by irradiating pretreated biomass and coupling THF or γ-valerolactone reaction; patent ZL201410006095.8 discloses A method for preparing cellulose and lignin with high-boiling alcohol as a solvent and atmospheric pressure ultrasonic assistance, cooking and separating cellulose and lignin in biomass in a high-boiling alcohol solution at 130°C to 140°C; patent ZL202010101379.0 Disclosed is an ionic liquid-high boiling alcohol composite system for efficiently separating lignocellulose and enzymatically hydrolyzing it, further improving the separation efficiency of biomass components through multi-step composite pretreatment. Although the method of organic solvent component separation can effectively break the lignocellulose structure and realize partial or complete separation of components, efficient component separation technology often requires high reaction temperature (>150°C), multi-step pretreatment The method brings complex process steps such as solvent circulation, hemicellulose and lignin separation, and problems of high energy consumption and high environmental pressure are likely to occur in the actual application process.
发明内容：Invention content:
本发明解决了现有技术存在的问题，提供一种有机溶液预处理木质纤维素类生物质组分分离的方法，利用三乙二醇酸性溶液体系，在温和环境下完成对生物质原料半纤维素的拆解和木质素的溶出，并高效保留纤维素组分滤渣，打破木质纤维素致密结构，实现木质纤维素类生物质中各组分的分离。The present invention solves the problems existing in the prior art, and provides a method for the separation of lignocellulosic biomass components in organic solution pretreatment, using triethylene glycol acidic solution system to complete the semi-fiber separation of biomass raw materials in a mild environment Dismantling of lignin and dissolution of lignin, and efficiently retaining the filter residue of cellulose components, breaking the dense structure of lignocellulose, and realizing the separation of various components in lignocellulosic biomass.
本发明的目的是提供一种有机溶剂预处理木质纤维素类生物质组分分离的方法，包括如下步骤：将木质纤维素类生物质和三乙二醇溶液加入反应容器中，所述的三乙二醇溶液为含有酸性催化剂的三乙二醇水溶液，80℃～140℃下反应0.1～6h后，固液分离，得到含纤维素组分的滤渣和溶有半纤维素、木质素的滤液；在滤液中加入反向溶剂，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收反向溶剂和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入盐酸溶液中搅拌后，固液分离，得到木质素组分残渣以及含有木糖和木聚糖的滤液。The object of the present invention is to provide a method for separating the components of lignocellulosic biomass with organic solvent pretreatment, comprising the following steps: adding lignocellulosic biomass and triethylene glycol solution into a reaction vessel, the three Ethylene glycol solution is an aqueous solution of triethylene glycol containing an acidic catalyst. After reacting at 80°C to 140°C for 0.1 to 6 hours, the solid and liquid are separated to obtain a filter residue containing cellulose components and a filtrate in which hemicellulose and lignin are dissolved. Add reverse solvent in filtrate, solid-liquid separation, obtain the filter residue that contains lignin and hemicellulose component, filtrate vacuum distillation, reclaim reverse solvent and triethylene glycol solution; Will contain lignin and hemicellulose After the filter residue of the components is added into the hydrochloric acid solution and stirred, the solid and liquid are separated to obtain the residue of the lignin component and a filtrate containing xylose and xylan.
优选地，所述的木质纤维素类生物质和三乙二醇溶液的质量体积比为1：(8～20)g/mL。Preferably, the mass volume ratio of the lignocellulosic biomass to the triethylene glycol solution is 1: (8-20) g/mL.
优选地，所述的三乙二醇溶液中三乙二醇的体积分数为50％～100％，酸性催化剂的浓度为0.05～0.20mol/L。Preferably, the volume fraction of triethylene glycol in the triethylene glycol solution is 50%-100%, and the concentration of the acidic catalyst is 0.05-0.20 mol/L.
优选地，所述的酸性催化剂为可溶的酸或强酸弱碱盐，酸选自硫酸、盐酸、甲酸和甲基苯磺酸中的一种，强酸弱碱盐选自硫酸铁、三氯化铝和硝酸铜中的一种。Preferably, the acidic catalyst is a soluble acid or a strong acid and weak base salt, the acid is selected from one of sulfuric acid, hydrochloric acid, formic acid and toluenesulfonic acid, and the strong acid and weak base salt is selected from ferric sulfate, trichloride One of aluminum and copper nitrate.
优选地，在滤液中加入8倍滤液体积的反向溶剂，所述的反向溶剂为乙醚。Preferably, 8 times the volume of the filtrate is added to the filtrate as a reverse solvent, and the reverse solvent is diethyl ether.
优选地，所述的含木质素和半纤维素组分的滤渣与盐酸溶液的质量体积比为1：10g/mL，盐酸溶液的质量浓度为1％。Preferably, the mass volume ratio of the filter residue containing lignin and hemicellulose components to the hydrochloric acid solution is 1:10 g/mL, and the mass concentration of the hydrochloric acid solution is 1%.
优选地，所述的木质纤维素类生物质的粒度为0.5～3mm。Preferably, the particle size of the lignocellulosic biomass is 0.5-3mm.
优选地，所述的木质纤维素类生物质为至少含有纤维素和木质素的能源植物或废弃物。能源植物包括狼尾草等。Preferably, the lignocellulosic biomass is an energy plant or waste containing at least cellulose and lignin. Energy plants include Pennisetum and the like.
进一步优选，所述的废弃物为林业废弃物、农业废弃物或加工废弃物。林业废弃物包括木屑等，农业废弃物包括秸秆等，加工废弃物为糖厂或酒厂加工废弃物，包括甘蔗渣、糠醛渣等。Further preferably, the waste is forestry waste, agricultural waste or processing waste. Forestry waste includes sawdust, etc., agricultural waste includes straw, etc., and processing waste is sugar factory or winery processing waste, including bagasse, furfural slag, etc.
本发明与现有技术相比，具有如下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明利用酸性三乙二醇优异的溶解木质素能力，在温和条件下组分分离木质纤维素类生物质，实现了以滤渣形式分离回收原料纤维素组分和木质素组分，并以溶解木糖和木聚糖的形式分离回收半纤维素组分。(1) The present invention utilizes the excellent lignin-dissolving ability of acidic triethylene glycol to separate lignocellulosic biomass under mild conditions, and realize the separation and recovery of raw cellulose components and lignin components in the form of filter residues, The hemicellulose fraction was separated and recovered in the form of dissolved xylose and xylan.
(2)本发明所得富含纤维素组分滤渣纤维素组分含量高，易于酶解转化利用。(2) The cellulose-rich component filter residue obtained in the present invention has a high content of cellulose component and is easy to enzymatically transform and utilize.
(3)本发明中高沸点三乙二醇的生物相容性好，反应过程压力低。(3) The biocompatibility of the high-boiling-point triethylene glycol in the present invention is good, and the reaction process pressure is low.
(4)本发明适应原料范围广，所用溶剂可循环使用，能有效降低成本。(4) The present invention is suitable for a wide range of raw materials, and the used solvent can be recycled, which can effectively reduce the cost.
具体实施方式：Detailed ways:
以下实施例是对本发明的进一步说明，而不是对本发明的限制。The following examples are to further illustrate the present invention, rather than limit the present invention.
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。除特别说明，本文中的实验材料和试剂均为本技术领域常规市购产品。Unless otherwise defined, all technical terms used hereinafter have the same meanings as commonly understood by those skilled in the art. The terminology used herein is only for the purpose of describing specific embodiments, and is not intended to limit the protection scope of the present invention. Unless otherwise specified, the experimental materials and reagents herein are conventional commercially available products in the technical field.
实施例1Example 1
以2g粒度0.5mm的甘蔗渣(含纤维素40.1％、半纤维素24.3％、木质素18.2％)为原料，按原料和三乙二醇溶液的质量体积比1：8g/mL的量加入硫酸浓度为0.2mol/L，三乙二醇体积分数100％的三乙二醇溶液于反应器中；100℃下反应0.5h后，固液分离，得到纤维素含量71.8％的滤渣1.02g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为80.1％)；滤液中加入8倍滤液体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收乙醚和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.22g，以可溶性木糖和木聚糖的形式回收43.3％的半纤维素组分。Using 2g of bagasse with a particle size of 0.5mm (containing 40.1% cellulose, 24.3% hemicellulose, and 18.2% lignin) as raw material, add sulfuric acid in an amount of 1:8 g/mL by mass volume ratio of raw material and triethylene glycol solution Concentration is 0.2mol/L, and the triethylene glycol solution of triethylene glycol volume fraction 100% is in reactor; After reacting at 100 ℃ for 0.5h, solid-liquid separation obtains cellulose content 71.8% filter residue 1.02g (bottom Concentration of 5%, CTec2 enzyme of 20FPU/g cellulose, 50 ℃ enzymolysis 72h, enzymolysis rate is 80.1%); Add 8 times the ether of filtrate volume in filtrate, solid-liquid separation, obtain lignin and hemicellulose The filter residue of the component, the filtrate is distilled under reduced pressure, and ether and triethylene glycol solution are recovered; the filter residue containing lignin and hemicellulose components is added to a dilute hydrochloric acid solution with a mass concentration of 1%, and the mass concentration of the filter residue and the dilute hydrochloric acid solution The volume ratio was 1:10g/mL. After stirring at 60°C for 2h, solid-liquid separation was performed to obtain 0.22g lignin filter residue, and 43.3% of the hemicellulose component was recovered in the form of soluble xylose and xylan.
对比例1Comparative example 1
对比例1的实施过程同实施例1，区别在于用乙二醇替代实施例1中使用的三乙二醇。The implementation process of Comparative Example 1 is the same as that of Example 1, except that the triethylene glycol used in Example 1 is replaced with ethylene glycol.
对比例2Comparative example 2
对比例2的实施过程同实施例1，区别在于用聚乙二醇400替代实施例1中使用的三乙二醇。The implementation process of Comparative Example 2 is the same as that of Example 1, except that polyethylene glycol 400 is used to replace the triethylene glycol used in Example 1.
对比例3Comparative example 3
对比例3的实施过程同实施例1，区别在于用乙醇替代实施例1中使用的三乙二醇。The implementation process of Comparative Example 3 is the same as that of Example 1, except that the triethylene glycol used in Example 1 is replaced with ethanol.
对比例4Comparative example 4
对比例4的实施过程同实施例1，区别在于用丙三醇替代实施例1中使用的三乙二醇。The implementation process of Comparative Example 4 is the same as that of Example 1, except that the triethylene glycol used in Example 1 is replaced with glycerol.
实施例1与对比例1-4的滤渣、木质素回收量如表1所示：The filter residue of embodiment 1 and comparative example 1-4, lignin recovery amount are as shown in table 1:
表1Table 1
由上表可知，三乙二醇溶液滤渣具有最高的纤维素含量和最高的纤维素酶解率，说明三乙二醇溶液与对比醇溶液相比在木质纤维素类生物质组分分离性能上具有明显优势。It can be seen from the above table that the triethylene glycol solution filter residue has the highest cellulose content and the highest cellulose enzymatic hydrolysis rate, indicating that the triethylene glycol solution is more effective in the separation of lignocellulosic biomass components than the comparison alcohol solution. has obvious advantages.
实施例2Example 2
以2g粒度0.5mm的甘蔗渣(含纤维素40.1％、半纤维素24.3％、木质素18.2％)为原料，按原料和三乙二醇溶液的质量体积比1：8g/mL的量加入硫酸浓度为0.05mol/L，三乙二醇体积分数50％的三乙二醇溶液于反应器中；80℃下反应6h后，固液分离，得到纤维素含量54.5％的滤渣1.36g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为43.3％)；滤液中加入8倍滤液体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收乙醚和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.16g，以可溶性木糖和木聚糖的形式回收30.8％的半纤维素组分。Using 2g of bagasse with a particle size of 0.5mm (containing 40.1% cellulose, 24.3% hemicellulose, and 18.2% lignin) as raw material, add sulfuric acid in an amount of 1:8 g/mL by mass volume ratio of raw material and triethylene glycol solution Concentration is 0.05mol/L, and the triethylene glycol solution of triethylene glycol volume fraction 50% is in reactor; After reacting 6h under 80 ℃, solid-liquid separation obtains the filter residue 1.36g of cellulose content 54.5% (substrate Concentration 5%, CTec2 enzyme of 20FPU/g cellulose, 50 ℃ enzymolysis 72h, enzymolysis rate is 43.3%); Add 8 times the ether of filtrate volume in filtrate, solid-liquid separation, obtain the group containing lignin and hemicellulose The filter residue that divides, filtrate vacuum distillation, recovery ether and triethylene glycol solution; The filter residue that will contain lignin and hemicellulose component is added in the dilute hydrochloric acid solution that mass concentration is 1%, the mass volume of filter residue and dilute hydrochloric acid solution The ratio was 1:10g/mL, after stirring at 60°C for 2h, solid-liquid separation was performed to obtain 0.16g of lignin filter residue, and 30.8% of the hemicellulose component was recovered in the form of soluble xylose and xylan.
实施例3Example 3
以2g粒度3.0mm的甘蔗渣(含纤维素40.1％、半纤维素24.3％、木质素18.2％)为原料，按原料和三乙二醇溶液的质量体积比1：20g/mL的量加入硫酸浓度为0.2mol/L，三乙二醇体积分数100％的三乙二醇溶液于反应器中；140℃下反应0.1h后，固液分离，得到纤维素含量86.9％的滤渣0.78g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为88.4％)；滤液中加入8倍体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收乙醚和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.23g，以可溶性木糖和木聚糖的形式回收46.7％的半纤维素组分。Using 2g of bagasse with a particle size of 3.0mm (containing 40.1% cellulose, 24.3% hemicellulose, and 18.2% lignin) as raw material, add sulfuric acid in an amount of 1:20 g/mL by mass volume ratio of raw material and triethylene glycol solution Concentration is 0.2mol/L, and the triethylene glycol solution of triethylene glycol volume fraction 100% is in reactor; After reacting 0.1h under 140 ℃, solid-liquid separation obtains the filter residue 0.78g of cellulose content 86.9% (bottom concentration of 5%, CTec2 enzyme of 20FPU/g cellulose, enzymolysis at 50°C for 72h, enzymolysis rate was 88.4%); 8 times volume of ether was added to the filtrate, and solid-liquid separation was carried out to obtain lignin and hemicellulose-containing group The filter residue that divides, filtrate vacuum distillation, recovery ether and triethylene glycol solution; The filter residue that will contain lignin and hemicellulose component is added in the dilute hydrochloric acid solution that mass concentration is 1%, the mass volume of filter residue and dilute hydrochloric acid solution The ratio was 1:10g/mL, after stirring at 60°C for 2h, solid-liquid separation was performed to obtain 0.23g of lignin filter residue, and 46.7% of hemicellulose components were recovered in the form of soluble xylose and xylan.
实施例4Example 4
以2g粒度3.0mm的甘蔗渣(含纤维素40.1％、半纤维素24.3％、木质素18.2％)为原料，按原料和三乙二醇溶液的质量体积比1：20g/mL的量加入硫酸浓度为0.1mol/L，三乙二醇体积分数100％的三乙二醇溶液于反应器中；100℃下反应2h后，固液分离，得到纤维素含量90.5％的滤渣0.83g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为91.7％)；滤液中加入8倍滤液体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收反向溶剂和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.26g，以可溶性木糖和木聚糖的形式回收52.3％的半纤维素组分。Using 2g of bagasse with a particle size of 3.0mm (containing 40.1% cellulose, 24.3% hemicellulose, and 18.2% lignin) as raw material, add sulfuric acid in an amount of 1:20 g/mL by mass volume ratio of raw material and triethylene glycol solution Concentration is 0.1mol/L, and the triethylene glycol solution of triethylene glycol volume fraction 100% is in reactor; After reacting 2h under 100 ℃, solid-liquid separation obtains the filter residue 0.83g of cellulose content 90.5% (substrate Concentration 5%, CTec2 enzyme of 20FPU/g cellulose, 50 ℃ enzymolysis 72h, enzymolysis rate is 91.7%); Add 8 times the ether of filtrate volume to filtrate, solid-liquid separation, obtain the group containing lignin and hemicellulose The filter residue that divides, filtrate depressurization distillation, recovery reverse solvent and triethylene glycol solution; The filter residue that will contain lignin and hemicellulose component is added in the dilute hydrochloric acid solution that mass concentration is 1%, the mixture of filter residue and dilute hydrochloric acid solution The mass-volume ratio was 1:10g/mL. After stirring at 60°C for 2 hours, solid-liquid separation was performed to obtain 0.26 g of lignin filter residue, and 52.3% of hemicellulose components were recovered in the form of soluble xylose and xylan.
实施例5Example 5
以2g粒度0.5mm的糠醛渣(含纤维素36.4％、半纤维素1.2％、木质素34.5％)为原料，按原料和三乙二醇溶液的质量体积比1：10g/mL的量加入盐酸浓度为0.1mol/L，三乙二醇体积分数100％的三乙二醇溶液于反应器中；100℃下反应2h后，固液分离，得到纤维素含量79.9％的滤渣0.86g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为84.5％)；滤液中加入8倍滤液体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收反向溶剂和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.23g。Using 2g of furfural slag with a particle size of 0.5mm (containing 36.4% cellulose, 1.2% hemicellulose, and 34.5% lignin) as raw material, add hydrochloric acid in an amount of 1:10 g/mL by mass volume ratio of raw material and triethylene glycol solution Concentration is 0.1mol/L, and the triethylene glycol solution of triethylene glycol volume fraction 100% is in reactor; After reacting 2h under 100 ℃, solid-liquid separation obtains the filter residue 0.86g of cellulose content 79.9% (substrate Concentration 5%, CTec2 enzyme of 20FPU/g cellulose, enzymolysis at 50°C for 72h, enzymolysis rate 84.5%); add ether 8 times the volume of the filtrate to the filtrate, and separate solid and liquid to obtain the lignin and hemicellulose-containing group The filter residue that divides, filtrate depressurization distillation, recovery reverse solvent and triethylene glycol solution; The filter residue that will contain lignin and hemicellulose component is added in the dilute hydrochloric acid solution that mass concentration is 1%, the mixture of filter residue and dilute hydrochloric acid solution The mass volume ratio was 1:10g/mL, and after stirring at 60°C for 2h, the solid-liquid separation was carried out to obtain 0.23g of lignin filter residue.
实施例6Example 6
以2g粒度0.5mm的杨木(含纤维素46.1％、半纤维素12.7％、木质素24.4％)为原料，按原料和三乙二醇溶液的质量体积比1：10g/mL的量加入氯化铝浓度为0.1mol/L，三乙二醇体积分数100％的三乙二醇溶液于反应器中；100℃下反应2h后，固液分离，得到纤维素含量64.8％的滤渣1.32g(底物浓度5％，20FPU/g纤维素的CTec2酶，50℃酶解72h，酶解率为55.3％)；滤液中加入8倍滤液体积的乙醚，固液分离，得到含木质素和半纤维素组分的滤渣，滤液减压蒸馏，回收乙醚和三乙二醇溶液；将含木质素和半纤维素组分的滤渣加入质量浓度为1％的稀盐酸溶液中，滤渣与稀盐酸溶液的质量体积比为1:10g/mL，60℃搅拌2h后，固液分离，得到木质素滤渣0.15g，以可溶性木糖和木聚糖的形式回收31.6％的半纤维素组分。Using 2g of poplar wood with a particle size of 0.5mm (containing 46.1% cellulose, 12.7% hemicellulose, and 24.4% lignin) as raw material, chlorine was added in an amount of 1:10 g/mL by mass volume ratio of raw material and triethylene glycol solution. The aluminum chloride concentration is 0.1mol/L, and the triethylene glycol solution of the triethylene glycol volume fraction 100% is in the reactor; After reacting at 100 ℃ for 2h, the solid-liquid separation obtains the filter residue 1.32g of the cellulose content 64.8% ( Substrate concentration 5%, CTec2 enzyme of 20FPU/g cellulose, enzymolysis at 50°C for 72h, enzymolysis rate 55.3%); add 8 times the volume of diethyl ether to the filtrate, and separate solid and liquid to obtain lignin and hemifiber The filter residue of the lignin component, the filtrate is distilled under reduced pressure, and the ether and triethylene glycol solution are reclaimed; the filter residue containing the lignin and hemicellulose components is added in a dilute hydrochloric acid solution with a mass concentration of 1%, and the mixture of the filter residue and the dilute hydrochloric acid solution The mass-volume ratio was 1:10g/mL. After stirring at 60°C for 2h, solid-liquid separation was performed to obtain 0.15g of lignin filter residue, and 31.6% of hemicellulose components were recovered in the form of soluble xylose and xylan.
以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想，应当指出，对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The descriptions of the above embodiments are only used to help understand the technical solutions and core ideas of the present invention. It should be pointed out that for those skilled in the art, some improvements can also be made to the present invention without departing from the principles of the present invention. and modifications, these improvements and modifications also fall within the protection scope of the claims of the present invention.
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| US4826566A (en) * | 1988-01-11 | 1989-05-02 | Le Tourneau College | Rapid disolution of lignin and other non-carbohydrates from ligno-cellulosic materials impregnated with a reaction product of triethyleneglycol and an organic acid |
| WO1997032075A1 (en) * | 1996-02-29 | 1997-09-04 | Burkart, Leonard | Process for the production of lignin and microcellulose |
| US5859236A (en) * | 1996-02-29 | 1999-01-12 | Burkart; Leonard | Process for preparation of lignin and microcellulose |
| CN103597085A (en) * | 2011-06-10 | 2014-02-19 | 先正达参股股份有限公司 | Methods for converting lignocellulosic material to useful products |
| CN109957983A (en) * | 2017-11-08 | 2019-07-02 | 地球循环株式会社 | Cellulose separation method |
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| US4826566A (en) * | 1988-01-11 | 1989-05-02 | Le Tourneau College | Rapid disolution of lignin and other non-carbohydrates from ligno-cellulosic materials impregnated with a reaction product of triethyleneglycol and an organic acid |
| WO1997032075A1 (en) * | 1996-02-29 | 1997-09-04 | Burkart, Leonard | Process for the production of lignin and microcellulose |
| US5859236A (en) * | 1996-02-29 | 1999-01-12 | Burkart; Leonard | Process for preparation of lignin and microcellulose |
| CN103597085A (en) * | 2011-06-10 | 2014-02-19 | 先正达参股股份有限公司 | Methods for converting lignocellulosic material to useful products |
| CN109957983A (en) * | 2017-11-08 | 2019-07-02 | 地球循环株式会社 | Cellulose separation method |
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