技术领域technical field
本发明涉及甘油氢解的方法，具体地说是关于一种在固定床反应器上采用负载型纳米铜基催化剂将甘油催化氢解合成丙二醇的方法。The invention relates to a method for hydrogenolysis of glycerol, in particular to a method for catalytic hydrogenolysis of glycerol to synthesize propylene glycol by using a loaded nanometer copper-based catalyst on a fixed-bed reactor.
背景技术Background technique
1，2-丙二醇和1，3-丙二醇作为重要的化工原料，因生物毒性低，在溶剂、印染、保湿剂、防冻剂、乳化剂等，在医药、化妆品、食品等领域被广泛应用而备受关注。丙二醇一般方法是由化石原料的石油衍生物丙烯氧化，然后将其水合制得。如果以生物柴油加工过程大量过剩甘油为原料，将甘油的1位或2位羟基转化为氢合成1，2-丙二醇和1，3-丙二醇，不仅为丙二醇的生产提供了一条绿色经济的合成路线，同时也为生物柴油的发展提供了经济性的保障。As important chemical raw materials, 1,2-propanediol and 1,3-propanediol are widely used in solvents, printing and dyeing, humectants, antifreezes, emulsifiers, etc., in medicine, cosmetics, food and other fields due to low biological toxicity. attention. Propylene glycol is generally produced by oxidizing propylene, a petroleum derivative of fossil raw materials, and then hydrating it. If a large amount of excess glycerol in the biodiesel processing process is used as a raw material, the 1- or 2-hydroxyl of glycerol is converted into hydrogen to synthesize 1, 2-propanediol and 1, 3-propanediol, which not only provides a green and economical synthetic route for the production of propylene glycol , but also provides an economic guarantee for the development of biodiesel.
丙二醇的生产方法一般有以下几种：Propylene glycol production methods generally have the following types:
环氧丙烷直接水合法：直接水合制丙二醇新工艺[J].化工设计，1999，9(3)以环氧丙烷为原料，环氧丙烷经泵从精馏塔顶部投料，进料摩尔比为水∶环氧丙烷＝1.5～3∶1，反应器与精馏塔进行耦合进行水合反应，反应精馏塔利用蒸汽间接加热，全回流操作，控制塔顶压力0.85MPa、温度175℃。Propylene oxide direct hydration method: a new process of direct hydration to propylene glycol [J]. Chemical Engineering Design, 1999, 9 (3) with propylene oxide as raw material, propylene oxide is fed from the top of the rectification tower through a pump, and the feed molar ratio is Water: propylene oxide = 1.5～3:1, the reactor is coupled with the rectification tower for hydration reaction, the reaction rectification tower is heated indirectly by steam, operated under full reflux, the pressure at the top of the tower is controlled to 0.85MPa, and the temperature is 175°C.
3-羟基丙酸甲酯催化加氢法：(CN101993352A)起始原料3-羟基丙酸甲酯，将活化溶剂和催化剂在一定条件下在高压釜内活化，再加入反应溶剂和原料，在140～200℃、5～10MPa氢气压力下，反应3～30h，3-羟基丙酸甲酯转化率可达92.31％，1，3-丙二醇的选择性可达85.43％。催化剂的活性组分是Cu、Mn和Zr的氧化物，此发明方法加入了反应溶剂和活化溶剂，污染环境。3-hydroxypropionate methyl ester catalytic hydrogenation method: (CN101993352A) starting material 3-hydroxypropionate methyl ester, activation solvent and catalyst are activated in autoclave under certain conditions, then add reaction solvent and raw material, at 140 Under ~200°C and 5~10MPa hydrogen pressure, react for 3~30h, the conversion rate of methyl 3-hydroxypropionate can reach 92.31%, and the selectivity of 1,3-propanediol can reach 85.43%. The active components of the catalyst are oxides of Cu, Mn and Zr, and the inventive method adds a reaction solvent and an activation solvent to pollute the environment.
丙烯醛水合法：(石油炼制与化工，2001，32，12，21-24)，是由丙烯醛水合、3-羟基丙醛加氢及精制三步组成，丙烯醛水合采用固定床反应器，3-羟基丙醛加氢在间歇式高压反应釜内进行。Acrolein hydration method: (Petroleum Refining and Chemical Industry, 2001, 32, 12, 21-24), consists of three steps: acrolein hydration, 3-hydroxypropionaldehyde hydrogenation and refining. Acrolein hydration uses a fixed bed reactor , 3-Hydroxypropionaldehyde hydrogenation is carried out in a batch-type autoclave.
微生物发酵法：(CN1434122A)将葡萄糖和甘油为混合双底物在好氧条件下培养和厌氧条件下的甘油转化集成在同一个发酵罐中进行。以葡萄糖消耗完作为好氧转厌氧的条件，在厌氧条件下甘油转化为1，3-丙二醇，该过程伴有副产物乙醇、乙酸和乳酸生成，并且乙醇对发酵液会产生毒副作用。生物发酵法酶成活期短、成本高，如何提高产物1，3-丙二醇的产率和浓度，产物如何有效分离，如何降低毒副产物的形成都是有待解决的问题。Microbial fermentation method: (CN1434122A) the culture of glucose and glycerol as a mixed double substrate under aerobic conditions and the conversion of glycerol under anaerobic conditions are integrated in the same fermenter. Depletion of glucose is the condition for aerobic to anaerobic conversion. Under anaerobic conditions, glycerol is converted to 1,3-propanediol. This process is accompanied by the production of by-products ethanol, acetic acid and lactic acid, and ethanol will have toxic side effects on the fermentation broth. The biological fermentation method has a short lifespan and high cost. How to increase the yield and concentration of the product 1,3-propanediol, how to effectively separate the product, and how to reduce the formation of toxic by-products are all problems to be solved.
甘油催化氢解法：Low-pressure hydrogenolysis of glycerol to propylene glycol[J].Applied Catalysis A：Genera1，2005，281(1-2)：225-231，报道采用Cu-Cr催化剂，甘油氢解分为两步反应，在200℃、200psi压力下，甘油质量分数80％条件下，第一步是甘油脱水生成丙酮醇，第二步是丙酮醇加氢得丙二醇，反应1，2-丙二醇的收率达73％，该催化剂使用金属铬污染环境。Catalytic hydrogenolysis of glycerol: Low-pressure hydrogenolysis of glycerol to propylene glycol[J].Applied Catalysis A: Genera1, 2005, 281(1-2): 225-231, reported using Cu-Cr catalyst, glycerol hydrogenolysis is divided into two Step reaction, under 200 ℃, 200psi pressure, under the condition of 80% glycerol mass fraction, the first step is glycerol dehydration to generate acetol, the second step is acetol hydrogenation to obtain propylene glycol, and the yield of reaction 1,2-propanediol reaches 73%, the catalyst uses metallic chromium to pollute the environment.
CN102059116A采用催化剂的组成至少含有Pt、W、高熔点氧化物或其前驱物，并同时含有一种载体。高熔点氧化物或其前驱物含有ZrO2或TiO2或其前驱物。载体是SiO2、A12O3、HZSM-5或活性炭中的一种，在110～260℃，氢气压力为0.1～8.0MPa，反应2.5～50h。甘油转化率可达15.3％，1，3-丙二醇选择性达50.5％。此方法使用贵金属，价格较高，甘油的转化率和丙二醇的选择性不高。CN102059116A adopts a catalyst composition containing at least Pt, W, refractory oxides or their precursors, and simultaneously contains a carrier. The refractory oxide or its precursor containsZrO2 orTiO2 or its precursor. The carrier is one of SiO2 , A12 O3 , HZSM-5 or activated carbon. At 110-260° C., the hydrogen pressure is 0.1-8.0 MPa, and the reaction is 2.5-50 hours. The conversion rate of glycerol can reach 15.3%, and the selectivity of 1,3-propanediol can reach 50.5%. This method uses precious metals, the price is higher, and the conversion rate of glycerol and the selectivity of propylene glycol are not high.
US4642394在有机疏质子溶剂中，30MPaH2、200℃条件下，在Rh(CO)2(acac)和HWO4均相催化，1，3-丙二醇的收率为21％。该反应条件苛刻，且使用有机溶剂不符合绿色清洁的要求。In US4642394, Rh(CO)2 (acac) and HWO4 are homogeneously catalyzed in an organic aprotic solvent under the conditions of 30MPaH2 and 200°C, and the yield of 1,3-propanediol is 21%. The reaction conditions are harsh, and the use of organic solvents does not meet the requirements of green cleaning.
目前，甘油催化氢解法大多采用贵金属催化剂，贵金属催化剂催化反应甘油的转化率不高，过程中条件苛刻不便于操作(见CN102059116A)。有些非贵金属催化剂在反应过程中，先将其甘油汽化，甘油沸点高，因此耗能高(见CN1090568A，CN101747150A)。因此开发一种高效的非贵金属催化剂使甘油在温和加氢条件下制备丙二醇，是具有现实意义和深远影响的课题。At present, most of the catalytic hydrogenolysis methods of glycerol use noble metal catalysts. The conversion rate of glycerol in the catalytic reaction of noble metal catalysts is not high, and the conditions in the process are harsh and inconvenient to operate (see CN102059116A). Some non-precious metal catalysts vaporize glycerol earlier in the reaction process, and glycerol has a high boiling point, so energy consumption is high (see CN1090568A, CN101747150A). Therefore, the development of an efficient non-precious metal catalyst to prepare propylene glycol from glycerol under mild hydrogenation conditions is a topic of practical significance and far-reaching impact.
发明内容Contents of the invention
本发明以铜作为主活性成分，添加一定量的助催化剂制备成一定比例的固体催化剂，使用非贵金属，价格便宜，甘油常温进料不需要汽化，反应的条件较温和易于操作，产率较高等优点。The present invention uses copper as the main active ingredient, adds a certain amount of co-catalyst to prepare a certain proportion of solid catalyst, uses non-precious metals, is cheap, does not need to be vaporized when feeding glycerin at room temperature, the reaction conditions are relatively mild and easy to operate, and the yield is high. advantage.
本发明的目的是提供一种价格廉价、操作条件温和的铜基催化剂应用于甘油制丙二醇的方法。The purpose of the present invention is to provide a method for the preparation of propylene glycol from glycerin using a copper-based catalyst with low price and mild operating conditions.
本发明提供的一种甘油催化氢解制丙二醇的方法，所用的反应器是固定床反应器，也可适应于高压釜反应器，原料为甘油或其水溶液。The present invention provides a method for preparing propylene glycol by catalytic hydrogenolysis of glycerin. The reactor used is a fixed-bed reactor, which can also be adapted to an autoclave reactor. The raw material is glycerin or its aqueous solution.
本发明中铜基催化剂采用共沉淀法制备，催化剂按照一定的比例配置成浓度一定的水溶液，金属氧化物的前驱物为硝酸铜的水溶液浓度范围为10～40wt％，沉淀剂采用氢氧化钠水溶液浓度为10～40wt％，金属助剂是TiCl3、TiCl4、钛酸四丁酯、Ce(NO3)3或其氧化物，采用载体为SiO2、A12O3等。沉淀温度30～85℃。老化温度在45～120℃，老化4～24h，pH值控制在9～12。经洗涤过滤、400～600℃焙烧4h～12h打片成型后装入固定床反应器中。In the present invention, the copper-based catalyst is prepared by a co-precipitation method, and the catalyst is configured into an aqueous solution with a certain concentration according to a certain ratio. The precursor of the metal oxide is copper nitrate in an aqueous solution with a concentration range of 10 to 40 wt%, and the precipitant is an aqueous sodium hydroxide solution. The concentration is 10-40wt%, the metal additives are TiCl3 , TiCl4 , tetrabutyl titanate, Ce(NO3 )3 or their oxides, and the carrier is SiO2 , Al2 O3 and the like. Precipitation temperature is 30-85°C. The aging temperature is 45-120°C, the aging time is 4-24 hours, and the pH value is controlled at 9-12. After washing and filtering, roasting at 400-600°C for 4h-12h, punching into pieces, and then loading into a fixed-bed reactor.
上述技术方案中所述的催化剂使用前必须经活化还原处理，催化剂经程序升温从25～300℃，并按照V(N2∶H2)＝170∶30在压力0.5～4MPa条件下进行还原活化处理。The catalyst described in the above technical scheme must be activated and reduced before use. The temperature of the catalyst is raised from 25 to 300°C, and the reduction and activation is carried out under the condition of V(N2 : H2 )=170:30 at a pressure of 0.5 to 4 MPa. deal with.
经上述活化处理的催化剂在固定床反应器中，调节反应压力0.5～5MPa，通入氢气，甘油水溶液用平流型计量泵进料，氢醇比为30～100，甘油水溶液浓度(质量比10～80％)，液空速在0.3～0.9h-1，反应温度在180～240℃下进行反应。In the fixed-bed reactor, adjust the reaction pressure of 0.5-5 MPa through the above-mentioned activated catalyst, feed hydrogen gas, and feed the glycerol aqueous solution with an advection metering pump. 80%), the liquid space velocity is 0.3-0.9h-1, and the reaction temperature is 180-240°C.
本发明所制备的催化剂能高效催化氢解甘油制得丙二醇，不仅操作条件温和，而且整个过程中不使用溶剂及有毒有害的金属组分，不污染环境。所制备的催化剂稳定性好，使用寿命较长，克服了使用贵金属催化条件苛刻、成本较高、选择性低等缺点。The catalyst prepared by the invention can efficiently catalyze the hydrogenolysis of glycerin to prepare propylene glycol, not only has mild operating conditions, but also does not use solvents and toxic and harmful metal components in the whole process, and does not pollute the environment. The prepared catalyst has good stability and long service life, and overcomes the disadvantages of harsh catalytic conditions, high cost and low selectivity of using precious metals.
实例example
下面就具体实例对本发明方法进一步说明The method of the present invention will be further described below with regard to specific examples
实例1Example 1
催化剂制备：称取10gCu(NO3)2.3H2O加水配制成将浓度20wt％的硝酸铜溶液，称取10克氢氧化钠加水配制成浓度16wt％氢氧化钠水溶液，同时将两种溶液并流滴加到烧瓶中，保持沉淀温度45℃，控制pH值为10～11，滴加完毕后，加入15克浓度30wt％的硅溶胶，升温至85℃下老化6小时，热水洗涤数次，经抽滤、120℃干燥12h，500℃焙烧6h，碾碎成型筛选15～40目颗粒待用。Catalyst preparation: take 10g of Cu(NO3 )2 .3H2 O and add water to make a copper nitrate solution with a concentration of 20wt%, and take 10 grams of sodium hydroxide and add water to make a 16wt% sodium hydroxide aqueous solution, and simultaneously mix the two solutions Add it dropwise to the flask, keep the precipitation temperature at 45°C, and control the pH value to 10-11. After the dropwise addition, add 15 grams of silica sol with a concentration of 30wt%, raise the temperature to 85°C and age for 6 hours, wash with hot water for several After suction filtration, drying at 120°C for 12 hours, roasting at 500°C for 6 hours, crushing, forming and screening 15-40 mesh particles for use.
采用微型固定床反应器，填装好催化剂，通入氮气和氢气V(N2∶H2)＝170∶30，调节体系压力为1.5MPa条件下，280℃将催化剂还原20小时。A miniature fixed-bed reactor was used, the catalyst was filled, nitrogen and hydrogen gas V(N2 :H2 )=170:30 were introduced, and the system pressure was adjusted to 1.5 MPa, and the catalyst was reduced at 280° C. for 20 hours.
还原结束后关闭氮气，调节体系压力和反应温度，将50％的甘油水溶液用平流计量泵进料，进料量为0.05sccm，氢气流量为225sccm，在180～240℃条件下反应，反应稳定后取样分析，用气相色谱仪进行分析。所得产物的选择性和甘油的转化率如下。After the reduction, turn off the nitrogen, adjust the system pressure and reaction temperature, feed the 50% glycerin aqueous solution with an advection metering pump, the feed amount is 0.05 sccm, the hydrogen flow rate is 225 sccm, react under the condition of 180-240 ° C, after the reaction is stable Sampling analysis was carried out by gas chromatography. The selectivity of the obtained product and the conversion of glycerin were as follows.
实例2Example 2
催化剂制备：分别称取10gCu(NO3)2.3H2O和25克18wt％的TiCl3溶液混合后加入100毫升水配制水溶液，称取15克氢氧化钠加水配制成浓度38wt％氢氧化钠水溶液，同时将两种溶液并流滴加到烧瓶中，保持沉淀温度45℃，控制pH值为10～11，滴加完毕后，加入5克氢氧化铝胶，升温至85℃下老化6小时，热水洗涤数次，经抽滤、120℃干燥12h，500℃焙烧6h，碾碎成型筛选15～40目颗粒待用。Catalyst preparation: Weigh 10g Cu(NO3 )2 .3H2 O and 25 grams of 18wt% TiCl3 solution and mix them, then add 100 milliliters of water to prepare an aqueous solution, weigh 15 grams of sodium hydroxide and add water to make a concentration of 38wt% sodium hydroxide Aqueous solution, add the two solutions into the flask simultaneously, keep the precipitation temperature at 45°C, and control the pH value to 10-11. After the dropwise addition, add 5 grams of aluminum hydroxide glue, and heat up to 85°C for aging for 6 hours , washed several times with hot water, filtered by suction, dried at 120°C for 12 hours, roasted at 500°C for 6 hours, crushed and formed to screen 15-40 mesh particles for use.
采用微型固定床反应器，填装好催化剂，通入氮气和氢气V(N2∶H2)＝170∶30，调节体系压力为1.5MPa条件下，280℃将催化剂还原20小时。A miniature fixed-bed reactor was used, the catalyst was filled, nitrogen and hydrogen gas V(N2 :H2 )=170:30 were introduced, and the system pressure was adjusted to 1.5 MPa, and the catalyst was reduced at 280° C. for 20 hours.
还原结束后关闭氮气，调节体系压力和反应温度，将90wt％的甘油水溶液用平流计量泵进料，进料量为0.04sccm，氢气流量为660sccm，在180～240℃条件下反应，反应稳定后取样分析，用气相色谱仪进行分析。改变反应的温度为180℃、200℃、220℃、240℃，所得产物的选择性和甘油的转化率如下。After the reduction, turn off the nitrogen, adjust the system pressure and reaction temperature, feed the 90wt% glycerol aqueous solution with an advection metering pump, the feed amount is 0.04sccm, the hydrogen flow rate is 660sccm, react under the condition of 180-240°C, after the reaction is stable Sampling analysis was carried out by gas chromatography. The temperature of the reaction was changed to 180° C., 200° C., 220° C., and 240° C., and the selectivity of the obtained product and the conversion rate of glycerin were as follows.
实例3Example 3
催化剂制备：分别称取10gCu(NO3)2.3H2O、2.5克硝酸铈和18wt％的TiCl3溶液10克混合后加入100毫升水配制水溶液，称取21克氢氧化钠加水配制成浓度15wt％氢氧化钠水溶液，同时将两种溶液并流滴加到烧瓶中，保持沉淀温度45℃，控制pH值为10～11，滴加完毕后，加入17克浓度30wt％的硅溶胶，升温至85℃下老化6小时，热水洗涤数次，经抽滤、120℃干燥12h，500℃焙烧6h，碾碎成型筛选15～40目颗粒待用。Catalyst preparation: Weigh 10g of Cu(NO3 )2 .3H2 O, 2.5 grams of cerium nitrate and 10 grams of 18wt% TiCl3 solution, mix them and add 100 milliliters of water to prepare an aqueous solution, weigh 21 grams of sodium hydroxide and add water to prepare the concentration 15wt% sodium hydroxide aqueous solution, simultaneously add two kinds of solutions to the flask dropwise, keep the precipitation temperature at 45°C, control the pH value to 10-11, after the dropwise addition, add 17 grams of silica sol with a concentration of 30wt%, and heat Aging at 85°C for 6 hours, washing with hot water for several times, suction filtration, drying at 120°C for 12 hours, roasting at 500°C for 6 hours, crushing, forming and screening 15-40 mesh particles for use.
按实例1的方法进行催化剂装填和还原。将30wt％的甘油水溶液用平流计量泵进料，进料量为0.10sccm，氢气流量为298sccm，在160～220℃条件下反应，反应稳定后取样分析，所得产物的选择性和甘油的转化率反应结果如下。Carry out catalyst packing and reduction by the method for example 1. The 30wt% glycerin aqueous solution is fed with an advection metering pump, the feed amount is 0.10sccm, the hydrogen flow rate is 298sccm, and the reaction is carried out at 160-220°C. After the reaction is stable, take a sample and analyze the selectivity of the obtained product and the conversion rate of glycerin The reaction results are as follows.
实例4Example 4
催化剂制备：分别称取10gCu(NO3)2.3H2O和1.2克硝酸铈和22.5克18wt％的TiCl3溶液混合后加入100毫升水配制水溶液，称取23克氢氧化钠加水配制成浓度15wt％氢氧化钠水溶液，同时将两种溶液并流滴加到烧瓶中，保持沉淀温度45℃，控制pH值为10～11，滴加完毕后，加入8克浓度30wt％的硅溶胶，升温至85℃下老化6小时，热水洗涤数次，经抽滤、120℃干燥12h，500℃焙烧6h，碾碎成型筛选15～40目颗粒待用。Catalyst preparation: Weigh 10g Cu(NO3 )2 .3H2 O and 1.2 grams of cerium nitrate and 22.5 grams of 18wt% TiCl3 solution and mix them, add 100 milliliters of water to prepare an aqueous solution, weigh 23 grams of sodium hydroxide and add water to prepare the concentration 15wt% sodium hydroxide aqueous solution, simultaneously add two kinds of solutions to the flask dropwise, keep the precipitation temperature at 45°C, control the pH value to 10-11, after the dropwise addition, add 8 grams of silica sol with a concentration of 30wt%, and heat Aging at 85°C for 6 hours, washing with hot water for several times, suction filtration, drying at 120°C for 12 hours, roasting at 500°C for 6 hours, crushing, forming and screening 15-40 mesh particles for use.
按实例1的方法进行催化剂装填和还原和反应。所得产物的选择性和甘油的转化率反应结果如下Carry out catalyst packing and reduction and reaction by the method for example 1. The selectivity of the product obtained and the conversion rate reaction result of glycerol are as follows
实例5Example 5
催化剂制备：分别称取10gCu(NO3)2.3H2O，1.2克硝酸铈混合后加入100毫升水配制水溶液，称取27克氢氧化钠加水配制成浓度38wt％氢氧化钠水溶液，同时将两种溶液并流滴加到烧瓶中，保持沉淀温度45℃，控制pH值为10～11，滴加完毕后，加入17克浓度30wt％的硅溶胶，升温至85℃下老化6小时，热水洗涤数次，经抽滤、120℃干燥12h，500℃焙烧6h，碾碎成型筛选15～40目颗粒待用。Catalyst preparation: Weigh 10g Cu(NO3 )2 .3H2 O and 1.2 grams of cerium nitrate respectively, add 100 milliliters of water to prepare an aqueous solution after mixing, weigh 27 grams of sodium hydroxide and add water to prepare a sodium hydroxide aqueous solution with a concentration of 38 wt%. The two solutions were added dropwise to the flask, the precipitation temperature was kept at 45°C, and the pH value was controlled to be 10 to 11. After the dropwise addition, 17 grams of silica sol with a concentration of 30wt% was added, and the temperature was raised to 85°C for aging for 6 hours. Wash with water for several times, filter with suction, dry at 120°C for 12 hours, roast at 500°C for 6 hours, crush and shape to screen 15-40 mesh particles for use.
按实例1的方法进行催化剂装填和还原和反应。所得产物的选择性和甘油的转化率反应结果如下。Carry out catalyst packing and reduction and reaction by the method for example 1. The reaction results of the selectivity of the obtained product and the conversion rate of glycerol are as follows.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419541.9ACN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419541.9ACN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| Publication Number | Publication Date |
|---|---|
| CN102924233A CN102924233A (en) | 2013-02-13 |
| CN102924233Btrue CN102924233B (en) | 2015-04-15 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210419541.9AExpired - Fee RelatedCN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| Country | Link |
|---|---|
| CN (1) | CN102924233B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045546B (en)* | 2014-06-27 | 2017-01-04 | 江苏大学 | A kind of catalyzing glycerol prepares the method for lactic acid |
| CN104045543B (en)* | 2014-06-27 | 2016-08-31 | 江苏大学 | A kind of method that Nanometer Copper catalyzing glycerol prepares lactic acid |
| AR098779A1 (en)* | 2014-12-17 | 2016-06-15 | Univ Nac Del Litoral | A CATALYTIC PROCESS FOR THE PRODUCTION OF PROPYLENGLYCOL FROM GLICEROL, A COPPER AND CERIUS CATALYST, AND A PROCESS TO PREPARE SUCH CATALYST |
| CN105344357A (en)* | 2015-09-30 | 2016-02-24 | 东南大学 | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis |
| CN106179366B (en)* | 2016-07-07 | 2019-01-18 | 淮安万邦香料工业有限公司 | A kind of CuO-CeO2-SiO2-Al2O3Catalyst and preparation method thereof prepares the application in 1,2- propylene glycol in glycerine hydrogenation with it |
| CN107774271B (en)* | 2017-10-25 | 2020-07-24 | 宏业生物科技股份有限公司 | High-selectivity catalyst for producing 1, 2-propylene glycol |
| CN111939918B (en)* | 2020-09-08 | 2022-12-23 | 安徽师范大学 | Rare earth oxide/copper oxide-zirconium oxide catalyst, preparation method thereof and method for preparing lactic acid from glycerol |
| CN113429260B (en)* | 2021-05-24 | 2023-04-07 | 中科合成油技术股份有限公司 | Method for preparing propylene glycol by catalytic hydrogenolysis of glycerol |
| CN114247451B (en)* | 2021-12-31 | 2023-12-22 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4642394A (en)* | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
| WO2007010299A1 (en)* | 2005-07-15 | 2007-01-25 | Davy Process Technology Ltd | Process |
| CN101195557A (en)* | 2006-12-07 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for preparing 1,2-propanediol by hydrogenation of glycerol |
| CN101239315A (en)* | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof |
| CN101456791A (en)* | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for producing 1,2-propanediol by using biological base glycerol |
| CN101898946A (en)* | 2010-06-29 | 2010-12-01 | 江苏大学 | A kind of method of catalytic glycerol hydrogenolysis |
| CN102225883A (en)* | 2011-03-10 | 2011-10-26 | 江苏大学 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4642394A (en)* | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
| WO2007010299A1 (en)* | 2005-07-15 | 2007-01-25 | Davy Process Technology Ltd | Process |
| CN101195557A (en)* | 2006-12-07 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for preparing 1,2-propanediol by hydrogenation of glycerol |
| CN101456791A (en)* | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for producing 1,2-propanediol by using biological base glycerol |
| CN101239315A (en)* | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof |
| CN101898946A (en)* | 2010-06-29 | 2010-12-01 | 江苏大学 | A kind of method of catalytic glycerol hydrogenolysis |
| CN102225883A (en)* | 2011-03-10 | 2011-10-26 | 江苏大学 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
| Publication number | Publication date |
|---|---|
| CN102924233A (en) | 2013-02-13 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102924233B (en) | Method for preparing propylene glycol by glycerin hydrogenolysis | |
| EP3199512B1 (en) | Method for preparing ethylene glycol | |
| CN102344341B (en) | Method for preparing 1,3-propylene glycol by utilizing glycerol one-step hydrogenolysis method | |
| CN103657658B (en) | Carboxylic ester hydrogenation catalyst and prepare the method for cyclohexanol and ethanol | |
| CN102600842A (en) | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof | |
| CN114522738B (en) | Method for preparing 1, 3-propylene glycol by one-step hydrogenation of 3-acetoxy propionaldehyde | |
| CN102407121A (en) | A kind of preparation method of hydrogenation catalyst using X/Ni/Al hydrotalcite as precursor | |
| CN102688768A (en) | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof | |
| CN102658165A (en) | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof | |
| CN107253937A (en) | A kind of synthetic method of γ valerolactones | |
| CN102211040A (en) | Mixed oxide supported mesoporous molecular sieve catalyst and application thereof in catalytic preparation of alpha-phenylethanol | |
| CN103240095A (en) | Methyl acetate hydrogenation catalyst and preparation method thereof | |
| CN102690170B (en) | Method for preparing ethanol by acetic acid gas phase hydrogenation | |
| CN101898946B (en) | Method for hydrogenolysis catalysis of glycerin | |
| CN106582666A (en) | Gamma-valerolactone hydrogenation catalyst, preparation method thereof and method for preparation of 1,4-pentanediol and 2-methyltetrahydrofuran | |
| CN116713003A (en) | A catalyst for hydrogenating dimethyl oxalate to produce methyl acetate or ethanol and its preparation method and application | |
| CN104710282A (en) | Method for production of ethanol and co-production of methanol | |
| CN110256198A (en) | A kind of production method of 1,4- pentanediol | |
| CN109369366A (en) | A kind of method that glycerine catalytic dehydrogenation prepares lactic acid | |
| CN101314134A (en) | Preparation method of bifunctional catalyst for direct preparation of dimethyl ether from synthesis gas | |
| CN109704917B (en) | A process for chemically converting corn cob furfural residue into bioethanol | |
| CN110054547B (en) | Method for preparing ethanol by oxalate hydrogenation under coupled catalysis of integrated catalyst | |
| CN105435798B (en) | Carboxylate hydrogenation copper base catalyst | |
| CN115894196B (en) | A method for continuously synthesizing cyclopentanone | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20150415 | |
| CF01 | Termination of patent right due to non-payment of annual fee |