[go: up one dir, main page]

CN107586254B - A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate - Google Patents

A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate Download PDF

Info

Publication number
CN107586254B
CN107586254B CN201610530368.8A CN201610530368A CN107586254B CN 107586254 B CN107586254 B CN 107586254B CN 201610530368 A CN201610530368 A CN 201610530368A CN 107586254 B CN107586254 B CN 107586254B
Authority
CN
China
Prior art keywords
ethylene glycol
oxalate
hydrophilic silica
catalyst
sio
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
Application number
CN201610530368.8A
Other languages
Chinese (zh)
Other versions
CN107586254A (en
Inventor
徐恒泳
葛庆杰
马俊国
孙剑
周佳
王伟
夏锐
夏伦超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Corps Modern Green Chlor Alkali Chemical Engineering Research Center Co ltd
Dalian Institute of Chemical Physics of CAS
Original Assignee
Xinjiang Corps Modern Green Chlor Alkali Chemical Engineering Research Center Co ltd
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xinjiang Corps Modern Green Chlor Alkali Chemical Engineering Research Center Co ltd, Dalian Institute of Chemical Physics of CAS filed Critical Xinjiang Corps Modern Green Chlor Alkali Chemical Engineering Research Center Co ltd
Priority to CN201610530368.8A priority Critical patent/CN107586254B/en
Publication of CN107586254A publication Critical patent/CN107586254A/en
Application granted granted Critical
Publication of CN107586254B publication Critical patent/CN107586254B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及一种草酸酯催化加氢合成乙二醇的方法,主要解决草酸酯加氢制乙二醇的催化反应过程中选择性低和催化剂寿命短的问题。本发明采用催化剂以金属铜或铜氧化物为活性组分,以亲水性二氧化硅或改性亲水性二氧化硅为载体,并加以合适金属氧化物助剂。本发明催化剂具有较高的反应性能和反应稳定性。The invention relates to a method for synthesizing ethylene glycol by catalytic hydrogenation of oxalate, and mainly solves the problems of low selectivity and short catalyst life in the catalytic reaction process of oxalate hydrogenation to ethylene glycol. The present invention adopts the catalyst with metal copper or copper oxide as active component, hydrophilic silica or modified hydrophilic silica as carrier, and adding suitable metal oxide auxiliary agent. The catalyst of the invention has higher reaction performance and reaction stability.

Description

一种草酸酯加氢合成乙二醇的方法A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate

技术领域technical field

本发明涉及草酸酯加氢制乙二醇的方法,主要解决草酸酯加氢制乙二醇反应一般催化反应中选择性低和催化剂寿命短的问题。The invention relates to a method for preparing ethylene glycol by hydrogenating oxalate, and mainly solves the problems of low selectivity and short catalyst life in the general catalytic reaction of oxalate hydrogenation to prepare ethylene glycol.

背景技术Background technique

乙二醇(EG)作为重要有机化工原料,不仅可生产聚酯树脂、醇酸树脂和聚酯纤维的单体,而且还可生产润滑剂、增塑剂、胶黏剂和表面活性剂等诸多产品的原材料。近年来乙二醇需求量不断持续增长。乙二醇传统生产工艺为环氧乙烷水合法,该方法工艺流程长,能耗高,乙二醇选择性低,且该生产工艺过度依赖石油资源。合成气经草酸酯制乙二醇是非石油路线合成乙二醇研究较多、相对成熟的方法。该法首先由非石油资源制备合成气(CO+H2),再由CO氧化偶联生成草酸酯,草酸酯进一步催化加氢生成乙二醇。该方法由于工艺流程简单,能耗低以及乙二醇选择性高而颇具应用前景。As an important organic chemical raw material, ethylene glycol (EG) can not only produce monomers of polyester resin, alkyd resin and polyester fiber, but also produce lubricants, plasticizers, adhesives and surfactants, etc. raw materials for the product. In recent years, the demand for ethylene glycol has continued to grow. The traditional production process of ethylene glycol is the ethylene oxide hydration method. This method has a long process flow, high energy consumption, low ethylene glycol selectivity, and the production process is overly dependent on petroleum resources. The synthesis of ethylene glycol from synthesis gas through oxalate is a relatively mature method for the synthesis of ethylene glycol through non-petroleum routes. In this method, syngas (CO+H 2 ) is first prepared from non-petroleum resources, and then oxalate is formed by oxidative coupling of CO, and oxalate is further catalyzed and hydrogenated to form ethylene glycol. The method has great application prospects due to its simple process flow, low energy consumption and high ethylene glycol selectivity.

草酸酯加氢制乙二醇过程被认为是该工艺的关键步骤,该过程主要发生如下反应:(1)草酸酯加氢生成中间产物乙醇酸甲酯;(2)乙醇酸甲酯进一步加氢生成乙二醇;(3)乙二醇继续加氢生成乙醇或其它二元醇副产物;(4) 乙二醇与其他单醇反应生成醚。因此,在草酸酯加氢制乙二醇过程中,如何提高产品选择性是关键。目前,研发选择性高、稳定性好的草酸酯加氢制乙二醇催化剂是该过程的一个研究热点。Oxalate hydrogenation to ethylene glycol process is considered to be the key step of this technology, and this process mainly occurs following reaction: (1) oxalate hydrogenation generates intermediate product methyl glycolate; (2) methyl glycolate further Hydrogenation generates ethylene glycol; (3) ethylene glycol continues to be hydrogenated to generate ethanol or other dihydric alcohol by-products; (4) ethylene glycol reacts with other monoalcohols to generate ether. Therefore, in the process of oxalate hydrogenation to ethylene glycol, how to improve the product selectivity is the key. At present, the development of catalysts for the hydrogenation of oxalate to ethylene glycol with high selectivity and good stability is a research hotspot in this process.

相对于均相加氢催化剂,非均相加氢催化剂因具有制备方法简单、反应条件温和、催化剂易分离等优点而成为近年草酸二甲酯加氢制乙二醇反应催化剂的研究重点,特别是活性高、价廉易得、制备简单的铜基催化剂更是引起愈来愈多的重视。人们对铜基催化剂的制备方法、载体选择和助剂改性等进行了大量研究,通过改进催化剂的抗毒性能、抗烧结等提高了催化剂的反应性能和反应稳定性。如:日本宇部专利(US 4,229,591)采用蒸氨法制备的铜基催化剂在180℃、氢酯比为300的反应条件下,草酸酯转化率可达100%,乙二醇选择性高达99.5%。福建物构所最早研究的Cu-Cr催化剂,在200~230℃,2.5~3MPa,气液比为46~60条件下,可获得99.8%的草酸酯转化率,乙二醇选择性可达95.3%.此外,天津大学、复旦大学、华东理工大学、浙江大学、中石化上海石油化工研究院等单位也相继开展了草酸酯加氢制乙二醇铜基催化剂的研究工作,改善了草酸酯加氢制乙二醇铜基催化剂的性能。Compared with homogeneous hydrogenation catalysts, heterogeneous hydrogenation catalysts have become the research focus of catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol in recent years due to their simple preparation method, mild reaction conditions, and easy separation of catalysts. Copper-based catalysts with high activity, low cost, easy preparation and simple preparation have attracted more and more attention. A lot of research has been done on the preparation method, carrier selection and modifier modification of copper-based catalysts, and the reaction performance and reaction stability of the catalyst have been improved by improving the anti-toxicity and anti-sintering properties of the catalyst. For example: Japanese Ube Patent (US 4,229,591) uses the copper-based catalyst prepared by the ammonia distillation method under the reaction conditions of 180 ° C and a hydrogen ester ratio of 300, the oxalate conversion rate can reach 100%, and the ethylene glycol selectivity can reach 99.5%. . The Cu-Cr catalyst firstly studied by the Fujian Institute of Physics and Architecture can obtain 99.8% oxalate conversion at 200-230℃, 2.5-3MPa, and gas-liquid ratio of 46-60, and the ethylene glycol selectivity can reach 99.8%. 95.3%. In addition, Tianjin University, Fudan University, East China University of Science and Technology, Zhejiang University, Sinopec Shanghai Petrochemical Research Institute and other units have also successively carried out research work on copper-based catalysts for oxalate hydrogenation to ethylene glycol, improving oxalic acid. Properties of copper-based catalysts for the hydrogenation of esters to ethylene glycol.

虽然这些研究在实验室中取得了良好效果,同时国内也建设了多套合成气经草酸酯生产乙二醇的工业放大试验装置,但其产品乙二醇的纯度距聚酯用乙二醇标准仍有一定距离,该催化剂的稳定性仍有待进一步改进。同时,文献中报道Cu基催化剂的SiO2载体多以硅溶胶为载体来源,虽然可提高催化剂分散度,但如果催化剂进行大规模放大,无疑会增加生产成本和环境负担。同时载体SiO2的结构和物化性能将对铜基催化剂的加氢性能有较大影响。Although these studies have achieved good results in the laboratory, and at the same time, several sets of industrial scale-up test equipment for the production of ethylene glycol from syngas through oxalate have also been built in China, but the purity of the product ethylene glycol is lower than that of polyester ethylene glycol. The standard is still a certain distance away, and the stability of the catalyst still needs to be further improved. At the same time, it is reported in the literature that the SiO 2 supports of Cu-based catalysts are mostly derived from silica sol. Although the dispersion of the catalyst can be improved, if the catalyst is scaled up on a large scale, it will undoubtedly increase the production cost and environmental burden. At the same time, the structure and physicochemical properties of supported SiO2 will have a great influence on the hydrogenation performance of copper-based catalysts.

本发明目的是通过改进载体SiO2的性能改善草酸酯加氢制乙二醇催化剂的选择性和反应稳定性,进而改善本发明反应过程的效率。The purpose of the present invention is to improve the selectivity and reaction stability of the catalyst for hydrogenating oxalate to ethylene glycol by improving the performance of the carrier SiO 2 , thereby improving the efficiency of the reaction process of the present invention.

发明内容SUMMARY OF THE INVENTION

本发明所要解决的技术问题是针对现有技术不足,提供一种草酸酯催化加氢制乙二醇的方法,该方法采用至少含有草酸酯和氢气的原料通过一种催化剂生产乙二醇。该方法采用的催化剂包含活性组分金属铜或铜氧化物或其混合物、载体亲水性二氧化硅或改性亲水性二氧化硅、助剂金属氧化物,其中所述催化剂中铜元素质量百分比为10-60%,所述催化剂中二氧化硅质量百分比为35-90%,所述催化剂中金属氧化物助剂的质量百分比不高于5%。本发明通过调控二氧化硅的亲水性和酸性来提高催化剂的选择性和稳定性。The technical problem to be solved by the present invention is to aim at the deficiencies of the prior art, and to provide a method for ethylene glycol by catalytic hydrogenation of oxalate, which adopts the raw material containing at least oxalate and hydrogen to produce ethylene glycol through a catalyst . The catalyst used in the method comprises active component metal copper or copper oxide or a mixture thereof, carrier hydrophilic silica or modified hydrophilic silica, auxiliary metal oxide, wherein the mass of copper element in the catalyst is The percentage is 10-60%, the mass percentage of silica in the catalyst is 35-90%, and the mass percentage of the metal oxide auxiliary agent in the catalyst is not higher than 5%. The present invention improves the selectivity and stability of the catalyst by regulating the hydrophilicity and acidity of the silica.

二氧化硅的亲水性与其表面存在的羟基(-OH)有直接关联,一般来说,其表面存在的羟基个数越多,其亲水能力越强。因此,我们通常采用SiO2表面羟基个数的多少来表示二氧化硅亲水性。通常采用表面活性剂的改性增加SiO2的亲水性,通过对表面进行疏水处理来降低SiO2的亲水性。对于作为催化剂载体的SiO2来说,其表面控制适当的亲水性有利于催化剂的性能发挥。The hydrophilicity of silica is directly related to the hydroxyl groups (-OH) present on its surface. Generally speaking, the more hydroxyl groups present on its surface, the stronger its hydrophilicity. Therefore, we usually use the number of hydroxyl groups on the surface of SiO 2 to represent the hydrophilicity of silica. Usually, the modification of surfactant is used to increase the hydrophilicity of SiO2 , and the hydrophilicity of SiO2 is reduced by hydrophobic treatment of the surface. For SiO 2 as a catalyst carrier, proper hydrophilicity control on its surface is beneficial to the performance of the catalyst.

本发明通过控制SiO2表面的羟基数目或采用疏水基团 适当取代SiO2的表面羟基进行SiO2的亲水性改性,具体的亲水性SiO2指的是其表面羟基数目在4~5个/nm2,且不含疏水基团 的二氧化硅。亲水性二氧化硅的改性,指的是具有0.1~40%、或0.1~25%的表面羟基被疏水基团取代的SiO2;改性后的亲水性二氧化硅表面羟基数目为2.4~5.0个/nm2、或为3.0~4.5个/nm2。所述疏水基团 指烷基、烷氧基、烯基,特别优化为甲基、甲氧基、乙烯基,特别优化为甲基。The present invention conducts hydrophilic modification of SiO 2 by controlling the number of hydroxyl groups on the surface of SiO 2 or appropriately replacing the surface hydroxyl groups of SiO 2 with hydrophobic groups. Pieces/nm 2 , silica without hydrophobic groups. The modification of hydrophilic silica refers to SiO 2 with 0.1-40%, or 0.1-25% of surface hydroxyl groups replaced by hydrophobic groups; the number of hydroxyl groups on the surface of the modified hydrophilic silica is 2.4 to 5.0 pieces/nm 2 , or 3.0 to 4.5 pieces/nm 2 . The hydrophobic group refers to an alkyl group, an alkoxy group, and an alkenyl group, and is particularly optimized to be a methyl group, a methoxy group, and a vinyl group, and a particularly optimized group is a methyl group.

本发明亲水性二氧化硅的制备包括:硅酸钠、硫酸钠和水同时加入到制备容器中,硅酸钠、硫酸钠和水的质量比例为1:0.01~0.5:5~15,室温搅拌,升温至80~90℃,滴加质量分数为2%~20%的硫酸溶液至体系pH 为10~11,陈化15~60分钟;加质量分数为2%~20%硫酸调整pH值至4~6.5 (过滤,水洗至无SO4 2-,乙醇洗涤除去水分,100~120℃干燥、200~800℃焙烧得白色粉末为亲水性SiO2;SiO2载体形成的原理为:硅酸钠在酸性条件下生成原硅酸,小分子硅酸通过脱水缩聚反应联接形成具有无规则链枝状结构的球形粒子SiO2;通过控制SiO2形成时的条件控制SiO2的表面羟基数目。The preparation of the hydrophilic silicon dioxide of the present invention includes: adding sodium silicate, sodium sulfate and water into the preparation container at the same time, the mass ratio of sodium silicate, sodium sulfate and water is 1:0.01-0.5:5-15, room temperature Stir, heat up to 80-90°C, add dropwise a sulfuric acid solution with a mass fraction of 2%-20% until the pH of the system is 10-11, and age for 15-60 minutes; add a mass fraction of 2%-20% sulfuric acid to adjust the pH value to 4~6.5 (filtered, washed with water until no SO 4 2- , washed with ethanol to remove water, dried at 100~120 ℃, calcined at 200~800 ℃ to obtain a white powder that is hydrophilic SiO 2 ; the principle of SiO 2 carrier formation is: silicon Sodium generates orthosilicic acid under acidic conditions, and small molecular silicic acid is linked by dehydration polycondensation to form spherical particles SiO 2 with random chain branch structure; the number of surface hydroxyl groups of SiO 2 is controlled by controlling the conditions of SiO 2 formation.

改性亲水性SiO2的制备包括: The preparation of modified hydrophilic SiO includes:

硅酸钠、硫酸钠和水同时加入到制备容器中,硅酸钠、硫酸钠和水的质量比例为1:0.01~0.5:5~15,室温搅拌,升温至80~90℃,滴加质量分数为2%~20%的硫酸溶液至体系pH为10~11,陈化15~60min;加质量分数为2%~20%硫酸调整pH至4-6.5,加入含疏水基团的化合物,陈化0.5~4h,过滤,水洗至无SO4 2-,乙醇洗涤除去水分,100~120℃干燥、200~800℃焙烧得白色粉末为改性亲水性SiO2Sodium silicate, sodium sulfate and water are added into the preparation container at the same time, the mass ratio of sodium silicate, sodium sulfate and water is 1:0.01~0.5:5~15, stirring at room temperature, warming up to 80~90℃, adding dropwise mass The pH of the system is 10-11 with a concentration of 2%-20% sulfuric acid solution, and aging for 15-60min; add a mass fraction of 2%-20% sulfuric acid to adjust the pH to 4-6.5, add a compound containing a hydrophobic group, and age Heat for 0.5-4 h, filter, wash with water until no SO 4 2- , wash with ethanol to remove water, dry at 100-120 ℃, calcinate at 200-800 ℃ to obtain a white powder which is modified hydrophilic SiO 2 .

改性亲水性SiO2形成的原理为:疏水基团的前驱体在酸性条件下可水解成小分子物质,这些水解产物与合成SiO2的表面羟基发生反应,带有疏水基团(如:甲基、乙烯基、乙氧基)的小分子有机物接枝到SiO2表面,得到改性亲水性SiO2The principle of the formation of modified hydrophilic SiO 2 is that the precursors of hydrophobic groups can be hydrolyzed into small molecular substances under acidic conditions, and these hydrolyzed products react with the surface hydroxyl groups of synthesizing SiO 2 with hydrophobic groups (such as: The small molecular organic compounds of methyl, vinyl, ethoxy) were grafted to the surface of SiO 2 to obtain modified hydrophilic SiO 2 .

SiO2表面具有酸性中心,其酸性强弱直接关系到SiO2载体与催化剂活性组分的相互作用,进而影响催化性能,控制适当的酸性范围对于发挥SiO2载体的催化反应作用有重要意义。通常,SiO2的酸性与其与水混合搅拌稳定后形成水溶液的pH值有直接关联。因此,本发明通过测定SiO2水溶液的pH 值来判断SiO2的酸性。本发明的亲水性SiO2或改性亲水性SiO2的4%水溶液 pH值小于6.1、或在2.2-6.0之间、或在3.0-5.0之间。The surface of SiO2 has an acid center, and its acidity is directly related to the interaction between the SiO2 support and the active components of the catalyst, which in turn affects the catalytic performance. Controlling the appropriate acidity range is of great significance for the catalytic reaction of the SiO2 support. Generally, the acidity of SiO 2 is directly related to the pH value of the aqueous solution formed after it is mixed with water and stabilized with stirring. Therefore, the present invention determines the acidity of SiO 2 by measuring the pH value of the SiO 2 aqueous solution. The pH value of the 4% aqueous solution of hydrophilic SiO 2 or modified hydrophilic SiO 2 of the present invention is less than 6.1, or between 2.2 and 6.0, or between 3.0 and 5.0.

为解决现有草酸酯加氢存在的技术问题,本发明采用催化剂制备的技术方案是:In order to solve the technical problem that existing oxalate hydrogenation exists, the technical scheme that the present invention adopts catalyst to prepare is:

一种草酸酯加氢制乙二醇催化剂,以金属Cu或铜氧化物或其混合物作为活性组分,其特征在于:催化剂以亲水性SiO2或改性亲水性SiO2为载体,所述催化剂中各组分的质量百分比为:活性元素Cu占10~60%,载体 SiO2占35-90%,金属氧化物助剂占比不高于5%。A kind of oxalate hydrogenation ethylene glycol catalyst, with metal Cu or copper oxide or its mixture as active component, it is characterized in that: catalyzer is with hydrophilic SiO 2 or modified hydrophilic SiO 2 as carrier, The mass percentage of each component in the catalyst is as follows: the active element Cu accounts for 10-60%, the carrier SiO 2 accounts for 35-90%, and the metal oxide assistant accounts for no more than 5%.

在一些实施方式中,所述亲水性SiO2的表面羟基未被疏水基团取代。在一些实施方式中,本申请所述亲水性二氧化硅的部分表面羟基被疏水基团取代,但仍保持其亲水特征。In some embodiments, the surface hydroxyl groups of the hydrophilic SiO 2 are not substituted with hydrophobic groups. In some embodiments, some of the surface hydroxyl groups of the hydrophilic silica described herein are replaced with hydrophobic groups, but still retain their hydrophilic character.

二氧化硅的表面羟基数可通过滴定法测定。滴定法包括以下步骤:首先,称取4.0g干燥的二氧化硅样品,加入50mL乙醇润湿,再加入150mL 20%的NaCl溶液,充分搅拌;其次,用0.1mol/L的HCl溶液调节溶液pH 至4.0;最后,用0.1mol/L的NaOH溶液滴定至pH=9.0,等待直至至少3 分钟不改变。硅氧化物的表面羟基数用将4.0g硅氧化物的pH值从4.0变至9.0所消耗的NaOH体积来表示。S(m2/g)为硅氧化物的BET比表面积, V(mL)为滴定所消耗的NaOH体积,计算二氧化硅表面的羟基个数/nm2的公式如下:The surface hydroxyl number of silica can be determined by titration. The titration method includes the following steps: first, weigh 4.0 g of dry silica sample, add 50 mL of ethanol to wet it, then add 150 mL of 20% NaCl solution, and stir well; secondly, adjust the pH of the solution with 0.1 mol/L HCl solution to 4.0; finally, titrate to pH=9.0 with 0.1 mol/L NaOH solution, waiting until no change for at least 3 minutes. The surface hydroxyl number of silicon oxide is expressed as the volume of NaOH consumed to change the pH of 4.0 g of silicon oxide from 4.0 to 9.0. S (m 2 /g) is the BET specific surface area of silicon oxide, V (mL) is the volume of NaOH consumed by the titration, and the formula for calculating the number of hydroxyl groups/nm 2 on the silica surface is as follows:

二氧化硅表面的羟基个数(个/nm2)=6.02×1023×(V/4)×10-4/(S ×1018)The number of hydroxyl groups on the silica surface (number/nm 2 )=6.02×10 23 ×(V/4)×10 -4 /(S×10 18 )

二氧化硅的表面羟基取代率可通过标准SiO2样品(表面羟基未被取代) 的表面羟基数减去经处理二氧化硅样品表面羟基数的结果除以标准二氧化硅样品的表面羟基数计算得出。任何二氧化硅经过硅烷化试剂例如卤代硅烷(如烷基氯)、硅氧烷,特别是二甲基硅氧烷(如六甲基二硅氧烷)或硅氮烷处理,其表面羟基基团将被疏水性基团取代。The surface hydroxyl substitution rate of silica can be calculated by subtracting the surface hydroxyl number of the treated silica sample from the surface hydroxyl number of the standard SiO sample ( surface hydroxyl groups are not substituted) and dividing the surface hydroxyl number of the standard silica sample inferred. Surface hydroxyl groups of any silica treated with silylating agents such as halosilanes (eg alkyl chlorides), siloxanes, especially dimethylsiloxanes (eg hexamethyldisiloxane) or silazanes groups will be replaced by hydrophobic groups.

本发明制备的亲水性二氧化硅经上述方法测定其表面羟基数目为4~5 个/nm2,且不含疏水基团 。本发明制备的改性亲水性二氧化硅经上述方法测定其表面羟基数目为2.4~5.0个/nm2、或为3.0~4.5个/nm2The hydrophilic silica prepared by the present invention has a surface hydroxyl number of 4-5/nm 2 as determined by the above method, and does not contain hydrophobic groups. The modified hydrophilic silica prepared by the present invention has a surface hydroxyl number of 2.4-5.0/nm 2 or 3.0-4.5/nm 2 as determined by the above method.

在一些实施方式中,本申请所述二氧化硅为酸性二氧化硅,其中二氧化硅4%水溶液的pH值低于7.0。二氧化硅的pH值可通过将4g干燥二氧化硅与100mL蒸馏水充分混合之后测量溶液的pH值而获得。在一些实施方式中,所述二氧化硅的4%水溶液pH值低于6.1,或低于6.0,或低于5.0,或低于4.0,或低于3.0,或低于2.2,或低于1.0。在一些实施方式中,所述二氧化硅的4%水溶液的pH值为2.0-6.0。在一些实施方式中,所述硅氧化物的4%水溶液pH值为3.0-5.0。In some embodiments, the silica described herein is an acidic silica, wherein the pH of a 4% aqueous solution of silica is below 7.0. The pH of the silica can be obtained by measuring the pH of the solution after thoroughly mixing 4 g of dry silica with 100 mL of distilled water. In some embodiments, the pH of the silica in a 4% aqueous solution is lower than 6.1, or lower than 6.0, or lower than 5.0, or lower than 4.0, or lower than 3.0, or lower than 2.2, or lower than 1.0 . In some embodiments, the pH of the 4% aqueous solution of silica is 2.0-6.0. In some embodiments, the 4% aqueous solution of silicon oxide has a pH of 3.0-5.0.

本发明所述金属氧化物助剂包括CeO2、TiO2等金属氧化物,助剂的质量百分含量不超过5%,优化为0.2~3%。The metal oxide auxiliary agent of the present invention includes CeO 2 , TiO 2 and other metal oxides, and the mass percentage content of the auxiliary agent is not more than 5%, and is optimized to be 0.2-3%.

本发明所述催化剂的制备过程为:a)将含铜盐、金属盐和氨水混合,其中所述金属盐可生成金属氧化物;b)在步骤(a)生成的溶液中加入二氧化硅;c)除去氨;d)焙烧、碾磨步骤c)的产物。The preparation process of the catalyst of the present invention is as follows: a) mixing copper-containing salt, metal salt and ammonia water, wherein the metal salt can generate metal oxide; b) adding silica to the solution generated in step (a); c) removal of ammonia; d) calcination, milling of the product of step c).

在一些实施方式中,在使用前还原所述催化剂,例如通过传统方法在还原剂如氢气、一氧化碳或其他还原剂存在的条件下加热制备得到的催化剂。在一些实施方式中,在氢气和/或一氧化碳存在的条件下通过加热还原所述催化剂。In some embodiments, the catalyst is reduced prior to use, eg, a catalyst prepared by conventional methods by heating in the presence of a reducing agent such as hydrogen, carbon monoxide, or other reducing agents. In some embodiments, the catalyst is reduced by heating in the presence of hydrogen and/or carbon monoxide.

本发明催化剂的反应性能评价采用如下方案:在连续流动气固相反应器中进行,催化剂填装量为1.0g.采用纯氢常压350℃还原催化剂,流速为 100mL/min,以1~2℃/min的速率从室温升温至350℃,并保持4h,降至反应温度后通入H2,用平流泵打入草酸二甲酯或其甲醇溶液进行反应。产物用气相色谱进行分析,色谱柱为30m FFAP型极性毛细柱,氢火焰检测器 (FID)检测反应原料和产物。The reaction performance evaluation of the catalyst of the present invention adopts the following scheme: it is carried out in a continuous flow gas-solid phase reactor, and the catalyst filling amount is 1.0 g. The catalyst is reduced with pure hydrogen at normal pressure at 350° C., the flow rate is 100 mL/min, and the rate of 1-2 The rate of ℃/min was raised from room temperature to 350 ℃, and kept for 4 h. After dropping to the reaction temperature, H 2 was introduced, and dimethyl oxalate or its methanol solution was pumped into the reaction with an advection pump. The product was analyzed by gas chromatography, the chromatographic column was a 30m FFAP type polar capillary column, and the reaction raw materials and products were detected by a hydrogen flame detector (FID).

催化剂转化率和选择性计算方法如下:Catalyst conversion and selectivity were calculated as follows:

Figure BDA0001043372130000041
Figure BDA0001043372130000041

Figure BDA0001043372130000051
Figure BDA0001043372130000051

上式中M指反应产物,如乙二醇(EG)、乙醇酸甲酯(MG)、2-甲氧基乙醚(2-MEO)、1,2-丙二醇(1,2-POD)、1,2-丁二醇(1,2-BOD)等。In the above formula, M refers to the reaction product, such as ethylene glycol (EG), methyl glycolate (MG), 2-methoxyethyl ether (2-MEO), 1,2-propanediol (1,2-POD), 1 , 2-butanediol (1,2-BOD) and so on.

所述草酸酯加氢反应制乙二醇反应,草酸酯转化率不低于70%或不低于80%或不低于90%或不低于95%;加氢产物乙二醇的选择性不低于85%或不低于90%或不低于95%。The oxalate hydrogenation reaction to prepare ethylene glycol reaction, the oxalate conversion rate is not less than 70% or not less than 80% or not less than 90% or not less than 95%; The selectivity is not less than 85% or not less than 90% or not less than 95%.

本发明解决了草酸酯加氢制乙二醇的催化反应过程中选择性低和催化剂寿命短的问题。本发明催化剂具有较高的反应性能和反应稳定性。The invention solves the problems of low selectivity and short catalyst life in the catalytic reaction process of oxalate hydrogenation to ethylene glycol. The catalyst of the invention has higher reaction performance and reaction stability.

本发明技术细节由下述实施例加以详尽描述。需要说明的是所举实施例,其作用只是进一步说明本发明技术特征,而不限定本发明。The technical details of the present invention are described in detail by the following examples. It should be noted that the examples are given, and their functions are only to further illustrate the technical features of the present invention, but not to limit the present invention.

具体实施方式Detailed ways

实施例1Example 1

亲水性SiO2的制备:Preparation of hydrophilic SiO :

在500ml烧瓶中加入20g硅酸钠、3g硫酸钠和233mL水,室温搅拌 1小时,升温至80~90℃,滴加质量分数为10%的硫酸溶液至体系pH为 10~11,陈化30min。加硫酸调整pH至5过滤,水洗至无SO4 2-,乙醇洗涤除去水分,干燥、焙烧得白色粉末为亲水性SiO2,记为SiO2-A,其如结构式1(A)所示,测其4%水溶液的pH值为4.0,测定其表面羟基数目为:4.8 个/nm2.Add 20g sodium silicate, 3g sodium sulfate and 233mL water to a 500ml flask, stir at room temperature for 1 hour, heat up to 80-90°C, add 10% sulfuric acid solution dropwise until the pH of the system is 10-11, and age for 30min . Add sulfuric acid to adjust pH to 5, filter, wash with water until there is no SO 4 2- , wash with ethanol to remove water, dry and calcine to obtain a white powder that is hydrophilic SiO 2 , denoted as SiO 2 -A, which is shown in structural formula 1(A) , the pH value of its 4% aqueous solution is 4.0, and the number of hydroxyl groups on its surface is: 4.8/nm 2 .

羟基硅油改性亲水性SiO2的制备:Preparation of Hydroxysilicone Oil - Modified Hydrophilic SiO:

在500ml烧瓶中加入20g硅酸钠、3g硫酸钠和233mL水,室温搅拌 1小时,升温至80~90℃,滴加质量分数为10%的硫酸溶液至体系pH为 10~11,陈化30min。加硫酸调整pH至5,加入羟基硅油,陈化1.5h,过滤,水洗至无SO4 2-,乙醇洗涤除去水分,干燥、焙烧得白色粉末为改性亲水性SiO2,记为SiO2-B,其结构式如结构式1(B)所示。Add 20g sodium silicate, 3g sodium sulfate and 233mL water to a 500ml flask, stir at room temperature for 1 hour, heat up to 80-90°C, add 10% sulfuric acid solution dropwise until the pH of the system is 10-11, and age for 30min . Add sulfuric acid to adjust pH to 5, add hydroxy silicone oil, age for 1.5h, filter, wash with water until there is no SO 4 2- , wash with ethanol to remove water, dry and calcine to obtain a white powder that is modified hydrophilic SiO 2 , denoted as SiO 2 -B, whose structural formula is shown in structural formula 1(B).

Figure BDA0001043372130000052
Figure BDA0001043372130000052

结构式1.亲水性SiO2的结构式Structural formula 1. Structural formula of hydrophilic SiO

通过控制制备过程中甘油的添加量,本实施例分别加入羟基硅油1g、2g、 3g,分别得到改性亲水性SiO2-B-1、SiO2-B-2、SiO2-B-3,测其4%水溶液的pH值分别为:4.3,4.5,4.9.测定其表面羟基数目分别为:4.0个/nm2、3.3 个/nm2、2.7个/nm2By controlling the amount of glycerin added in the preparation process, 1g, 2g, and 3g of hydroxy silicone oil were added in this example to obtain modified hydrophilic SiO 2 -B-1, SiO 2 -B-2, and SiO 2 -B-3. , the pH values of its 4% aqueous solution were measured as: 4.3, 4.5, and 4.9. The number of hydroxyl groups on the surface was measured as: 4.0/nm 2 , 3.3/nm 2 , and 2.7/nm 2 .

上述制备过程中采用1g乙烯基三乙氧基硅烷替代1g羟基硅油,可得到改性亲水性SiO2-C,测其4%水溶液的批pH值为4.6,测其表面羟基数目为4.2个/nm2.In the above-mentioned preparation process, 1 g of vinyl triethoxysilane is used to replace 1 g of hydroxy silicone oil, and modified hydrophilic SiO 2 -C can be obtained. The batch pH value of its 4% aqueous solution is 4.6, and the number of hydroxyl groups on its surface is 4.2. /nm 2 .

实施例2Example 2

称量36.3g Cu(NO3)2·3H2O,配成500mL 0.3mol/L的Cu(NO3)2溶液。量取157mL Cu(NO3)2溶液放入250mL烧杯中,然后将18mL氨水(25wt%) 逐滴滴入Cu(NO3)2溶液中,从而使得终溶液的pH值在约9-10之间。将12 g SiO2-B-2(4%水溶液的pH值为4.5)在搅拌下加入到铜氨溶液中。把烧杯放置在35℃水溶液中老化4小时,升温至90℃,并在该温度下维持2.5小时以挥发氨气。将得到的沉淀物过滤、洗涤至滤液pH值为7左右,接着将滤饼移入干锅,在烘箱中120℃干燥12小时,450℃焙烧4小时。将得到的材料压碎并通过20-40目网筛筛选。反应得到的催化剂表示为催化剂 A,催化剂A包含铜与铜氧化物的混合物以及SiO236.3 g of Cu(NO 3 ) 2 ·3H 2 O were weighed to prepare 500 mL of 0.3 mol/L Cu(NO 3 ) 2 solution. Measure 157 mL of Cu(NO 3 ) 2 solution into a 250 mL beaker, and then drop 18 mL of ammonia water (25wt%) into the Cu(NO 3 ) 2 solution dropwise, so that the pH of the final solution is between about 9-10 between. 12 g of SiO2 -B-2 (pH 4.5 in a 4% aqueous solution) were added to the cuprammonium solution with stirring. The beaker was aged for 4 hours in a 35°C aqueous solution, raised to 90°C, and maintained at this temperature for 2.5 hours to volatilize ammonia gas. The obtained precipitate was filtered and washed until the pH value of the filtrate was about 7, and then the filter cake was moved into a dry pan, dried at 120° C. for 12 hours in an oven, and calcined at 450° C. for 4 hours. The resulting material was crushed and screened through a 20-40 mesh screen. The catalyst obtained by the reaction is denoted as catalyst A, and catalyst A comprises a mixture of copper and copper oxide and SiO 2 .

对比实施例1Comparative Example 1

制备步骤同实施例2,只是采用市售SiO2(4%水溶液pH值为7,测其表面羟基数目为1.8个/nm2)替代SiO2-B-2,得到催化剂A’,催化剂A’包含铜与铜氧化物的混合物以及SiO2The preparation step is the same as in Example 2, except that commercially available SiO 2 (4% aqueous solution pH value is 7, and the number of hydroxyl groups on its surface is measured as 1.8/nm 2 ) is used to replace SiO 2 -B-2 to obtain catalyst A', catalyst A' Contains a mixture of copper and copper oxide and SiO 2 .

实施例3~6Examples 3 to 6

制备步骤同实施例2,只是采用亲水性SiO2-A、改性亲水性SiO2-B-1、 SiO2-B-3、SiO2-C替代载体SiO2-B-2,分别得到催化剂B、C、D、E,催化剂包含铜与铜氧化物的混合物以及SiO2The preparation steps are the same as in Example 2, except that hydrophilic SiO 2 -A, modified hydrophilic SiO 2 -B-1, SiO 2 -B-3 and SiO 2 -C are used to replace carrier SiO 2 -B-2, respectively. Catalysts B, C, D, E were obtained, comprising a mixture of copper and copper oxides and SiO 2 .

实施例7Example 7

制备步骤同实施例2,只是向157ml浓度为0.3mol/L的Cu(NO3)2溶液中,加入0.19g的Ce(NO3)3·6H2O。该实施例制备得到催化剂F,催化剂F 包含铜与铜氧化物的混合物、CeO2以及SiO2The preparation steps were the same as those in Example 2, except that 0.19 g of Ce(NO 3 ) 3 ·6H 2 O was added to 157 ml of Cu(NO 3 ) 2 solution with a concentration of 0.3 mol/L. Catalyst F is prepared in this example, and catalyst F comprises a mixture of copper and copper oxides, CeO 2 and SiO 2 .

实施例8Example 8

制备步骤同实施例2,只是将SiO2的加入量由12g改变为27g。该实施例制备得到催化剂G,催化剂G包含铜与铜氧化物的混合物和SiO2.The preparation steps are the same as those in Example 2, except that the amount of SiO 2 added is changed from 12g to 27g. Catalyst G is prepared in this example, and catalyst G comprises a mixture of copper and copper oxide and SiO 2 .

实施例9Example 9

制备步骤同实施例2,只是将SiO2的加入量由12g改变为4.5g。该实施例制备得到催化剂H,催化剂H包含铜与铜氧化物的混合物和SiO2.The preparation steps are the same as those in Example 2, except that the amount of SiO 2 added is changed from 12g to 4.5g. Catalyst H is prepared in this example, and catalyst H comprises a mixture of copper and copper oxides and SiO 2 .

实施例10Example 10

制备步骤同实施例2,只是向157ml浓度为0.3mol/L的Cu(NO3)2溶液中,加入2g的Ce(NO3)3·6H2O。该实施例制备得到催化剂I,催化剂I包含铜与铜氧化物的混合物、CeO2以及SiO2The preparation steps were the same as those in Example 2, except that 2g of Ce(NO 3 ) 3 ·6H 2 O was added to 157 ml of Cu(NO 3 ) 2 solution with a concentration of 0.3 mol/L. Catalyst I was prepared in this example, and catalyst I comprised a mixture of copper and copper oxides, CeO 2 and SiO 2 .

上述实施例制备的催化剂组成列于表1。The compositions of the catalysts prepared in the above examples are listed in Table 1.

表1.制备催化剂的成分Table 1. Components for preparing catalysts

Figure BDA0001043372130000071
Figure BDA0001043372130000071

实施例11:Example 11:

实施例2~6和对比实施例1制备催化剂A~E和A’在210℃、3MPa、 150氢酯比、0.5h-1LHSVDMO条件下的草酸二甲酯加氢制乙二醇反应性能列于表2。Reaction performance of dimethyl oxalate hydrogenation to ethylene glycol under the conditions of 210°C, 3MPa, 150 hydrogen ester ratio, 0.5h -1 LHSV DMO for the catalysts A to E and A' prepared in Examples 2 to 6 and Comparative Example 1 listed in Table 2.

表2.载体SiO2性能对铜基催化剂草酸二甲酯加氢制乙二醇反应性能影响Table 2. Effect of supported SiO 2 properties on the reaction performance of copper-based catalysts for hydrogenation of dimethyl oxalate to ethylene glycol

Figure BDA0001043372130000072
Figure BDA0001043372130000072

表2可看出,亲水性SiO2为载体的催化剂表现出明显的高草酸酯加氢制乙二醇反应性能,A~E催化剂表现出较优的乙二醇选择性。同性能较差催化剂A’的SiO2载体相比,反应性能较好催化剂SiO2载体具有以下特点: (1)与水组成的悬浮液显酸性;(2)具有较强的亲水性能。这表明亲水性的酸性SiO2载体适合作为本草酸酯加氢制乙二醇催化剂的载体。It can be seen from Table 2 that the catalysts with hydrophilic SiO 2 as the carrier show obvious reaction performance for the hydrogenation of high oxalate to ethylene glycol, and the A-E catalysts show better ethylene glycol selectivity. Compared with the SiO 2 carrier of catalyst A' with poor performance, the catalyst SiO 2 carrier with better reaction performance has the following characteristics: (1) The suspension composed of water is acidic; (2) It has strong hydrophilic properties. This indicates that the hydrophilic acidic SiO2 support is suitable as the support for the hydrogenation of this oxalate to ethylene glycol catalyst.

实施例12:Example 12:

实施例2,8~9制备催化剂A、G和H在190℃、3.5MPa、120氢酯比、 0.5h-1LHSVDMO条件下的草酸二甲酯加氢制乙二醇反应性能列于表3。Examples 2, 8-9 Preparation of catalysts A, G and H at 190 ° C, 3.5 MPa, 120 hydrogen ester ratio, 0.5 h -1 LHSV DMO The reaction performance of dimethyl oxalate hydrogenation to ethylene glycol is listed in the table 3.

表3.铜含量对铜基催化剂上草酸二甲酯加氢制乙二醇反应性能的影响

Figure BDA0001043372130000081
Table 3. Effect of copper content on the reaction performance of dimethyl oxalate hydrogenation to ethylene glycol over copper-based catalysts
Figure BDA0001043372130000081

从表3可看出,随Cu含量的增加,催化剂的草酸酯加氢活性逐渐增强,在Cu含量增到20%时,DMO转化率达到100%,EG选择性同时达到最佳值93.1%。而随Cu含量继续增加,EG的选择性略微下降,而EO和2-MEO 等副产物的选择性增加,同时MG的选择性下降,这是由于随Cu含量增加,催化剂加氢性能逐渐增强的,目标产物EG会进一步加氢生成二次反应产物。It can be seen from Table 3 that with the increase of Cu content, the oxalate hydrogenation activity of the catalyst is gradually enhanced. When the Cu content increases to 20%, the DMO conversion rate reaches 100%, and the EG selectivity simultaneously reaches the optimum value of 93.1%. . However, as the Cu content continued to increase, the selectivity of EG decreased slightly, while the selectivity of by-products such as EO and 2-MEO increased, while the selectivity of MG decreased, which was due to the gradual enhancement of the hydrogenation performance of the catalyst with the increase of Cu content. , the target product EG will be further hydrogenated to form a secondary reaction product.

实施例13:Example 13:

实施例2,7,10制备催化剂A、F和I在200℃、2.0MPa、100氢酯比、 0.35h-1LHSVDMO条件下的草酸二甲酯加氢制乙二醇反应性能列于表4。从表中结果可看出,催化剂添加CeO2助剂后,草酸酯加氢制乙二醇反应的目标产物乙二醇选择性进一步增加。在CeO2含量增加至5%时,乙二醇选择性略有下降。Example 2, 7, 10 Preparation of catalysts A, F and I at 200 ° C, 2.0 MPa, 100 hydrogen ester ratio, 0.35 h -1 LHSV DMO conditions The reaction performance of dimethyl oxalate hydrogenation to ethylene glycol is listed in the table 4. From the results in the table, it can be seen that after the addition of CeO 2 to the catalyst, the selectivity of ethylene glycol, the target product of oxalate hydrogenation to ethylene glycol, is further increased. The ethylene glycol selectivity decreased slightly when the CeO content increased to 5 %.

表4.CeO2助剂对铜基催化剂草酸二甲酯加氢制乙二醇反应性能的影响Table 4. Effect of CeO 2 promoter on the reaction performance of copper-based catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Figure BDA0001043372130000082
Figure BDA0001043372130000082

实施例14Example 14

实施例2催化剂A在3.0MPa、80氢酯比、0.5h-1LHSVDMO纯酯进料条件下的草酸二甲酯加氢制乙二醇反应性能随反应温度变化结果列于表5。Example 2 Catalyst A under the conditions of 3.0MPa, 80 hydrogen ester ratio, and 0.5h -1 LHSV DMO pure ester feed reaction performance of dimethyl oxalate hydrogenation to produce ethylene glycol The results are listed in Table 5 as a function of reaction temperature.

表5.反应温度铜基催化剂上草酸二甲酯加氢制乙二醇反应性能Table 5. Reaction temperature reaction performance of dimethyl oxalate hydrogenation to ethylene glycol over copper-based catalyst

Figure BDA0001043372130000091
Figure BDA0001043372130000091

表5的实验结果显示,在考察的反应温度范围内,催化剂A显示较高的草酸酯加氢制乙二醇反应性能,DMO几乎完全转化,乙二醇选择性保持在90%以上。随反应温度增加,乙二醇(EG)选择性逐渐降低,副产物乙醇 (EO)、1,2-丙二醇(1,2-POD)、1,2-丁二醇(1,2-BOD)的选择性逐渐增加。这是由于随反应温度增加催化剂的加氢能力增强,反应产物乙二醇进一步加氢所致。The experimental results in Table 5 show that within the investigated reaction temperature range, catalyst A shows higher reaction performance of oxalate hydrogenation to ethylene glycol, DMO is almost completely converted, and ethylene glycol selectivity is maintained above 90%. With the increase of reaction temperature, the selectivity of ethylene glycol (EG) gradually decreased, and the by-products ethanol (EO), 1,2-propanediol (1,2-POD), 1,2-butanediol (1,2-BOD) selectivity gradually increases. This is because the hydrogenation capacity of the catalyst increases with the increase of the reaction temperature, and the reaction product ethylene glycol is further hydrogenated.

实施例15:Example 15:

实施例2催化剂A在210℃,3.0MPa、0.5h-1LHSVDMO条件下的草酸二甲酯加氢制乙二醇反应性能随原料氢酯比变化结果列于表6。Example 2 The reaction performance of catalyst A in the hydrogenation of dimethyl oxalate to ethylene glycol under the conditions of 210 ° C, 3.0 MPa, 0.5 h -1 LHSV DMO with the ratio of raw material hydrogen to ester is listed in Table 6.

从表6可看出,在考察的氢酯比范围内,催化剂A均显示了优良的反应性能,DMO转化率大于99%,EG选择性大于91%。随氢酯比增加,加氢产物EG的选择性增加,在氢酯比为100时达到最佳值,而后略有下降。副产物MG随氢酯比增加下降,EO、1,2-POD、1,2-BOD的选择性随氢酯比增加而增加。这是由于氢酯比增加有利于催化剂的加氢性能。It can be seen from Table 6 that in the range of the investigated hydrogen ester ratio, catalyst A all showed excellent reaction performance, the DMO conversion rate was greater than 99%, and the EG selectivity was greater than 91%. With the increase of hydrogen ester ratio, the selectivity of hydrogenation product EG increased, reached the optimum value when the hydrogen ester ratio was 100, and then decreased slightly. The by-product MG decreased with the increase of the hydrogen ester ratio, and the selectivity of EO, 1,2-POD and 1,2-BOD increased with the increase of the hydrogen ester ratio. This is because the increased hydrogen ester ratio is beneficial to the hydrogenation performance of the catalyst.

表6.氢酯比变化对铜基催化剂上草酸二甲酯加氢制乙二醇反应性能影响Table 6. Effect of hydrogen ester ratio change on reaction performance of dimethyl oxalate hydrogenation to ethylene glycol over copper-based catalyst

Figure BDA0001043372130000092
Figure BDA0001043372130000092

实施例16:Example 16:

实施例2制备催化剂A在175℃,3MPa、80氢酯比、0.5h-1LHSVDMO、纯酯进料的条件下1000小时的反应稳定性试验结果列于表7。Example 2 Preparation of catalyst A at 175°C, 3MPa, 80 hydrogen-to-ester ratio, 0.5h -1 LHSV DMO , pure ester feed for 1000 hours The reaction stability test results are listed in Table 7.

表7.铜基催化剂上草酸二甲酯加氢制乙二醇反应稳定性结果Table 7. Stability results of the hydrogenation of dimethyl oxalate to ethylene glycol over copper-based catalysts

Figure BDA0001043372130000101
Figure BDA0001043372130000101

由表7可看出,实施例2制备催化剂A在考察的1000小时反应稳定性试验过程中,DMO保持完全转化,EG选择性可维持在97%以上。试验结果表明,催化剂A不仅具有良好的草酸酯加氢制乙二醇反应性能,而且具有良好的反应稳定性。It can be seen from Table 7 that during the 1000-hour reaction stability test of the catalyst A prepared in Example 2, DMO remained completely converted, and the EG selectivity could be maintained above 97%. The test results show that catalyst A not only has good reaction performance of oxalate hydrogenation to ethylene glycol, but also has good reaction stability.

Claims (23)

1.一种草酸酯加氢制乙二醇的方法,其特征在于:该方法采用至少含有草酸酯和氢气的原料通过一种催化剂生产乙二醇;该方法采用的催化剂包含金属铜或铜氧化物中的一种或二种混合物、亲水性二氧化硅或改性亲水性二氧化硅中的一种或二种,含有或不含有金属氧化物助剂,其中所述催化剂中铜元素质量百分比为10-60%,所述催化剂中二氧化硅质量百分比为35-90%,所述催化剂中金属氧化物助剂的质量百分比不高于5%;1. a method for producing ethylene glycol by hydrogenation of oxalate, is characterized in that: the method adopts the raw material containing at least oxalate and hydrogen to produce ethylene glycol by a kind of catalyzer; The catalyzer that this method adopts comprises metallic copper or One or two mixtures of copper oxides, one or two of hydrophilic silica or modified hydrophilic silica, with or without metal oxide additives, wherein the catalyst is The mass percentage of copper element is 10-60%, the mass percentage of silica in the catalyst is 35-90%, and the mass percentage of metal oxide auxiliary agent in the catalyst is not higher than 5%; 其中所述催化剂组分亲水性二氧化硅,指的是SiO2表面羟基数目在4~5个/nm2,且不含疏水基团的二氧化硅;所述改性亲水性二氧化硅,指的是具有0.1~40%的表面羟基被疏水基团取代的SiO2Wherein, the catalyst component hydrophilic silica refers to silica with 4~5 hydroxyl groups/nm 2 on the surface of SiO 2 and no hydrophobic group; the modified hydrophilic silica Silicon refers to SiO 2 with 0.1~40% of surface hydroxyl groups replaced by hydrophobic groups; 改性后的亲水性二氧化硅表面羟基数目为2.4~4.995个/nm2;所述疏水基团指烷基、烷氧基、烯基中的一种或二种以上;The number of hydroxyl groups on the surface of the modified hydrophilic silica is 2.4 to 4.995/nm 2 ; the hydrophobic group refers to one or more of alkyl groups, alkoxy groups, and alkenyl groups; 亲水性二氧化硅的制备方法为:The preparation method of hydrophilic silica is: 硅酸钠、硫酸钠和水同时加入到制备容器中,硅酸钠、硫酸钠和水的质量比例为1:0.01~0.5: 5~15,室温搅拌,升温至80~90℃,滴加质量分数为2%~20%的硫酸溶液至体系pH为10~11,陈化15~60分钟;加质量分数为2%~20%硫酸调整pH值至4~6.5过滤,水洗至无SO4 2-,乙醇洗涤除去水分,100~120℃干燥、200~800oC焙烧得白色粉末为亲水性SiO2Sodium silicate, sodium sulfate and water are added into the preparation container simultaneously, the mass ratio of sodium silicate, sodium sulfate and water is 1:0.01~0.5:5~15, stirring at room temperature, warming up to 80~90 ℃, adding dropwise mass Add 2%~20% sulfuric acid solution to pH 10~11, and age for 15~60 minutes; add 2%~20% sulfuric acid to adjust pH to 4~6.5, filter, wash with water until no SO 4 2 - , washed with ethanol to remove water, dried at 100~120 ℃, calcined at 200~800 o C to obtain a white powder which is hydrophilic SiO 2 ; 改性亲水性SiO2的制备方法为:The preparation method of modified hydrophilic SiO2 is: 硅酸钠、硫酸钠和水同时加入到制备容器中,硅酸钠、硫酸钠和水的质量比例为1:0.01~0.5: 5~15,室温搅拌,升温至80~90℃,滴加质量分数为2%~20%的硫酸溶液至体系pH为10~11,陈化15~60min;加质量分数为2%~20%硫酸调整pH至4-6.5,加入含疏水基团的化合物,陈化0.5~4 h,过滤,水洗至无SO4 2-,乙醇洗涤除去水分,100~120℃干燥、200~800℃焙烧得白色粉末为改性亲水性SiO2Sodium silicate, sodium sulfate and water are added into the preparation container simultaneously, the mass ratio of sodium silicate, sodium sulfate and water is 1:0.01~0.5:5~15, stirring at room temperature, warming up to 80~90 ℃, adding dropwise mass The pH of the system is 10-11 with a concentration of 2%-20% sulfuric acid solution, and ageing for 15-60min; adding a mass fraction of 2%-20% sulfuric acid to adjust the pH to 4-6.5, adding a compound containing a hydrophobic group, aging It was heated for 0.5~4 h, filtered, washed with water until there was no SO 4 2- , washed with ethanol to remove water, dried at 100~120 ℃ and calcined at 200~800 ℃ to obtain a white powder which was modified hydrophilic SiO 2 . 2.根据权利要求1所述的方法,其特征在于:所述改性亲水性二氧化硅,指的是具有0.1~25%的表面羟基被疏水基团取代的SiO22 . The method according to claim 1 , wherein the modified hydrophilic silica refers to SiO 2 having 0.1-25% of surface hydroxyl groups substituted by hydrophobic groups. 3 . 3.根据权利要求1所述的方法,其特征在于:所述改性亲水性二氧化硅,指的是具有10~25%的表面羟基被疏水基团取代的SiO23 . The method according to claim 1 , wherein the modified hydrophilic silica refers to SiO 2 having 10-25% of surface hydroxyl groups substituted by hydrophobic groups. 4 . 4.根据权利要求1所述的方法,其特征在于:4. method according to claim 1, is characterized in that: 改性后的亲水性二氧化硅表面羟基数目为3.0~4.995个/nm2The number of hydroxyl groups on the surface of the modified hydrophilic silica is 3.0 to 4.995/nm 2 ; 其中所述疏水基团指甲基、甲氧基、乙烯基中的一种或二种以上。The hydrophobic group refers to one or more of methyl group, methoxy group and vinyl group. 5.根据权利要求1所述的方法,其特征在于:5. method according to claim 1, is characterized in that: 改性后的亲水性二氧化硅表面羟基数目为3.0~4.5个/nm2The number of hydroxyl groups on the surface of the modified hydrophilic silica is 3.0 to 4.5/nm 2 ; 其中所述疏水基团为甲基。wherein the hydrophobic group is methyl. 6.根据权利要求1所述方法,其特征在于:含疏水基团的化合物为含有烷基、烷氧基和烯基中的一种或二种以上的化合物。6 . The method according to claim 1 , wherein the hydrophobic group-containing compound is a compound containing one or more of an alkyl group, an alkoxy group and an alkenyl group. 7 . 7.根据权利要求1所述方法,其特征在于:含疏水基团的化合物为六甲基硅氮烷、甲基硅烷钠、乙基硅烷钠、羟基硅油、乙烯基三乙氧基硅烷中的一种或二种以上。7. The method according to claim 1, wherein the hydrophobic group-containing compound is hexamethylsilazane, sodium methylsilane, sodium ethylsilane, hydroxysilicone oil, and vinyltriethoxysilane. one or more than two. 8.根据权利要求1所述方法,其特征在于:含疏水基团的化合物为羟基硅油、乙烯基三乙氧基硅烷中的一种或二种。8 . The method according to claim 1 , wherein the hydrophobic group-containing compound is one or both of hydroxysilicone oil and vinyltriethoxysilane. 9 . 9.根据权利要求1~5任一所述方法,其特征在于:其中所述亲水性二氧化硅或改性亲水性二氧化硅均为酸性二氧化硅。9. The method according to any one of claims 1 to 5, wherein the hydrophilic silica or the modified hydrophilic silica are both acidic silica. 10.根据权利要求9所述方法,其特征在于:所述亲水性二氧化硅或改性亲水性二氧化硅的4wt%的水溶液的pH值小于6.1。10 . The method according to claim 9 , wherein the pH value of the 4 wt % aqueous solution of the hydrophilic silica or modified hydrophilic silica is less than 6.1. 11 . 11.根据权利要求9所述方法,其特征在于:所述亲水性二氧化硅或改性亲水性二氧化硅的4wt%的水溶液的pH值在2.2-6.0之间。11 . The method according to claim 9 , wherein the pH value of the 4 wt % aqueous solution of the hydrophilic silica or modified hydrophilic silica is between 2.2 and 6.0. 12 . 12.根据权利要求9所述方法,其特征在于:所述亲水性二氧化硅或改性亲水性二氧化硅的4wt%的水溶液的pH值在3.0-5.0之间。12 . The method according to claim 9 , wherein the pH value of the 4 wt % aqueous solution of the hydrophilic silica or modified hydrophilic silica is between 3.0 and 5.0. 13 . 13.根据权利要求1所述方法,其金属氧化物助剂指CeO2、TiO2中的一种或二种混合物。13. The method according to claim 1, wherein the metal oxide auxiliary agent refers to one or a mixture of two of CeO2 and TiO2 . 14.一种权利要求1-8中任一项所述的方法,其特征在于:所述催化剂的制备过程为,14. A method according to any one of claims 1-8, characterized in that: the preparation process of the catalyst is, a)将含可溶性铜盐、可溶性金属盐和质量浓度为10~35%氨水混合,其中所述金属盐最终可生成相应的金属氧化物助剂,溶液中铜盐摩尔浓度0.05~2 mol/L;a) Mix the soluble copper salt, soluble metal salt and ammonia water with a mass concentration of 10 to 35%, wherein the metal salt can finally generate a corresponding metal oxide auxiliary, and the molar concentration of the copper salt in the solution is 0.05 to 2 mol/L ; b)在步骤a)生成的溶液中加入亲水性二氧化硅或改性亲水性二氧化硅;b) adding hydrophilic silica or modified hydrophilic silica to the solution generated in step a); c)除去溶液中氨;c) remove ammonia in solution; d)300~600℃焙烧、碾磨步骤c)的产物。d) calcining and grinding the product of step c) at 300-600°C. 15.根据权利要求1所述的方法,其特征在于:所述草酸酯是指草酸单甲酯、草酸单乙酯、草酸二甲酯,草酸二乙酯中的一种或二种以上。15. The method according to claim 1, wherein the oxalic acid ester refers to one or more of oxalic acid monomethyl ester, oxalic acid monoethyl ester, oxalic acid dimethyl ester, and oxalic acid diethyl ester. 16.根据权利要求1所述的方法,其特征在于:所述草酸酯是指草酸二甲酯或草酸二乙酯中的一种或二种。16. The method according to claim 1, wherein the oxalate is one or both of dimethyl oxalate or diethyl oxalate. 17.根据权利要求1所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在160-230℃的温度下进行,在0.5~6MPa压力下进行,在10~200的氢酯摩尔比下进行。17. The method according to claim 1, characterized in that: the oxalic acid ester hydrogenation to ethylene glycol reaction is carried out at a temperature of 160-230 ° C, under a pressure of 0.5 to 6 MPa, and at a pressure of 10 to 200 °C. under the molar ratio of hydrogen ester. 18.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在160~200℃的温度下进行。18 . The method according to claim 17 , wherein the hydrogenation of the oxalate to ethylene glycol is carried out at a temperature of 160-200° C. 19 . 19.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在0.5~4Mpa的压力下进行。19. The method according to claim 17, characterized in that: the oxalate hydrogenation reaction to ethylene glycol is carried out under a pressure of 0.5-4Mpa. 20.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在1~2Mpa的压力下进行。20. The method according to claim 17, wherein the hydrogenation of the oxalate to ethylene glycol reaction is carried out under a pressure of 1 to 2 Mpa. 21.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在30~150的氢酯摩尔比下进行。21. The method according to claim 17, characterized in that: the oxalate hydrogenation reaction to produce ethylene glycol is carried out at a hydrogen ester molar ratio of 30 to 150. 22.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在50~150的氢酯摩尔比下进行。22. The method according to claim 17, characterized in that: the oxalate hydrogenation reaction to ethylene glycol is carried out at a hydrogen ester molar ratio of 50 to 150. 23.根据权利要求17所述的方法,其特征在于:所述草酸酯加氢制乙二醇反应,在50~100的氢酯摩尔比下进行。23. The method according to claim 17, characterized in that: the oxalate hydrogenation reaction to ethylene glycol is carried out at a hydrogen ester molar ratio of 50 to 100.
CN201610530368.8A 2016-07-07 2016-07-07 A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate Active CN107586254B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610530368.8A CN107586254B (en) 2016-07-07 2016-07-07 A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610530368.8A CN107586254B (en) 2016-07-07 2016-07-07 A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate

Publications (2)

Publication Number Publication Date
CN107586254A CN107586254A (en) 2018-01-16
CN107586254B true CN107586254B (en) 2020-06-23

Family

ID=61045552

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610530368.8A Active CN107586254B (en) 2016-07-07 2016-07-07 A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate

Country Status (1)

Country Link
CN (1) CN107586254B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108325532B (en) * 2018-03-13 2020-09-11 浙江师范大学 Catalyst in the synthesis process of methyl glycolate and its preparation method and application
CN110773165B (en) * 2019-11-05 2022-07-08 中催技术有限公司 Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation
CN112973677A (en) * 2019-12-13 2021-06-18 山西潞安矿业(集团)有限责任公司 Preparation method and application of hydrophobic noble metal catalyst
CN111330581B (en) * 2020-03-10 2021-07-27 中国科学院山西煤炭化学研究所 A kind of acid-resistant hydrogenation catalyst and preparation method and application thereof
CN111389460A (en) * 2020-04-13 2020-07-10 天津大学 Copper-silicon catalyst modified by silanization and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104043455A (en) * 2013-03-13 2014-09-17 中国石油化工股份有限公司 Preparation method of catalyst for preparation of glycol by oxalate hydrogenation
CN104174407A (en) * 2013-05-23 2014-12-03 中国科学院大连化学物理研究所 Catalyst for preparation of glycol by oxalate hydrogenation and use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104043455A (en) * 2013-03-13 2014-09-17 中国石油化工股份有限公司 Preparation method of catalyst for preparation of glycol by oxalate hydrogenation
CN104174407A (en) * 2013-05-23 2014-12-03 中国科学院大连化学物理研究所 Catalyst for preparation of glycol by oxalate hydrogenation and use thereof

Also Published As

Publication number Publication date
CN107586254A (en) 2018-01-16

Similar Documents

Publication Publication Date Title
CN107586254B (en) A kind of method for synthesizing ethylene glycol by hydrogenation of oxalate
CN102218320B (en) Catalyst for hydrogenation, preparation method and application thereof
CN102105222B (en) Catalyst for synthesizing methanol from synthesis gas and preparation method thereof
CN102302934B (en) Catalyst for the catalytic hydrogenation of carbon dioxide to methanol modified by a novel additive and its preparation method
CN101474563B (en) Preparation method of catalyst for hydrogen production by steam reforming of methanol
CN104959143A (en) Catalyst for slurry bed CO2 hydrogenation to methanol, preparation method and application
CN111659402B (en) CO (carbon monoxide) 2 Catalyst for preparing low-carbon alcohol by hydrogenation, preparation method and application thereof
CN113289632B (en) A kind of catalyst for hydrogenation of dimethyl oxalate to ethanol and its preparation method and application
CN114939433A (en) Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof
WO2019128914A1 (en) Copper-based catalyst for synthesizing dihydric alcohol by means of ester hydrogenation and preparation method therefor and use thereof
CN106861752A (en) Solid catalyst and its preparation and application for ethanol synthesis butadiene
WO2008071059A1 (en) A slurry catalyst and the preparation thereof
CN102658165A (en) Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof
CN108144610A (en) The copper-based hydrogenation catalyst of flame injection cracking process preparation and its preparation and application
CN111229247B (en) Catalyst for hydrogenation of oxalate to ethanol, preparation method and application thereof
CN107778138A (en) A method for preparing 1,4-butanediol by two-stage hydrogenation of 1,4-butynediol
CN103447059A (en) Preparation method of acetate hydrogenation catalyst
CN106540674B (en) A kind of metal-doped zirconia catalyst and preparation method thereof with catalyzing and synthesizing the application in gas catalyzed conversion
CN101983765B (en) Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof
CN104163747B (en) The method of one-step method from syngas preparing low-carbon olefins
CN108654617A (en) Hydrogenation of oxalate for preparing ethylene glycol catalyst carrier method of modifying and catalyst and application
CN104174407A (en) Catalyst for preparation of glycol by oxalate hydrogenation and use thereof
CN107398273B (en) Catalyst and method for hydrogenation of cyclobutane diketone compounds
CN102863335A (en) Preparation method of diethyl succinate
CN103910602A (en) Method for producing cyclohexanol

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