CN115259995B - 一种木质纤维素催化氢解制备邻位二元醇的方法 - Google Patents
一种木质纤维素催化氢解制备邻位二元醇的方法 Download PDFInfo
- Publication number
- CN115259995B CN115259995B CN202110483647.4A CN202110483647A CN115259995B CN 115259995 B CN115259995 B CN 115259995B CN 202110483647 A CN202110483647 A CN 202110483647A CN 115259995 B CN115259995 B CN 115259995B
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- lignocellulose
- diol
- ortho
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000002009 diols Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 abstract description 11
- 229920002678 cellulose Polymers 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- 229940015975 1,2-hexanediol Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 2
- 239000002029 lignocellulosic biomass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 150000000180 1,2-diols Chemical class 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 101710172711 Structural protein Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/202—Ethylene glycol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/205—1,3-Propanediol; 1,2-Propanediol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种木质纤维素催化氢解制备邻位二元醇的方法，在类石墨烯碳壳层包裹的磁性金属催化剂的作用下，纤维素高效地转化为邻位二元醇，且所用催化剂价格低廉，储备量大，制备方法简单，条件温和，且无需再次加氢还原，在反应过程中所表现出的催化剂活性优异、效率高，具有成本低可大规模推广应用的优点。
Description
技术领域：
本发明涉及一种木质纤维素催化氢解制备邻位二元醇的方法。
背景技术：
木质纤维素类生物质是地球上最为丰富的生物质资源，其主要来源于植物和农林废弃物。木质纤维素类生物质主要由纤维素(占干物质重的30-50％)、半纤维素(占干物质重的20-40％)及木质素(占干物质重的15-25％)三部分构成，此外还包括少量的结构蛋白、脂类和灰分。纤维素是葡萄糖单元通过β-1,4糖苷键线性连接形成的均相聚合物，纤维素之间通过氢键相互作用，并可以形成结晶区域和无定型区域。植物不同其组分的含量也不同。
邻位二元醇(主要包括：乙二醇，1,2-丙二醇，1,2-丁二醇，1,2-己二醇等)是非常重要的基础有机工业原料。其中，乙二醇主要用于制聚酯树脂、吸湿剂，表面活性剂，合成纤维和化妆品，并用作染料、油墨等的溶剂、配制发动机的抗冻剂，也可用于生产合成树脂PET，用于制作矿泉水瓶等。除用作汽车用防冻剂外，还用于工业冷量的输送，一般称呼为载冷剂，同时，也可以与水一样用作冷凝剂。1,2-丙二醇是环氧树脂、聚氨酯树脂的重要原料，这方面的用量约占丙二醇总消费量的45％左右，这种不饱和聚酯大量用于表面涂料和增强塑料。除此之外，由于它的粘性和吸湿性好，在食品、医药和化妆品工业中也广泛用作吸湿剂、抗冻剂、润滑剂和溶剂。1,2-丁二醇主要用途是用做聚酯和聚氨酯树脂改性的二醇单体和用做PVC树脂的增塑剂生产原料。1,2位的二醇类因为有更好的抑菌效果而被应用于化妆品和防腐剂方面，其中1,2-己二醇作为温和、无刺激抑菌剂或者防腐增效剂被发掘并得到广泛应用。
随着石油资源的大量消耗和越来越重视的环境保护问题，由可再生的生物质制备精细化学品的研究己经成为近年来的热点课题之一。生物质原料丰富、来源广泛，同时还具有可再生、污染少等显著优点，因此由生物质替代传统石油为原料制备精细化学品开发已经得到世界上许多国家的普遍重视。其中木质纤维素具有特定的立体结构和光学结构，利用这些易于检测的结构可以做到对转化产物的定向调控和分析，减少副反应的发生，因此成为科研工作者关注的热点。以生物质原料替代化石原料制备小分子二元醇，不仅具有原料资源丰富，经济压力小，工艺路线灵活，节能减排等优势，而且还可以同时解决农林废弃物带来的愈发严重的环境污染问题。
发明内容：
本发明的目的是提供一种木质纤维素催化氢解制备邻位二元醇的方法，在类石墨烯碳壳层包裹的磁性金属催化剂的作用下，纤维素高效地转化为邻位二元醇，且所用催化剂价格低廉，储备量大，制备方法简单，条件温和，且无需再次加氢还原，在反应过程中所表现出的催化剂活性优异、效率高，具有成本低可大规模推广应用的优点。
本发明是通过以下技术方案予以实现的：
一种木质纤维素催化氢解制备邻位二元醇的方法，该方法包括以下步骤：以液体酸的水溶液为溶剂在类石墨烯碳壳层包裹的磁性金属催化剂的作用下将木质纤维素原料进行加氢反应转化为邻位二元醇，反应温度为180-220℃，优选为200-220℃，反应时间为2-4h，反应体系中氢气压力为5.5MPa；所述类石墨烯碳壳层包裹金属催化剂的制备方法如下：金属盐、有机酸和去离子水，80-100℃下搅拌6个小时，升温至100℃，保持12小时，得到粉末样品在600-800℃范围内，优选为600-700℃范围内，在N2气氛保护下焙烧3小时得到目标催化剂，其中金属盐、有机物的摩尔比为1：1，所述金属盐的金属离子选自VIIIB族的过渡金属中的一种或两种，优选为Cu、Fe、Co、Ni、Pt中的一种以上，最优选为Co，所述的金属盐为氯化盐、硝酸盐和硫酸盐中的一种或两种；所述的液体酸选自盐酸、硫酸、磷酸；优选为磷酸，所述的有机酸为柠檬酸。
本发明的有益效果如下：
本发明类石墨烯碳壳层包裹的磁性金属催化剂，具有价格低廉，储备量大，制备方法简单，条件温和，且无需再次加氢还原等优点，能高效地催化剂木质纤维素转化为邻位二元醇类产品，且活性优异、效率高，可重复使用。
附图说明：
图1是实施例1中600℃下焙烧得到的碳包裹Co催化剂的TEM图，可见催化剂为球形状态，其中内核为金属Co颗粒，壳层为碳层。
图2是类石墨烯壳层包裹金属Co催化剂制备时不同焙烧温度下得到的催化剂XRD图，其中，Co@CA-600指焙烧温度为600℃，Co@CA-700指焙烧温度为700℃，Co@CA-800指焙烧温度为800℃，从图中可见C的(002)晶面峰和Co的(111)，(200)和(220)晶面峰，表明催化剂主要成分为Co金属单质。
图3是不同焙烧温度下得到的催化剂Raman谱图，其中，Co@CA-600指焙烧温度为600℃，Co@CA-700指焙烧温度为700℃，Co@CA-800指焙烧温度为800℃，图中1583cm-1位置明显的G峰表明包裹在金属Co颗粒外层的确为石墨烯层，与TEM测试结果相符合。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：催化剂的制备
在烧杯中加入10mL去离子水，0.03mol的金属盐，0.03mol的有机物搅拌，搅拌速率为300rpm，80℃下保持6小时，升温至100℃直至样品完全干燥。将得到的粉末在惰性气体N2气氛中，升温至600℃或700℃或800℃，并保持3小时得到类石墨烯碳壳层包裹金属Co催化剂，分别记为Co@CA-600、Co@CA-700、Co@CA-800。
实施例2：
将实施例1制备得到的0.05g类石墨烯碳壳层包裹金属Co催化剂Co@CA-600，0.1g的纤维素和5.0ml磷酸水溶液放入到10ml高压反应釜中，密封反应釜，用H2置换釜内气体4次，充H2增压至5.5MPa。开启搅拌桨(800rpm)，以6℃/min的加热速率将反应釜升温至210℃，开始计时反应。反应时间为3h。邻位二元醇产物收率为60.8％。
实施例3-12：
参考实施例2，不同之处在于反应温度和反应时间不同，考察反应温度和反应时间对纤维素催化氢解制备邻位二元醇收率的影响。具体参见表1。
表1
实施例13-18：
参考实施例2，不同之处在于类石墨烯碳壳层包裹金属Co催化剂制备时的焙烧温度不同以及催化剂的添加剂量不同，考察不同温度下焙烧的类石墨烯碳壳层包裹金属Co催化剂以及不同催化剂用量对纤维素催化加氢制备邻位二元醇产物产率的影响，具体参见表2
表2
实施例19-24：不同液体酸及不同液体酸(磷酸)浓度对纤维素催化氢解制备邻位二元醇收率的影响。
参考实施例2，不同之处在于所使用的液体酸不同，以及所用液体酸的浓度不同，具体参见表3。
表3
实施例25-29：
考察类石墨烯碳壳层包裹金属Co催化剂循环次数对纤维素催化氢解制备邻位二元醇收率的影响。
实施例30-38：
考察类石墨烯碳壳层包裹一种或两种金属催化剂对纤维素催化氢解制备邻位二元醇收率的影响。
| 实施例 | 催化剂 | 邻位二元醇收率(％) |
| 30 | Fe@CA | 34.7 |
| 31 | Co@CA | 60.8 |
| 32 | Ni@CA | 55.6 |
| 33 | Cu@CA | 40.3 |
| 34 | Pt@CA | 35.3 |
| 35 | Fe-Co@CA | 40.2 |
| 36 | Ni-Co@CA | 57.8 |
| 37 | Cu-Co@CA | 43.1 |
| 38 | Pt-Co@CA | 50.9 |
Claims (1)
1.一种木质纤维素催化氢解制备邻位二元醇的方法，其特征在于，该方法包括以下步骤：
以液体酸的水溶液为溶剂在类石墨烯碳壳层包裹的磁性金属催化剂的作用下将木质纤维素原料进行加氢反应转化为邻位二元醇，反应温度为200-220℃，反应时间为2-4h，反应体系中氢气压力为5.5MPa；所述类石墨烯碳壳层包裹金属催化剂的制备方法如下：金属盐、有机酸和去离子水，80-100℃下搅拌6个小时，升温至100℃，保持12小时，得到粉末样品在600-700℃范围内，在N2气氛保护下焙烧3小时得到目标催化剂，其中金属盐、有机酸的摩尔比为1：1，所述金属盐的金属为Co，所述的金属盐为氯化盐、硝酸盐和硫酸盐中的一种或两种；所述的液体酸选自盐酸、硫酸、磷酸中的任一种，所述的有机酸为柠檬酸。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483647.4A CN115259995B (zh) | 2021-04-30 | 2021-04-30 | 一种木质纤维素催化氢解制备邻位二元醇的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483647.4A CN115259995B (zh) | 2021-04-30 | 2021-04-30 | 一种木质纤维素催化氢解制备邻位二元醇的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115259995A CN115259995A (zh) | 2022-11-01 |
| CN115259995B true CN115259995B (zh) | 2024-01-23 |
Family
ID=83745429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110483647.4A Active CN115259995B (zh) | 2021-04-30 | 2021-04-30 | 一种木质纤维素催化氢解制备邻位二元醇的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115259995B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442886A (zh) * | 2010-10-09 | 2012-05-09 | 中国科学院青岛生物能源与过程研究所 | 一种由生物纤维聚糖直接制备二醇的方法 |
| CN103420798A (zh) * | 2012-05-18 | 2013-12-04 | 中国科学院大连化学物理研究所 | 一种高效催化转化纤维素类原料到二元醇的方法 |
| CN109485543A (zh) * | 2018-11-29 | 2019-03-19 | 中国科学技术大学 | 由纤维素一步制备乙二醇和1,2-丙二醇的方法及其催化剂 |
| CN110028393A (zh) * | 2019-05-17 | 2019-07-19 | 中国科学院广州能源研究所 | 一种纤维素催化加氢制备丙酮醇和羟基丁酮的方法 |
| CN110028389A (zh) * | 2019-05-17 | 2019-07-19 | 中国科学院广州能源研究所 | 一种木质纤维素催化加氢制备多元醇和芳香化合物的方法 |
| CN110092708A (zh) * | 2019-05-17 | 2019-08-06 | 中国科学院广州能源研究所 | 一种木质纤维素催化加氢制备乙醇的方法 |
-
2021
- 2021-04-30 CN CN202110483647.4A patent/CN115259995B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442886A (zh) * | 2010-10-09 | 2012-05-09 | 中国科学院青岛生物能源与过程研究所 | 一种由生物纤维聚糖直接制备二醇的方法 |
| CN103420798A (zh) * | 2012-05-18 | 2013-12-04 | 中国科学院大连化学物理研究所 | 一种高效催化转化纤维素类原料到二元醇的方法 |
| CN109485543A (zh) * | 2018-11-29 | 2019-03-19 | 中国科学技术大学 | 由纤维素一步制备乙二醇和1,2-丙二醇的方法及其催化剂 |
| CN110028393A (zh) * | 2019-05-17 | 2019-07-19 | 中国科学院广州能源研究所 | 一种纤维素催化加氢制备丙酮醇和羟基丁酮的方法 |
| CN110028389A (zh) * | 2019-05-17 | 2019-07-19 | 中国科学院广州能源研究所 | 一种木质纤维素催化加氢制备多元醇和芳香化合物的方法 |
| CN110092708A (zh) * | 2019-05-17 | 2019-08-06 | 中国科学院广州能源研究所 | 一种木质纤维素催化加氢制备乙醇的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115259995A (zh) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pagliaro et al. | Recent advances in the conversion of bioglycerol into value‐added products | |
| CN110092708B (zh) | 一种木质纤维素催化加氢制备乙醇的方法 | |
| CN101298566A (zh) | 一种制备生物基炭质固体酸催化剂及生物柴油的方法 | |
| CN110028389B (zh) | 一种木质纤维素催化加氢制备多元醇和芳香化合物的方法 | |
| CN104711007A (zh) | 一种航空煤油或柴油范围液态烷烃的制备方法 | |
| CN101314138A (zh) | 直接磺化生物质制备的炭质固体酸催化剂 | |
| Antunes et al. | Bioenergy and biofuels: nanotechnological solutions for sustainable production | |
| CN108671960A (zh) | 一种高水热稳定性MOFs催化剂、制备及用于纤维素转化制备化学品的方法 | |
| Xu et al. | Improved production of adipic acid from a high loading of corn stover via an efficient and mild combination pretreatment | |
| CN108097312A (zh) | 一种木质纤维素基固体酸催化剂的制备方法及其应用 | |
| Saikia et al. | Sulphonated cellulose-based carbon as a green heterogeneous catalyst for biodiesel production: process optimization and kinetic studies | |
| CN102442886A (zh) | 一种由生物纤维聚糖直接制备二醇的方法 | |
| CN110117499A (zh) | 一种由含氧有机化合物加氢脱氧制备烷烃的方法 | |
| KR101730034B1 (ko) | 고체산 촉매를 이용한 바이오매스 유래 당화액의 제조방법 | |
| CN115259995B (zh) | 一种木质纤维素催化氢解制备邻位二元醇的方法 | |
| KR101358967B1 (ko) | 바이오매스로부터 레불린산 또는 이의 에스테르 화합물 제조용 촉매 및 이를 이용한 레불린산 또는 이의 에스테르 화합물의 제조방법 | |
| CN110102343B (zh) | 一种复合酸催化剂及其催化糖类制备5-羟甲基糠醛的方法 | |
| CN108675920A (zh) | 一种无溶剂快速氧化裂解环氧脂肪酸甲酯制备醛类物质的方法 | |
| CN104788408A (zh) | 一种由半纤维素生产γ-戊内酯的方法 | |
| Bhuyan et al. | Advances in nanotechnology for biofuel production | |
| CN101870638A (zh) | 一种利用植物秸秆制备乙二醇的方法 | |
| CN106397495B (zh) | 木质素的加氢降解产物及木质素的加氢降解方法 | |
| CN114057554B (zh) | 一种木质纤维素催化加氢制备2,5-己二酮的方法 | |
| CN113289680B (zh) | 一种双相催化剂及其制备方法和在木质纤维素生物质转化中的应用 | |
| CN103058966A (zh) | 一种稀土生物基功能材料及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |