CN102617287B - Method for preparing hexitol or hydroxy-acetone - Google Patents
Method for preparing hexitol or hydroxy-acetone Download PDFInfo
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- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims abstract description 53
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229920002678 cellulose Polymers 0.000 claims abstract description 104
- 239000001913 cellulose Substances 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 24
- 239000008103 glucose Substances 0.000 claims abstract description 24
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 23
- 239000005715 Fructose Substances 0.000 claims abstract description 22
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 22
- 229930091371 Fructose Natural products 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 100
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 17
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 17
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 17
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 241000332371 Abutilon x hybridum Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 229920001131 Pulp (paper) Polymers 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 44
- 238000004458 analytical method Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 18
- 150000005846 sugar alcohols Polymers 0.000 description 17
- 239000007791 liquid phase Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- 238000000926 separation method Methods 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- -1 antifreeze Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000002537 cosmetic Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种制备己糖醇或羟基丙酮的方法。该方法包括如下步骤：在氢气气氛和催化剂的作用下，纤维素、葡萄糖或果糖在水中进行反应，即得己糖醇或羟基丙酮；所述催化剂为负载型金属催化剂，所述负载型金属催化剂的活性组分为由修饰剂修饰的金属，所述金属为Pt、Ru、Ni和Cu中任一种；所述负载型金属催化剂的载体为Al2O3、TiO2、ZrO2、SiO2和活性炭中任一种。本发明提供的方法经一锅反应选择性地从纤维素、葡萄糖或果糖得到己糖醇或羟基丙酮，过程简单，反应迅速，高效节能，易于工业化；催化剂可回收循环利用，节约成本，绿色环保；且该方法对设备要求低，对设备无腐蚀，投资小。The invention discloses a method for preparing hexitol or hydroxyacetone. The method comprises the following steps: under the action of a hydrogen atmosphere and a catalyst, cellulose, glucose or fructose are reacted in water to obtain hexitol or hydroxyacetone; the catalyst is a supported metal catalyst, and the supported metal catalyst The active component of the catalyst is a metal modified by a modifier, and the metal is any one of Pt, Ru, Ni and Cu; the carrier of the supported metal catalyst is Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 and activated carbon. The method provided by the invention selectively obtains hexitol or hydroxyacetone from cellulose, glucose or fructose through a one-pot reaction. The process is simple, the reaction is rapid, high efficiency and energy saving, and it is easy to industrialize; the catalyst can be recycled and reused, saving costs and being environmentally friendly. ; and the method has low requirements on equipment, no corrosion to equipment, and small investment.
Description
技术领域 technical field
本发明涉及一种制备己糖醇或羟基丙酮的方法。The invention relates to a method for preparing hexitol or hydroxyacetone.
背景技术 Background technique
生物质来源丰富，可再生，并且含有碳元素和羟基官能团，是极具潜力的化石资源替代品。纤维素是生物质最主要的组成之一，它的有效转化是生物质利用的重要内容。纤维素是葡萄糖单体通过1，4-β-糖苷键聚合成链，链与链之间通过丰富的氢键连接成具有高聚合度和高结晶度的晶体结构。将纤维素解聚为葡萄糖单体，再将它们加氢转化为多元醇是纤维素有效转化的可行途径之一。Biomass is rich in sources, renewable, and contains carbon elements and hydroxyl functional groups. It is a potential substitute for fossil resources. Cellulose is one of the most important components of biomass, and its effective conversion is an important content of biomass utilization. Cellulose is glucose monomers polymerized into chains through 1,4-β-glucosidic bonds, and the chains are connected by abundant hydrogen bonds to form a crystal structure with a high degree of polymerization and high crystallinity. Depolymerization of cellulose into glucose monomers and hydrogenation of them into polyols is one of the feasible routes for the efficient conversion of cellulose.
多元醇广泛应用于食物、溶剂、抗冻剂、药物和化妆品中。目前从纤维素及其衍生物出发高效合成多元醇的方法较少，因此开发有效的转化路径意义重大。已有的方法大量集中在山梨醇和甘露醇等己糖醇的生产上，如利用负载型Pt和Ru加氢催化剂在高温水中可将纤维素转化为己糖醇，以及通过球磨等物理方法或是磷酸处理的化学方法处理纤维素再耦合Ru、Pt或Ni等加氢催化剂可提高己糖醇的收率。然而，从纤维素及其衍生物出发制备乙二醇、1，2-丙二醇和羟基丙酮的方法极少。仅有两例，即利用负载的Ni-W催化剂可高效地催化转化纤维素为乙二醇以及利用Ru/C和WO3可选择性转化纤维素为乙二醇和1，2-丙二醇。但是目前为止，将纤维素及其衍生物高效地转化为羟基丙酮的方法尚未有报道。Polyols are widely used in food, solvents, antifreeze, pharmaceuticals and cosmetics. At present, there are few methods for efficiently synthesizing polyols from cellulose and its derivatives, so it is of great significance to develop effective conversion pathways. A large number of existing methods focus on the production of hexitols such as sorbitol and mannitol, such as using supported Pt and Ru hydrogenation catalysts to convert cellulose into hexitols in high temperature water, and by physical methods such as ball milling or The chemical method of phosphoric acid treatment can improve the yield of hexitol by treating cellulose and coupling hydrogenation catalysts such as Ru, Pt or Ni. However, there are few methods for preparing ethylene glycol, 1,2-propanediol and hydroxyacetone from cellulose and its derivatives. There are only two examples, that is, the efficient catalytic conversion of cellulose to ethylene glycol using supported Ni-W catalysts and the selective conversion of cellulose to ethylene glycol and 1,2-propanediol using Ru/C and WO 3 . But so far, there is no report on the efficient conversion of cellulose and its derivatives to hydroxyacetone.
发明内容 Contents of the invention
本发明的目的是提供一种制备己糖醇或羟基丙酮的方法，可选择性地制备目标多元醇。The purpose of the present invention is to provide a method for preparing hexitol or hydroxyacetone, which can selectively prepare target polyols.
为此，本发明所提供的一种制备己糖醇或羟基丙酮的方法，包括如下步骤：For this reason, a kind of method for preparing hexitol or hydroxyacetone provided by the present invention comprises the steps:
在氢气气氛和催化剂的作用下，纤维素、葡萄糖或果糖在水中进行反应，即得己糖醇或羟基丙酮；Under the action of hydrogen atmosphere and catalyst, cellulose, glucose or fructose react in water to obtain hexitol or hydroxyacetone;
所述催化剂为负载型金属催化剂，所述负载型金属催化剂的活性组分为由修饰剂修饰的金属，所述金属为Pt、Ru、Ni和Cu中任一种；所述负载型金属催化剂的载体为Al2O3、TiO2、ZrO2、SiO2和活性炭中任一种。The catalyst is a supported metal catalyst, the active component of the supported metal catalyst is a metal modified by a modifier, and the metal is any one of Pt, Ru, Ni and Cu; the supported metal catalyst The carrier is any one of Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 and activated carbon.
上述的方法中，所述反应的温度可为200℃～250℃，具体可为200℃或240℃，时间可为0.5小时～5小时，具体可为0.5小时或5小时，压力可为2MPa～8Mpa，具体可为2MPa、6Mpa或8Mpa。In the above method, the temperature of the reaction may be 200°C to 250°C, specifically 200°C or 240°C, the time may be 0.5 hours to 5 hours, specifically 0.5 hours or 5 hours, and the pressure may be 2 MPa to 5 hours. 8Mpa, specifically 2MPa, 6Mpa or 8Mpa.
上述的方法中，所述己糖醇可为山梨醇和/或甘露醇。In the above method, the hexitol may be sorbitol and/or mannitol.
上述的方法中，所述纤维素可为微晶纤维素、棉花、纸浆、桔梗或木材等。In the above method, the cellulose can be microcrystalline cellulose, cotton, pulp, bellflower or wood, etc.
上述的方法中，所述负载型金属催化剂中，所述活性组分中的金属的质量百分含量为0.5％～50％，如2％、5％或50％。In the above method, in the supported metal catalyst, the mass percentage of the metal in the active component is 0.5%-50%, such as 2%, 5% or 50%.
上述的方法中，所述活性组分中，所述修饰剂可为SnOx、CeOx、Al2Ox、ZnOx和MgOx中任一种，其中x为0～4之间的数，但不为零。In the above method, in the active component, the modifier can be any one of SnO x , CeO x , Al 2 O x , ZnO x and MgO x , wherein x is a number between 0 and 4, but not zero.
上述的方法中，所述活性组分中，所述修饰剂与所述金属的摩尔份数比可为(0～10)∶1，但所述氧化物的量不为零，具体可为0.3∶1、0.5∶1、4.0∶1或10.0∶1。In the above method, in the active component, the molar ratio of the modifying agent to the metal may be (0-10): 1, but the amount of the oxide is not zero, specifically 0.3 :1, 0.5:1, 4.0:1 or 10.0:1.
上述的方法中，所述负载型金属催化剂可按照包括下述方法制备：向所述修饰剂的前体化合物与所述金属的前体化合物的混合物中加入盐酸水溶液，然后加入所述载体，经干燥、焙烧和还原即得所述催化剂；所述修饰剂的前体化合物为所述修饰剂中相应金属的氯化物；所述金属的前体化合物为所述金属的氯化物。In the above method, the supported metal catalyst can be prepared according to the following method: adding aqueous hydrochloric acid to the mixture of the precursor compound of the modifying agent and the precursor compound of the metal, and then adding the carrier, through The catalyst is obtained by drying, calcining and reducing; the precursor compound of the modifier is the chloride of the corresponding metal in the modifier; the precursor compound of the metal is the chloride of the metal.
上述的方法中，所述催化剂与所述纤维素、葡萄糖或果糖的质量份数比可为(0.1～10)∶1，具体可为0.4∶1、0.5∶1或2∶1。In the above method, the mass fraction ratio of the catalyst to the cellulose, glucose or fructose may be (0.1-10):1, specifically 0.4:1, 0.5:1 or 2:1.
本发明提供的制备方法是在高温水条件下转化纤维素、葡萄糖或果糖，通过引入修饰剂修饰的Pt、Ru、Ni和Cu等负载型催化剂，选择性地转化为己糖醇或羟基丙酮，通过实施例可知，低Sn/M比例(M＝Pt、Ru、Ni和Cu等)催化剂可以促进纤维素水解得到的葡萄糖中间体加氢，从而提高己糖醇的选择性；高Sn/M比例催化剂可以促进纤维素水解得到的葡萄糖中间体异构为果糖，然后果糖反羟醛缩合生成甘油醛等中间体，这些中间体通过脱水和加氢反应可得到羟基丙酮；本发明提供的方法经一锅反应选择性地从纤维素、葡萄糖或果糖得到己糖醇或羟基丙酮，过程简单，反应迅速，高效节能，易于工业化；催化剂可回收循环利用，节约成本，绿色环保；且该方法对设备要求低，对设备无腐蚀，投资小；通过调变催化剂中二元组分的比例，可以选择性转化为己糖醇或羟基丙酮，如在纤维素转化率为20％，通过调变二元组分的比例可分别获得82.8％己糖醇和49.7％羟基丙酮(C3多元醇选择性可达75％)。The preparation method provided by the invention is to convert cellulose, glucose or fructose under high-temperature water conditions, and selectively convert hexitol or hydroxyacetone by introducing load-type catalysts such as Pt, Ru, Ni and Cu modified by modifiers, It can be seen from the examples that the low Sn/M ratio (M=Pt, Ru, Ni and Cu, etc.) catalyst can promote the hydrogenation of the glucose intermediate obtained by cellulose hydrolysis, thereby improving the selectivity of hexitol; the high Sn/M ratio The catalyst can promote the isomerization of glucose intermediates obtained by cellulose hydrolysis into fructose, and then the fructose is trans-aldolized to generate intermediates such as glyceraldehyde, and these intermediates can be dehydrated and hydrogenated to obtain hydroxyacetone; The pot reaction selectively obtains hexitol or hydroxyacetone from cellulose, glucose or fructose. The process is simple, the reaction is rapid, high efficiency and energy saving, and it is easy to industrialize; the catalyst can be recycled and reused, saving costs and being environmentally friendly; and the method requires Low, no corrosion to equipment, small investment; by adjusting the ratio of binary components in the catalyst, it can be selectively converted into hexitol or hydroxyacetone, such as 20% conversion rate of cellulose, by adjusting the ratio of binary components The proportion of points can obtain 82.8% hexitol and 49.7% hydroxyacetone respectively (C 3 polyhydric alcohol selectivity can reach 75%).
具体实施方式 Detailed ways
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
下述实施例中的方法是以SnOx修饰的负载型金属催化剂为例，如无特别说明，此方法同样适用于CeOx、Al2Ox、ZnOx和MgOx等修饰的催化剂。The methods in the following examples are based on SnO x modified supported metal catalysts as an example. Unless otherwise specified, this method is also applicable to CeO x , Al 2 O x , ZnO x and MgO x modified catalysts.
实施例1、水解纤维素制备己糖醇Embodiment 1, hydrolysis cellulose prepares hexitol
负载型金属催化剂Pt-SnOx/Al2O3的制备：将SnCl2·2H2O与H2PtCl6·6H2O以摩尔份数比为0.3进行混合，然后滴加1滴37％的盐酸溶液并加入水，待形成均匀溶液后加入Al2O3；经室温干燥后置于110℃烘箱中进行干燥过夜，然后依次经焙烧(在400℃和空气气氛中焙烧4小时)和还原(在400℃和20％H2/N2的气氛下还原4小时)即得。Preparation of supported metal catalyst Pt-SnO x /Al 2 O 3 : Mix SnCl 2 2H 2 O with H 2 PtCl 6 6H 2 O at a molar ratio of 0.3, then add 1 drop of 37% Hydrochloric acid solution and water were added, and Al 2 O 3 was added after a uniform solution was formed; after drying at room temperature, it was dried overnight in an oven at 110°C, and then roasted (at 400°C and air atmosphere for 4 hours) and reduced ( Reduction at 400° C. and 20% H 2 /N 2 atmosphere for 4 hours).
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g上述制备的2％(活性组分中的金属Pt的质量百分含量)Pt-SnOx/Al2O3(Sn/Pt＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline cellulose, available from Alfa Aesar) is placed in a 100ml reaction kettle with a sufficient amount of water (50ml), and 0.4g of the 2% prepared above (the mass percent of metal Pt in the active component) is added. content) Pt-SnO x /Al 2 O 3 (Sn/Pt = 0.3, x is 0-4), filled with H 2 , the pressure in the reactor was 60 atm, heated to 200°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和己糖醇的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hexitol were detected:
将未反应掉的纤维素在天平上称量质量，为0.8g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)；分析结果表明反应产物主要为山梨醇和甘露醇(己糖醇)，定量为0.184g，其他少量产物为C2-C5多元醇。The unreacted cellulose was weighed on a balance, and it was 0.8g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min); analysis results showed that the reaction products were mainly sorbitol and mannitol (hexitol), with a quantitative value of 0.184g, and other minor products were C 2 -C 5 polyhydric alcohols.
按照下述公式计算纤维素转化率，反应产物的选择性和产率：Calculate the cellulose conversion rate, the selectivity and the productive rate of the reaction product according to the following formula:
结果表明，纤维素转化率为19.8％，纤维素主要转化为己糖醇，选择性达82.8％，收率为16.4％。The results showed that the conversion rate of cellulose was 19.8%, and the cellulose was mainly converted into hexitol, with a selectivity of 82.8% and a yield of 16.4%.
纤维素转化率计算：Cellulose conversion rate calculation:
其中，转化的纤维素质量＝纤维素投料质量-纤维素剩余质量Wherein, converted cellulose mass=cellulose feed mass-cellulose remaining mass
己糖醇的选择性计算(选择性定义为产物的碳摩尔数与所转化原料的碳摩尔数之比)：Selectivity calculation for hexitols (selectivity is defined as the ratio of the number of carbon moles of the product to the number of carbon moles of the converted feedstock):
己糖醇的产率计算：Calculation of the yield of hexitol:
实施例2、水解纤维素制备己糖醇Embodiment 2, hydrolyzing cellulose to prepare hexitol
负载型金属催化剂Pt-SnOx/Al2O3的制备：具体制备方法同实施例1，不同之处在于：SnCl2·2H2O与H2PtCl6·6H2O的摩尔份数比为0.5。Preparation of supported metal catalyst Pt-SnO x /Al 2 O 3 : the specific preparation method is the same as in Example 1, except that the molar ratio of SnCl 2 2H 2 O to H 2 PtCl 6 6H 2 O is 0.5.
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Pt-SnOx/Al2O3(Sn/Pt＝0.5，x为0～4)，充入H2，使反应釜中的压力为20atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Pt-SnO x /Al 2 O 3 (Sn/Pt= 0.5, x is 0-4), filled with H 2 , the pressure in the reactor was 20atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和己糖醇的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hexitol were detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为己糖醇，定量为0.366g，其他少量产物为C2-C5多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hexitol, with a quantitative value of 0.366g, and other minor products were C 2 -C 5 polyhydric alcohols.
按照实施例1所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 1, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为己糖醇，选择性达32.6％，收率为32.6％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hexitol, with a selectivity of 32.6% and a yield of 32.6%.
实施例3、水解纤维素制备羟基丙酮Embodiment 3, hydrolysis cellulose prepares hydroxyacetone
负载型金属催化剂Pt-SnOx/Al2O3的制备：具体制备方法同实施例1，不同之处在于：SnCl2·2H2O与H2PtCl6·6H2O的摩尔份数比为4.0。Preparation of supported metal catalyst Pt-SnO x /Al 2 O 3 : the specific preparation method is the same as in Example 1, except that the molar ratio of SnCl 2 2H 2 O to H 2 PtCl 6 6H 2 O is 4.0.
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Pt-SnOx/Al2O3(Sn/Pt＝4.0，x为0～4)，充入H2，使反应釜中的压力为80atm，加热至200℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Pt-SnO x /Al 2 O 3 (Sn/Pt= 4.0, x is 0-4), filled with H 2 , the pressure in the reactor was 80atm, heated to 200°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0.779g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.052g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0.779g; the reaction product was analyzed and quantified by high performance liquid phase (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.052g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照下述公式计算纤维素转化率，反应产物的选择性和产率：Calculate the cellulose conversion rate, the selectivity and the productive rate of the reaction product according to the following formula:
结果表明，纤维素转化率为22.1％。纤维素主要转化为羟基丙酮，选择性达25.6％，收率为5.7％。The results showed that the conversion rate of cellulose was 22.1%. Cellulose was mainly converted to hydroxyacetone with a selectivity of 25.6% and a yield of 5.7%.
纤维素转化率计算：Cellulose conversion rate calculation:
其中，转化的纤维素质量＝纤维素投料质量-纤维素剩余质量Wherein, converted cellulose mass=cellulose feed mass-cellulose remaining mass
羟基丙酮的选择性计算(选择性定义为产物的碳摩尔数与所转化原料的碳摩尔数之比)：Selectivity calculation for hydroxyacetone (selectivity is defined as the ratio of the number of carbon moles of the product to the number of carbon moles of the converted raw material):
羟基丙酮的产率计算：The yield calculation of hydroxyacetone:
实施例4、水解纤维素制备羟基丙酮Embodiment 4, hydrolysis cellulose prepares hydroxyacetone
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Pt-SnOx/Al2O3(Sn/Pt＝4.0)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Pt-SnO x /Al 2 O 3 (Sn/Pt= 4.0), filled with H 2 , the pressure in the reactor was 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20AHPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.117g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20AHPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.117g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达12.8％，收率为12.8％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 12.8% and a yield of 12.8%.
实施例5、水解纤维素制备羟基丙酮Embodiment 5, hydrolysis cellulose prepares hydroxyacetone
负载型金属催化剂Pt-SnOx/Al2O3的制备：具体制备方法同实施例1，不同之处在于：SnCl2·2H2O与H2PtCl6·6H2O的摩尔份数比为10.0。Preparation of supported metal catalyst Pt-SnO x /Al 2 O 3 : the specific preparation method is the same as in Example 1, except that the molar ratio of SnCl 2 2H 2 O to H 2 PtCl 6 6H 2 O is 10.0.
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Pt-SnOx/Al2O3(Sn/Pt＝10.0，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Pt-SnO x /Al 2 O 3 (Sn/Pt= 10.0, x is 0-4), filled with H 2 , the pressure in the reactor was 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.148g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.148g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达16.2％，收率为16.2％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 16.2% and a yield of 16.2%.
实施例6、水解纤维素制备羟基丙酮Embodiment 6, hydrolysis cellulose prepares hydroxyacetone
负载型金属催化剂Ni-SnOx/Al2O3的制备：将SnCl2·2H2O与NiCl2·6H2O以摩尔份数比为0.5进行混合，然后滴加2滴37％的盐酸溶液并加入水，待形成均匀溶液后加入Al2O3；经室温干燥后置于110℃烘箱中进行干燥过夜，然后依次经焙烧(在400℃和空气气氛中焙烧4小时)和还原(在600℃和20％H2/N2的气氛下还原3小时)和还原即得。Preparation of supported metal catalyst Ni-SnO x /Al 2 O 3 : Mix SnCl 2 2H 2 O and NiCl 2 6H 2 O at a molar ratio of 0.5, then add 2 drops of 37% hydrochloric acid solution And add water, after forming a uniform solution, add Al 2 O 3 ; after drying at room temperature, put it in an oven at 110°C to dry overnight, and then sequentially roast (calculate at 400°C and air atmosphere for 4 hours) and reduce (at 600°C °C and 20% H 2 /N 2 atmosphere for 3 hours) and reduction.
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应5小时。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Ni-SnO x /Al 2 O 3 (Sn/Ni= 0.5, x is 0-4), filled with H 2 , the pressure in the reactor was 60atm, heated to 200°C, and reacted for 5 hours.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20AHPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.300g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20AHPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone with a quantitative value of 0.300g, and the other small amount of products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达32.8％，收率为32.8％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 32.8% and a yield of 32.8%.
实施例7、水解纤维素制备羟基丙酮Embodiment 7, hydrolysis cellulose prepares hydroxyacetone
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Ni-SnO x /Al 2 O 3 (Sn/Ni= 0.5, x is 0 to 4), filled with H 2 to make the pressure in the reactor 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.319g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.319g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达34.9％，收率为34.9％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 34.9% and a yield of 34.9%.
实施例8、水解纤维素制备羟基丙酮Embodiment 8, hydrolysis cellulose prepares hydroxyacetone
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 5％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 5% Ni-SnO x /Al 2 O 3 (Sn/Ni= 0.5, x is 0 to 4), filled with H 2 to make the pressure in the reactor 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.332g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.332g, and the other small amount of products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达36.3％，收率为36.3％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 36.3% and a yield of 36.3%.
实施例9、水解纤维素制备羟基丙酮Embodiment 9, hydrolyzing cellulose to prepare hydroxyacetone
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 50％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 50% Ni-SnO x /Al 2 O 3 (Sn/Ni= 0.5, x is 0 to 4), filled with H 2 to make the pressure in the reactor 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.358g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.358g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达39.2％，收率为39.2％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 39.2% and a yield of 39.2%.
实施例10、水解纤维素制备羟基丙酮Embodiment 10, hydrolyzing cellulose to prepare hydroxyacetone
负载型金属催化剂Cu-SnOx/Al2O3的制备：将SnCl2·2H2O与CuCl2·3H2O以摩尔份数比为0.3进行混合，然后滴加2滴37％的盐酸溶液并加入水，待形成均匀溶液后加入Al2O3；经室温干燥后置于110℃烘箱中进行干燥过夜，然后依次经焙烧(在400℃和空气气氛中焙烧4小时)和还原(在400℃和20％H2/N2的气氛下还原4小时)即得。Preparation of supported metal catalyst Cu-SnO x /Al 2 O 3 : Mix SnCl 2 2H 2 O with CuCl 2 3H 2 O at a molar ratio of 0.3, then add 2 drops of 37% hydrochloric acid solution And add water, after forming a uniform solution, add Al 2 O 3 ; after drying at room temperature, put it in an oven at 110°C to dry overnight, and then sequentially roast (calculate at 400°C and air atmosphere for 4 hours) and reduce (at 400°C) °C and 20% H 2 /N 2 atmosphere for 4 hours).
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Cu-SnOx/Al2O3(Sn/Cu＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Cu—SnO x /Al 2 O 3 (Sn/Cu= 0.3, x is 0 to 4), filled with H 2 to make the pressure in the reactor 60atm, heated to 200°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0.852g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.055g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0.852g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.055g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为14.8％，纤维素主要转化为羟基丙酮，选择性达40.8％，收率为6.0％。The results showed that the conversion rate of cellulose was 14.8%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 40.8% and a yield of 6.0%.
实施例11、水解纤维素制备羟基丙酮Embodiment 11, hydrolyzing cellulose to prepare hydroxyacetone
负载型金属催化剂Ru-SnOx/Al2O3的制备：将SnCl2·2H2O与RuCl3·xH2O以摩尔份数比为0.3进行混合，然后滴加2滴37％的盐酸溶液并加入水，待形成均匀溶液后加入Al2O3；经室温干燥后置于110℃烘箱中进行干燥过夜，然后依次经焙烧(在400℃和空气气氛中焙烧4小时)和还原(在400℃和20％H2/N2的气氛下还原4小时)即得。Preparation of supported metal catalyst Ru-SnO x /Al 2 O 3 : Mix SnCl 2 2H 2 O and RuCl 3 xH 2 O at a molar ratio of 0.3, then add 2 drops of 37% hydrochloric acid solution And add water, after forming a uniform solution, add Al 2 O 3 ; after drying at room temperature, put it in an oven at 110°C to dry overnight, and then sequentially roast (calculate at 400°C and air atmosphere for 4 hours) and reduce (at 400°C) °C and 20% H 2 /N 2 atmosphere for 4 hours).
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ru-SnOx/Al2O3(Sn/Ru＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline cellulose, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Ru-SnO x /Al 2 O 3 (Sn/Ru= 0.3, x is 0 to 4), filled with H 2 to make the pressure in the reactor 60atm, heated to 200°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0.874g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.056g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0.874g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.056g, and other minor products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为12.6％，纤维素主要转化为羟基丙酮，选择性达48.8％，收率为6.1％。The results showed that the conversion rate of cellulose was 12.6%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 48.8% and a yield of 6.1%.
实施例12、水解纤维素制备羟基丙酮Embodiment 12, hydrolyzing cellulose to prepare hydroxyacetone
将1g微晶纤维素(microcrystalline，购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ru-SnOx/Al2O3(Sn/Ru＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至240℃，反应30分钟。1g of microcrystalline cellulose (microcrystalline cellulose, purchased from Alfa Aesar) was placed in a 100ml reaction kettle filled with sufficient water (50ml), and 0.4g of 2% Ru-SnO x /Al 2 O 3 (Sn/Ru= 0.3, x is 0-4), filled with H 2 , the pressure in the reactor was 60atm, heated to 240°C, and reacted for 30 minutes.
按照下述方法，检测纤维素的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of cellulose and the selectivity of hydroxyacetone are detected:
将未反应掉的纤维素在天平上称量质量，为0g；将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRad Aminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明反应产物主要为羟基丙酮，定量为0.283g，其他少量产物为C2-C6多元醇。The unreacted cellulose was weighed on a balance, and it was 0g; the reaction product was analyzed by high performance liquid phase and quantified (Shimadazu LC-20A HPLC; separation column: BioRad Aminex HPX-87H; analysis conditions: mobile phase was 0.01 M H 2 SO 4 , 40°C, 0.6ml/min), the analysis results showed that the reaction product was mainly hydroxyacetone, with a quantitative value of 0.283g, and the other small amount of products were C 2 -C 6 polyhydric alcohols.
按照实施例3所述的公式计算纤维素转化率，反应产物的选择性和产率。According to the formula described in Example 3, the cellulose conversion rate, the selectivity and the productive rate of the reaction product were calculated.
结果表明，纤维素转化率为100％，纤维素主要转化为羟基丙酮，选择性达31.0％，收率为31.0％。The results showed that the conversion rate of cellulose was 100%, and the cellulose was mainly converted into hydroxyacetone with a selectivity of 31.0% and a yield of 31.0%.
实施例13、葡萄糖制备羟基丙酮Embodiment 13, glucose prepares hydroxyacetone
将0.2g葡萄糖(购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。0.2g of glucose (purchased from Alfa Aesar) was placed in a 100ml reactor filled with sufficient water (50ml), and 0.4g of 2% Ni-SnO x /Al 2 O 3 (Sn/Ni=0.5, x was 0-4), fill in H 2 , make the pressure in the reaction vessel 60 atm, heat to 200° C., and react for 30 minutes.
按照下述方法，检测葡萄糖的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of glucose and the selectivity of hydroxyacetone are detected:
将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRadAminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明葡萄糖为0g，反应产物主要为羟基丙酮，定量为0.087g，其他少量产物为C2-C6多元醇。The reaction product was analyzed and quantified by high performance liquid phase (Shimadazu LC-20A HPLC; separation column: BioRadAminex HPX-87H; analysis conditions: mobile phase: 0.01M H 2 SO 4 , 40°C, 0.6ml/min), and the analysis results showed that glucose 0g, the reaction product is mainly hydroxyacetone, quantitatively 0.087g, and other minor products are C 2 -C 6 polyhydric alcohols.
按照下述公式计算羟基丙酮的选择性和产率。Calculate the selectivity and yield of hydroxyacetone according to the following formula.
结果表明，葡萄糖转化率为100％，葡萄糖主要转化为羟基丙酮，选择性达53.0％，收率为53.0％。The results showed that the conversion rate of glucose was 100%, and the glucose was mainly converted into hydroxyacetone with a selectivity of 53.0% and a yield of 53.0%.
羟基丙酮的选择性计算：Selectivity calculation for hydroxyacetone:
羟基丙酮的产率计算：The yield calculation of hydroxyacetone:
实施例14、葡萄糖制备羟基丙酮Embodiment 14, glucose prepares hydroxyacetone
将0.2g葡萄糖(购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ru-SnOx/Al2O3(Sn/Ru＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。0.2g of glucose (purchased from Alfa Aesar) was placed in a 100ml reactor filled with sufficient water (50ml), and 0.4g of 2% Ru-SnO x /Al 2 O 3 (Sn/Ru=0.3, x was 0-4), fill in H 2 , make the pressure in the reaction vessel 60 atm, heat to 200° C., and react for 30 minutes.
按照下述方法，检测葡萄糖的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of glucose and the selectivity of hydroxyacetone are detected:
将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRadAminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明葡萄糖为0g，反应产物主要为羟基丙酮，定量为0.077g，其他少量产物为C2-C6多元醇。The reaction product was analyzed and quantified by high performance liquid phase (Shimadazu LC-20A HPLC; separation column: BioRadAminex HPX-87H; analysis conditions: mobile phase: 0.01M H 2 SO 4 , 40°C, 0.6ml/min), and the analysis results showed that glucose 0g, the reaction product is mainly hydroxyacetone, quantitatively 0.077g, and other minor products are C 2 -C 6 polyhydric alcohols.
按照实施例13所述的公式计算羟基丙酮的选择性和产率。The selectivity and yield of hydroxyacetone were calculated according to the formula described in Example 13.
结果表明，葡萄糖转化率为100％，葡萄糖主要转化为羟基丙酮，选择性达47.0％，收率为47.0％。The results showed that the conversion rate of glucose was 100%, the glucose was mainly converted into hydroxyacetone, the selectivity was 47.0%, and the yield was 47.0%.
实施例15、果糖制备羟基丙酮Embodiment 15, fructose prepares hydroxyacetone
将0.2g果糖(购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ni-SnOx/Al2O3(Sn/Ni＝0.5，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。0.2g fructose (purchased from Alfa Aesar) is placed in the 100ml reactor that sufficient water (50ml) is housed, adds 0.4g 2%Ni-SnO x /Al 2 O 3 (Sn/Ni=0.5, x is 0-4), fill in H 2 , make the pressure in the reaction vessel 60 atm, heat to 200° C., and react for 30 minutes.
按照下述方法，检测果糖的转化率和羟基丙酮的选择性：According to the following method, the conversion rate of fructose and the selectivity of hydroxyacetone were detected:
将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRadAminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明果糖为0g，反应产物主要为羟基丙酮，定量为0.120g，其他少量产物为C2-C6多元醇。The reaction product was analyzed and quantified by high performance liquid phase (Shimadazu LC-20A HPLC; separation column: BioRadAminex HPX-87H; analysis conditions: mobile phase: 0.01M H 2 SO 4 , 40°C, 0.6ml/min), and the analysis results showed that fructose 0g, the reaction product is mainly hydroxyacetone, quantitatively 0.120g, and other small amount of products are C 2 -C 6 polyhydric alcohols.
按照下述公式计算羟基丙酮的选择性和产率。Calculate the selectivity and yield of hydroxyacetone according to the following formula.
结果表明，果糖转化率为100％，果糖主要转化为羟基丙酮，选择性达72.8％，收率为72.8％。The results showed that the conversion rate of fructose was 100%, and the fructose was mainly converted into hydroxyacetone with a selectivity of 72.8% and a yield of 72.8%.
羟基丙酮的选择性计算：Selectivity calculation for hydroxyacetone:
羟基丙酮的产率计算：The yield calculation of hydroxyacetone:
实施例16、果糖制备羟基丙酮Embodiment 16, fructose prepares hydroxyacetone
将0.2g果糖(购自Alfa Aesar)置于装有足量的水(50ml)的100ml反应釜中，加入0.4g 2％Ru-SnOx/Al2O3(Sn/Ru＝0.3，x为0～4)，充入H2，使反应釜中的压力为60atm，加热至200℃，反应30分钟。按照下述方法，检测果糖的转化率和羟基丙酮的选择性：0.2g fructose (purchased from Alfa Aesar) is placed in the 100ml reactor that sufficient amount of water (50ml) is housed, add 0.4g 2% Ru-SnO x /Al 2 O 3 (Sn/Ru=0.3, x is 0-4), fill in H 2 , make the pressure in the reaction vessel 60 atm, heat to 200° C., and react for 30 minutes. According to the following method, the conversion rate of fructose and the selectivity of hydroxyacetone were detected:
将反应产物进行高效液相分析并定量(Shimadazu LC-20A HPLC；分离柱：BioRadAminex HPX-87H；分析条件：流动相为0.01M H2SO4，40℃，0.6ml/min)，分析结果表明果糖为0g，反应产物主要为羟基丙酮，定量为0.113g，其他少量产物为C2-C6多元醇。The reaction product was analyzed and quantified by high performance liquid phase (Shimadazu LC-20A HPLC; separation column: BioRadAminex HPX-87H; analysis conditions: mobile phase: 0.01M H 2 SO 4 , 40°C, 0.6ml/min), and the analysis results showed that fructose 0g, the reaction product is mainly hydroxyacetone, quantitatively 0.113g, and other minor products are C 2 -C 6 polyhydric alcohols.
按照实施例15所述的公式计算羟基丙酮的选择性和产率。The selectivity and yield of hydroxyacetone were calculated according to the formula described in Example 15.
结果表明，果糖转化率为100％。果糖主要转化为羟基丙酮，选择性达68.8％，收率为68.8％。The results showed that the conversion rate of fructose was 100%. Fructose is mainly converted into hydroxyacetone with a selectivity of 68.8% and a yield of 68.8%.
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