WO2016066071A1 - 一种碳水化合物制备乙醇酸酯的方法 - Google Patents

一种碳水化合物制备乙醇酸酯的方法 Download PDF

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WO2016066071A1
WO2016066071A1 PCT/CN2015/092839 CN2015092839W WO2016066071A1 WO 2016066071 A1 WO2016066071 A1 WO 2016066071A1 CN 2015092839 W CN2015092839 W CN 2015092839W WO 2016066071 A1 WO2016066071 A1 WO 2016066071A1
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tungsten
carbohydrate
glycolate
reaction
acid
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王爱琴
徐刚
张涛
郑明远
庞纪峰
王�华
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids

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  • the invention relates to a method for preparing a glycolic acid ester, in particular to a method for preparing a glycolate by a one-step catalytic reaction of a carbohydrate in an alcohol solution through a tungsten-containing catalyst.
  • glycolate is widely used in many fields such as chemical, pharmaceutical, pesticide, feed, perfume and dye. It is an important intermediate for organic synthesis and drug synthesis, and also an important chemical intermediate.
  • glycolate has the following applications: hydrogenation to ethylene glycol, hydrolysis to glycolic acid, production of polyester fiber and use as a cleaning agent; carbonylation to malonate; aminolysis to glycine; oxidation Dehydrogenation to glyoxylate, and then production of glyoxylic acid, can be used to produce vanillin, oral penicillin and allantoin, etc., to form a downstream product branch centered on glycolate, which has broad application prospects.
  • the novel method is the C1 synthesis route, which synthesizes oxalate from syngas and prepares glycolate by controlling the hydrogenation process
  • the object of the present invention is to provide a method for catalytic conversion by which carbohydrates (including cellulose, starch, hemicellulose, sucrose, glucose, fructose, fructan, xylose, soluble xylooligosaccharides, And the natural lignocellulosic raw material containing the above-mentioned carbohydrates) is subjected to reverse aldol condensation and esterification to prepare glycolate in a one-pot method with high yield and high selectivity.
  • carbohydrates including cellulose, starch, hemicellulose, sucrose, glucose, fructose, fructan, xylose, soluble xylooligosaccharides, And the natural lignocellulosic raw material containing the above-mentioned carbohydrates
  • the technical solution adopted by the present invention is: taking carbohydrates, including cellulose, starch, hemicellulose, sucrose, glucose, fructose, fructan, xylose, soluble xylooligosaccharide, and the above-mentioned carbon water.
  • the natural lignocellulosic raw material of the compound is a reaction raw material, and the catalytic reaction is carried out in a closed high-pressure reaction vessel using an alcohol as a solvent.
  • the catalyst is tungsten oxide, tungsten sulfide, tungsten chloride, tungsten carbide, tungsten hydrogen.
  • the cations of tungstate, metatungstate, paratungstate, peroxytungstate and tungsten heteropolyacid salt are one or two of lithium, sodium, potassium, magnesium, calcium ions and ammonium ions.
  • the anion containing a tungsten heteropolyacid salt is one or more of a phosphotungstate ion and a silicotungstate ion.
  • the reaction is stirred in a reaction vessel at a reaction temperature of 100 to 400 ° C and a reaction time of not less than 0.5 minutes; during use, the amount of the active component tungsten metal in the catalyst is 0.05 to 50% by mass of the carbohydrate of the reaction raw material.
  • the reaction alcohol solvent is one or more selected from the group consisting of methanol, ethanol, n-propanol and 2-propanol.
  • the amount of carbohydrate and alcohol in the reaction raw material may be partially or completely liquid under the reaction conditions, and stirring under such conditions may uniformly heat the reactants, thereby avoiding the occurrence of scorching of the raw materials caused by excessive local temperature.
  • the mass ratio of the raw material carbohydrate to the alcohol is from 1:200 to 1:1, preferably from 1:100 to 1:10.
  • glycolic acid ester has the advantages of renewable and non-polluting raw material resources, and meets the requirements of sustainable development.
  • the tungsten-based catalyst used is simple and easy to obtain, has convenient separation, and has good catalytic cycle performance, and has good industrial application prospects.
  • the present invention achieves high selectivity of carbohydrates and high yields of glycolate.
  • the heating rate of /min was raised to 550 ° C, and then the temperature was raised to 900 ° C at a heating rate of 1 ° C / min for 1 h, and the hydrogen flow rate was 120 mL / min.
  • the theoretical loading of W in the prepared catalyst was 30% by weight.
  • CMK-3 The preparation procedure was similar to that of Example 2 except that the AC carrier was replaced with CMK-3.
  • the preparation process of CMK-3 is as follows: 1.25 g of sucrose is dissolved in 5 g of deionized water, 0.14 g of concentrated sulfuric acid is added, 1 g of SBA-15 is added to the obtained mixed solution, and after immersion for 6 hours at room temperature, it is dried at 100 ° C and 160 ° C for 6 h respectively. .
  • the obtained taupe powder was again immersed in a solution consisting of 0.8 g of sucrose, 0.09 g of concentrated sulfuric acid and 5 g of deionized water, and the drying step was repeated.
  • sucrose was completely carbonized by transferring to a tube furnace and maintaining the temperature at 900 ° C for 6 h under a nitrogen atmosphere.
  • 50 ml of 4 wt% hydrofluoric acid was added to the obtained black powder, stirred at room temperature for 2 h, and filtered/washed. This process was repeated three times to completely remove the silica, and finally dried overnight in an oven at 120 ° C to obtain ordered mesoporous carbon CMK. -3.
  • Catalytic conversion experiment 0.5 g of carbohydrate, 0.2 g of catalyst, and 50 ml of methanol were added to a 100 ml reaction vessel, stirred at 800 rpm, and simultaneously heated to 260 ° C for 2 h. After the reaction was completed, the mixture was cooled to room temperature, and the liquid product and the catalyst were separated by centrifugation, and the liquid product was analyzed by gas chromatography. The yield of the product is (moles of carbon from the carbohydrate in the product) / (total moles of carbon in the carbohydrate) x 100%, of which only the target product methyl glycolate, methyl lactate, methyl 2-hydroxybutyrate Methyl levulinate is calculated. Other liquid products include methyl acetate, methyl formate, 1,1,2-3 methoxyethane, 2 methoxyethanol, methyl glucoside and gaseous products (CO, The yield was not calculated for CO 2 , CH 4 , etc.).
  • Example 4 Replace the type of catalyst, the reaction conditions are the same as in Example 4, compare various types of tungsten-containing catalysts H 2 WO 4 , WO 3 , Na 2 WO 4 , AMT, W 2 C/CMK-3, H 3 O 40 PW 12 , H 3
  • the catalytic conversion results of cellulose catalyzed by O 40 SiW 12 , Cs 2.5 H 0.5 PW 12 O 40 are shown in Table 1.
  • cellulose can be converted to methyl glycolate in a high yield on various tungsten-containing catalysts involved in the present invention, wherein the yield on H 2 WO 4 can reach 38.7%.
  • cellulose can be efficiently converted to glycolate in various alcohol solvents of the present invention.
  • the cellulose catalyzed by H 2 WO 4 has excellent methyl glycolate yield, and the preferred temperature is 220-260 °C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

本发明提供了一种碳水化物，包括纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、以及含有上述碳水化合物成分的天然木质纤维原材料制乙醇酸酯的方法。该方法以碳水化合物或含有碳水化合物成分的天然木质纤维原材料为反应原料，以钨的氧化物，钨的硫化物，钨的氯化物，钨的碳化物，钨的氢氧化物，钨青铜，钨酸，含钨酸盐，偏钨酸，偏钨酸盐，仲钨酸，仲钨酸盐，过氧钨酸，过氧钨酸盐，含钨杂多酸，含钨杂多酸盐中的一种或两种以上为催化剂，在100-400℃醇溶剂中经过一步催化转化过程，实现碳水化合物高选择性，高收率制备乙醇酸酯。本发明所提供的反应具有原料为可再生资源，原子经济性高的显著优点。

Description

一种碳水化合物制备乙醇酸酯的方法 技术领域
本发明涉及乙醇酸酯的制备方法，具体地说是碳水化合物在醇溶液中经过含钨催化剂一步催化制乙醇酸酯的方法。
背景技术
乙醇酸酯广泛应用于化工、医药、农药、饲料、香料及染料等许多领域，是作为有机合成和药物合成的重要中间体，同时也是重要的化工中间体。乙醇酸酯作为化工中间体有以下用途：加氢还原制乙二醇，水解制乙醇酸，可用于生产聚酯纤维及用作清洗剂；羰化制丙二酸酯；氨解制甘氨酸；氧化脱氢制乙醛酸酯，进而生产乙醛酸，可用于生产香兰素、口服青霉素及尿囊素等，从而形成以乙醇酸酯为中心的下游产品分支，具有广阔的应用前景。
目前乙醇酸酯的工业生产主要采用氯乙酸与氢氧化钠反应再酯化等一系列过程【文献1：王保伟，乙醇酸甲酯的合成及应用，天然气化工2005,4(30):64-68】，该方法对环境的危害较大，对生产条件的要求较为苛刻。美国Texaco公司Yeakey等人采用(CH3O)2CH2(甲缩醛)和HCOOH为原料,在一种有机过氧化物存在的情况下,并于非酸性条件下制备乙醇酸酯，但反应需分段进行，且产物分离困难【文献2:Production of Alkyl glycolates,Patent No.US 4602102】。另外还有乙二醛甲醇一步法【文献3:羟基乙酸酯的制造方法,Patent No.JP 08-104665】，甲酸甲酯与甲醛(或聚甲醛等)偶联法等【文献4:杞卫东,乙醇酸甲酯偶联反应的研究进展，云南化工，2002,29(4):33-35】。在这些方法中，乙二醛有剧毒，强烈刺激皮肤黏膜，且价格昂贵，不利于工业生产，而偶联法需要用到多聚甲醛和固体强酸，成本较高。目前较新颖的方法是C1合成路线，由合成气合成草酸酯，通过控制加氢过程制备乙醇酸酯【文献5：Catalyst for hydrogenation of dimethyl oxalate to methyl glycolate,comprises copper as active component,auxiliary active component and aluminum as structural carrier,in specified weight ratio,patent No.CN103801303-A；文献6:张旭，草酸二乙酯气相加氢催化剂助剂的研究[D],天津大学,2008】，但容易过度加氢到乙二醇导致选择性降低。
上述方法除了各自缺点外还有个共同的弊端，即原料均来自于石化资源。而利用可再生生物质资源制备乙醇酸酯，可以减少人类对化石资源的依赖，有利于实现环境友好和经济可持续发展。多羟基化合物，包括纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖在自然界中广泛存在。随着农业技术的发展，其产量日益增长。发展碳水化合物制备乙醇酸酯不仅能部分降低对石油资源的依赖，同时有助于实现农产品深加工制高附加值化学品。从目前文献的调研结果看，尚未有任何报道是以碳水化合物为原料高效、高选择性地催化降解制取乙醇酸酯。
发明内容
本发明的目的在于提供一种催化转化的方法，利用该方法可使碳水化合物(包括纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、以及含有上述碳水化合物的天然木质纤维原材料)经过逆羟醛缩合和酯化反应，一锅法高收率、高选择性地制备乙醇酸酯。
为实现上述目的，本发明采取的技术方案为：以碳水化合物，包括纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、以及含有上述碳水 化合物的天然木质纤维原材料为反应原料，以醇为溶剂，在密闭高压反应釜内进行催化反应，催化剂为钨的氧化物，钨的硫化物，钨的氯化物，钨的碳化物，钨的氢氧化物，钨青铜，钨酸，含钨酸盐，偏钨酸，偏钨酸盐，仲钨酸，仲钨酸盐，过氧钨酸，过氧钨酸盐，含钨杂多酸，含钨杂多酸盐中的一种或两种以上；
钨酸盐、偏钨酸盐、仲钨酸盐、过氧钨酸盐和含钨杂多酸盐的阳离子为锂、钠、钾、镁、钙离子及铵根离子中的一种或两种以上，含钨杂多酸盐的阴离子为磷钨酸根离子、硅钨酸根离子中的一种或两种以上。
在反应釜内搅拌反应，反应温度100-400℃，反应时间不少于0.5分钟；在使用过程中，催化剂中活性组分钨金属的量为反应原料碳水化合物质量的0.05-50％。
所述反应醇溶剂为甲醇，乙醇，正丙醇，2-丙醇中的一种或两种以上。反应原料碳水化合物与醇的用量以反应条件下反应物料部分或完全为液态即可，在此条件下进行搅拌，可以使反应物受热均匀，避免局部温度过高引起原料烧焦现象发生。较佳的反应条件下反应原料碳水化合物与醇的质量比为1:200-1:1，优选1:100-1:10。
本发明具有如下优点：
1.以碳水化合物(包括纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、以及含有上述碳水化合物的天然木质纤维原材料)为反应原料制备乙醇酸酯，相对于现有的乙醇酸酯工业合成路线中的原料，具有原料资源可再生无污染的优点，符合可持续发展的要求。
2.所使用的钨基催化剂简单易得，分离方便，且具有良好的催化循环性能，具有很好的工业应用前景。
3.本发明实现碳水化合物高选择性，高收率制备乙醇酸酯。
具体实施方式
下面通过具体实施例对本发明进行详细说明，但这些实施例并不对本发明的内容构成限制。
实施例1
Cs2.5H0.5PW12O40催化剂的制备
分别把2.5g CS2CO3和18.12g预处理得到的H3PW12O40·6H20配成0.1mol·L-1和0.08mol·L-1的溶液，0.1mol.L-1的Cs2CO3溶液以1mL·min-1的速率在室温下滴加到0.08mol·L-1H3PW12040溶液中。滴加完毕，继续搅拌0.5h后，于室温下静置20h。然后在323K下缓慢蒸发水分，得白色固体，然后在110℃左右烘干，用前在300℃焙烧2h，比表面积为108m2·g-1。
实施例2
W2C/AC的制备：称50g活性炭(AC),250mL 33wt％HNO3，置于500mL三口烧瓶中，80℃水浴处理24h,洗涤至中性，120℃烘干24h。将1g预处理过的AC倒入含0.588g偏钨酸铵的水溶液中，经120℃烘箱干燥后，将此催化剂前体于氢气中进行程序升温还原，具体反应过程为：由室温以8.8℃/min的升温速率升至550℃，然后以1℃/min的升温速率升温至900℃并保持1h，氢气流速为120mL/min。所制备的催化剂中W的理论担载量为30wt％。
实施例3
W2C/CMK-3的制备：制备过程类似于实施例2，不同之处在于AC载体替换为CMK-3。CMK-3制备过程为：取1.25g蔗糖溶于5g去离子水中，加入0.14g浓硫酸，在得到的混合溶液加入1g SBA-15，室温下浸渍6h后分别在100℃和160℃下干燥6h。将得到的灰褐色粉末再次浸渍在由0.8g蔗糖、0.09g浓硫酸和5g去离子水组成的溶 液中，重复干燥步骤。转入管式炉中于氮气气氛下900℃恒温6h，使蔗糖完全炭化。向得到的黑色粉末中加入50ml 4wt％氢氟酸，室温下搅拌2h、过滤/洗涤，此过程重复三次以彻底去除二氧化硅，最后于120℃烘箱中过夜干燥，得到有序介孔炭CMK-3。
实施例4
催化转化实验：将0.5g碳水化合物，0.2g催化剂,和50ml甲醇加入到100ml反应釜中，以800转/min的速度进行搅拌，同时升温到260℃，反应2h。反应结束后，降至室温、离心分离液体产物与催化剂，液体产物采用气相色谱分析。产物的收率为(产物中来自碳水化合物的碳摩尔数)/(碳水化合物中碳总摩尔数)×100％，其中仅对目标产物乙醇酸甲酯，乳酸甲酯，2羟基丁酸甲酯，乙酰丙酸甲酯进行计算，其它液体产物包括乙酸甲酯，甲酸甲酯，1,1,2-3甲氧基乙烷，2甲氧基乙醇，甲基葡萄糖苷以及气体产物(CO,CO2，CH4等)未计算其收率。
实施例5
替换催化剂的种类，反应条件同实施例4,比较各类含钨催化剂H2WO4，WO3，Na2WO4,AMT,W2C/CMK-3,H3O40PW12,H3O40SiW12,Cs2.5H0.5PW12O40催化下纤维素的催化转化结果，见表1。
表1各种催化剂上纤维素催化转化性能的比较
Figure PCTCN2015092839-appb-000001
如表所示，纤维素能够在本发明中所涉及的各种含钨催化剂上高收率地转化为乙醇酸甲酯，其中，H2WO4上的收率可以达到38.7％。
实施例6
替换溶剂种类，反应条件同实施例4，比较甲醇，乙醇，正丙醇体系中纤维素催化转化结果，见表2。
表2各种醇溶剂中纤维素催化转化性能的比较
Figure PCTCN2015092839-appb-000002
如表所示，纤维素能在本发明所涉及的各类醇溶剂中有效转化为乙醇酸酯。
实施例7
替换碳水化合物种类，反应条件同实施例4，比较纤维素，纤维二糖，葡萄糖，淀粉的催化转化结果，见表3。
表3各种碳水化合物催化转化性能的比较
Figure PCTCN2015092839-appb-000003
如表所示，各种碳水化合物均能够在本发明所涉及的含钨催化体系中有效的转化为乙醇酸甲酯。该体系具有比较广泛的应用领域。
实施例8
不同反应温度下H2WO4催化剂上纤维素催化转化性能的比较。见表4，除反应温度不同外，反应条件同实施例4。
表4不同反应温度下H2WO4催化剂上纤维素催化转化性能的比较
Figure PCTCN2015092839-appb-000004
从表中可以看出，在一定的温度范围内，用H2WO4催化纤维素均有优良的乙醇酸甲酯收率，较佳温度是220-260℃。
实施例9
不同反应时间下H2WO4催化剂上纤维素催化转化性能的比较。见表5，除反应时间不同外，反应条件同实施例4。
表5不同反应时间下H2WO4催化剂上纤维素催化转化性能的比较
Figure PCTCN2015092839-appb-000005
从表中可以看出，在一定的时间范围内，用H2WO4催化纤维素均有优良的乙醇酸甲酯收率，较佳时间是1-5h。

Claims (8)

  1. 一种碳水化合物制备乙醇酸酯的方法，其特征在于：以碳水化合物为反应原料，以醇为溶剂，以含钨化合物为催化剂在密闭高压反应釜内进行催化反应，得到产物乙醇酸酯。
  2. 按照权利要求1所述的方法，其特征在于：所述碳水化合物为纤维素、淀粉、半纤维素、蔗糖、葡萄糖、果糖、果聚糖、木糖、可溶性低聚木糖、以及含有上述碳水化合物成分的天然木质纤维原材料中的一种或两种以上。
  3. 按照权利要求2所述的方法，其特征在于：所述天然木质纤维原材料为稻秆、麦秆、麻秆、苇秆、高粱秆，甘蔗渣，锯末，芒草，柳枝稷，芦竹，菊芋中的一种或两种以上；可溶性低聚木糖为木二糖、木三糖、木四糖中的一种或两种以上。
  4. 按照权利要求1所述的方法，其特征在于：所述醇溶剂为甲醇、乙醇、正丙醇、2-丙醇中的一种或两种以上。
  5. 按照权利要求1所述的方法，其特征在于：所述产物乙醇酸酯为乙醇酸甲酯、乙醇酸乙酯、乙醇酸丙酯、乙醇酸异丙酯中的一种或两种以上。
  6. 按照权利要求1所述的方法，其特征在于：所述含钨化合物为钨的氧化物，钨的硫化物，钨的氯化物，钨的碳化物，钨的氢氧化物，钨青铜，钨酸，钨酸盐，偏钨酸，偏钨酸盐，仲钨酸，仲钨酸盐，过氧钨酸，过氧钨酸盐，含钨杂多酸，含钨杂多酸盐中的一种或两种以上。
  7. 按照权利要求1所述的方法，其特征在于：反应温度为100-400℃，优选的反应温度为180-300℃，反应时间不少于0.5分钟，优选反应时间为1h-5h。
  8. 按照权利要求1、2、4、6或7所述的方法，其特征在于：所述碳水化合物与醇的质量比为1:200-1:1，优选1:100-1:10；催化剂中活性组分钨金属的量为反应原料碳水化合物质量的0.05-50％，优选5-15％。
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