发明领域field of invention
本发明是丙酮酸的制备方法，具体的说是一种利用钼钒铌复合金属氧化物催化剂高效催化酒石酸生成丙酮酸的方法。The invention is a preparation method of pyruvic acid, specifically a method for efficiently catalyzing tartaric acid to generate pyruvic acid using a molybdenum vanadium niobium composite metal oxide catalyst.
背景技术Background technique
丙酮酸是最小的具有羰基和羧基两种官能团的分子，常用做药物合成和有机合成的中间体。在医药保健方面，可作合成治疗高血压的药物及合成抗病毒剂、镇静剂等，丙酮酸的衍生物丙酮酸钙是目前市场上销售的高效减肥保健药物中的主要成分；在农业上它被用于杀菌剂和除草剂的合成；在日用化工方面，可用作增白剂、防腐剂、抗氧剂、保鲜剂。此外，丙酮酸是α-酮酸中最简单的分子结构，在生物体的化学代谢途径中扮演重要作用。Pyruvate is the smallest molecule with two functional groups, carbonyl and carboxyl, and is often used as an intermediate in drug synthesis and organic synthesis. In terms of medicine and health care, it can be used to synthesize drugs for the treatment of high blood pressure, antiviral agents, sedatives, etc. Calcium pyruvate, a derivative of pyruvate, is the main component of high-efficiency weight-loss health care drugs currently on the market; it is used in agriculture. Used in the synthesis of fungicides and herbicides; in daily chemical industry, it can be used as whitening agent, preservative, antioxidant and preservative. In addition, pyruvate is the simplest molecular structure among α-keto acids, and plays an important role in the chemical metabolic pathway of organisms.
迄今为止，丙酮酸的合成方法主要分为两大类：化学合成法和生物合成法。生物合成法又包括酶法和微生物发酵法，CN102199632（谷劲松，一种转化DL-乳酸制备丙酮酸的生产方法，CN102199632，2011）采用荧光假单胞菌含有的乳酸氧化酶和过氧化氢酶转化乳酸生成丙酮酸，转化率得到提高。CN102121035（刘立明，汪军，陈坚，一种提高丙酮酸产量的方法，CN102121035，2010）采用光滑球拟酵母，在pH分别为4.5、5.5条件下添加天冬氨酸，丙酮酸产量分别为30.4g/L、55.8g/L，技术效果很好。酶法和微生物对发酵用营养液的要求较高，且产物分离成本较高，工业化生产难度较大。So far, the synthesis methods of pyruvate are mainly divided into two categories: chemical synthesis and biosynthesis. The biosynthesis method also includes enzymatic method and microbial fermentation method, CN102199632 (Gu Jinsong, a production method for converting DL-lactic acid to prepare pyruvate, CN102199632, 2011) adopts lactic acid oxidase and catalase contained in Pseudomonas fluorescens Lactic acid is converted into pyruvic acid, and the conversion rate is improved. CN102121035 (Liu Liming, Wang Jun, Chen Jian, a method for increasing the yield of pyruvate, CN102121035, 2010) adopts Torulopsis glabrata, adds aspartic acid under the conditions of pH 4.5 and 5.5 respectively, and the yield of pyruvate is 30.4 g/L, 55.8g/L, the technical effect is very good. The enzymatic method and microorganisms have higher requirements on the nutrient solution for fermentation, and the cost of product separation is higher, making industrial production more difficult.
目前丙酮酸的工业化主要生产工艺是酒石酸脱水脱羧法，该方法采用酒石酸，同硫酸氢钾在200-230℃下反应后经真空精馏得到丙酮酸。该方法使用的硫酸氢钾在酒石酸在脱水脱羧过程中不断被消耗，并以气体污染物SOx的形式排放至大气中，造成环境污染，不符合环保的要求，同时催化剂硫酸氢钾也在不断损耗损失。由于丙酮酸在药物合成、日用化工和食品工业上的广泛应用，使得丙酮酸的商业需求不断膨胀，但是，硫酸氢钾催化酒石酸法会产生SOx，对环境造成污染，阻碍了其商业应用。At present, the main industrial production process of pyruvic acid is tartaric acid dehydration and decarboxylation method, which uses tartaric acid, reacts with potassium bisulfate at 200-230 ° C, and then undergoes vacuum distillation to obtain pyruvic acid. The potassium hydrogen sulfate used in this method is constantly consumed in the dehydration and decarboxylation process of tartaric acid, and is discharged into the atmosphere in the form of gas pollutant SOx, causing environmental pollution and does not meet the requirements of environmental protection, while the catalyst potassium hydrogen sulfate is also constantly being consumed loss. Due to the wide application of pyruvate in drug synthesis, daily chemical industry and food industry, the commercial demand of pyruvate continues to expand. However, potassium bisulfate catalyzed tartaric acid method will produce SOx, which will pollute the environment and hinder its commercial application.
因此急需一种能够高效、同时对环境几乎没有任何污染的制备丙酮酸的方法。Therefore, there is an urgent need for a method for preparing pyruvic acid that can be highly efficient and has almost no pollution to the environment.
发明内容Contents of the invention
本发明的目的在于提供一种以钼钒铌复合金属氧化物为催化剂催化酒石酸脱水脱羧生成丙酮酸的生产方法。The object of the present invention is to provide a kind of production method that uses molybdenum vanadium niobium composite metal oxide as catalyst to catalyze dehydration and decarboxylation of tartaric acid to generate pyruvic acid.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
一种制备丙酮酸的方法,采用钼钒铌复合金属氧化物作为催化剂，在高沸点溶剂存在下，在160-210℃、氧化性气氛、负压条件下反应，催化原料酒石酸脱水脱羧生成丙酮酸；反应时间0.5-3h，催化剂用量占原料量的5-50%。A method for preparing pyruvic acid, using molybdenum-vanadium-niobium composite metal oxide as a catalyst, reacting in the presence of a high-boiling point solvent at 160-210°C, an oxidative atmosphere, and negative pressure conditions, and catalyzing the dehydration and decarboxylation of tartaric acid to generate pyruvic acid ; The reaction time is 0.5-3h, and the amount of catalyst accounts for 5-50% of the amount of raw materials.
产物蒸汽离开反应釜的温度在110-140℃，而后再经冷处理，处理后精制分离得到较高纯度的丙酮酸。The temperature of the product vapor leaving the reactor is 110-140°C, and then undergoes cold treatment. After treatment, it is refined and separated to obtain pyruvic acid with higher purity.
所述高沸点溶剂为耐高温、不易挥发、性质稳定的高沸点溶剂。The high-boiling-point solvent is a high-boiling-point solvent with high temperature resistance, low volatility and stable properties.
所述高沸点溶剂为导热油、石蜡油、硅油中的一种或几种的混合。The high boiling point solvent is one or a mixture of heat conduction oil, paraffin oil, and silicone oil.
所述氧化性气氛为纯氧气、空气、氧气、氮气中的一种或几种的混合。The oxidizing atmosphere is one or a mixture of pure oxygen, air, oxygen and nitrogen.
所述负压在0.05MPa-0.09MPa。The negative pressure is in the range of 0.05MPa-0.09MPa.
所述催化剂钼钒铌复合金属氧化物通式为MoxVyNbzO3x+2.5y+2.5z，其中x为0.1-2.0，y为0.1-1.5，z为0.01-0.5。The general formula of the catalyst molybdenum vanadium niobium composite metal oxide is Mox Vy Nbz O3x+2.5y+2.5z , wherein x is 0.1-2.0, y is 0.1-1.5, and z is 0.01-0.5.
所述催化剂为可负载型催化剂；其中，负载型催化剂按重量百分比计为5-50%的钼钒铌复合金属氧化物和50-95%的载体。The catalyst is a loadable catalyst; wherein, the supported catalyst is 5-50% molybdenum-vanadium-niobium composite metal oxide and 50-95% carrier by weight percentage.
所述负载型催化剂的载体为氧化硅、氧化铝、氧化钛、分子筛、活性炭中的一种或几种的混合。The carrier of the supported catalyst is one or a mixture of silicon oxide, aluminum oxide, titanium oxide, molecular sieve, and activated carbon.
载体可以是粉末状或者小颗粒状，为了便于工业化生产中催化剂的回收再利用，优选颗粒状载体。The carrier can be in the form of powder or small particles. In order to facilitate the recovery and reuse of catalysts in industrial production, granular carriers are preferred.
催化剂的制备采用溶剂热合成法，将一定比例的钼源、钒源、铌源在草酸存在下于40-60℃下混合溶解，该混合液在75-95℃条件下真空搅拌蒸发至催化剂成半固体状，然后将半固体状催化剂置于100℃-140℃温度下干燥过夜，脱除表面水分，随后在350℃-450℃空气气氛下煅烧3-5小时，经过造粒后即得无负载的催化剂颗粒。The preparation of the catalyst adopts the solvothermal synthesis method. A certain proportion of molybdenum source, vanadium source and niobium source are mixed and dissolved in the presence of oxalic acid at 40-60°C, and the mixture is stirred and evaporated in vacuum at 75-95°C until the catalyst is formed. semi-solid, then dry the semi-solid catalyst overnight at a temperature of 100°C-140°C to remove surface moisture, and then calcinate it at 350°C-450°C in an air atmosphere for 3-5 hours, and obtain no supported catalyst particles.
负载型催化剂可在上述混合溶液中加入上述负载物，混合均匀后进行蒸发、过夜干燥、350℃-450℃空气气氛焙烧。For the supported catalyst, the above-mentioned load can be added to the above-mentioned mixed solution, and after mixing uniformly, it is evaporated, dried overnight, and calcined in an air atmosphere at 350°C-450°C.
本发明所具有的优点：The advantages that the present invention has:
本发明采用酒石酸为反应原料，钼钒铌复合金属氧化物为催化剂，经过酒石酸的脱水脱羧反应得到丙酮酸产品。本发明的催化剂为非均相催化剂，催化剂活性高，产物与催化剂容易分离，催化剂可回收再利用，成本降低，且反应温度低，工艺操作简单，对丙酮酸有较高的选择性，同时对环境几乎没有任何污染。The invention adopts tartaric acid as reaction raw material, molybdenum vanadium niobium composite metal oxide as catalyst, and obtains pyruvic acid product through dehydration and decarboxylation reaction of tartaric acid. The catalyst of the present invention is a heterogeneous catalyst with high catalyst activity, easy separation of the product and the catalyst, recyclable catalyst, reduced cost, low reaction temperature, simple process operation, high selectivity to pyruvic acid, and simultaneously The environment is almost free of any pollution.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步说明，但本发明不局限于以下具体实施例。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following specific examples.
实施例1Example 1
钼钒铌复合金属氧化物Mo0.61V0.31Nb0.08O2.81的制备：将7.2g草酸（C2H2O4·2H2O），3.63g偏钒酸铵（NH4VO3）溶于25ml超纯水中，10.77g仲钼酸铵（(NH4)6Mo7O24·4H2O）溶于25ml超纯水中，将完全溶解的上述两种溶液在40-60℃温度下混合均匀，取2.42g铌酸铵草酸盐水合物（C4H4NNbO9·xH2O）溶于25ml超纯水中，然后将该溶液逐滴加入含钼、钒的混合溶液中，在90℃温度真空搅拌下至溶剂几乎完全挥发，得到半固体状催化剂，将该催化剂置于120℃温度下烘干过夜，之后将烘干后的催化剂在400℃温度、足量空气气氛下焙烧4h左右，即得催化剂Mo0.61V0.31Nb0.08O2.81。Preparation of molybdenum vanadium niobium composite metal oxide Mo0.61 V0.31 Nb0.08 O2.81 : 7.2g oxalic acid (C2 H2 O4 2H2 O), 3.63g ammonium metavanadate (NH4 VO3 ) were dissolved in 25ml Dissolve 10.77g of ammonium paramolybdate ((NH4 )6 Mo7 O24 4H2 O) in ultrapure water in 25ml of ultrapure water, and mix the completely dissolved above two solutions at 40-60°C Evenly, take 2.42g of ammonium niobate oxalate hydrate (C4 H4 NNbO9 ·xH2 O) and dissolve it in 25ml of ultrapure water, then add the solution dropwise to the mixed solution containing molybdenum and vanadium, in Stir under vacuum at a temperature of 90°C until the solvent is almost completely volatilized to obtain a semi-solid catalyst. Dry the catalyst at a temperature of 120°C overnight, and then bake the dried catalyst at a temperature of 400°C in a sufficient air atmosphere for 4 hours or so, the catalyst Mo0.61 V0.31 Nb0.08 O2.81 is obtained.
酒石酸制备丙酮酸:在反应器中加入5g酒石酸，60ml导热油，两者搅拌均匀后缓慢升温至186℃，然后向反应器加入2.5g Mo0.61V0.31Nb0.08O2.81催化剂，搅拌均匀后通入空气，空气流量40ml/min，反应在低负压（约-0.06MPa）下进行，反应40min得到一定的液体产物，此时几乎全部酒石酸原料及钼钒铌催化剂都留在反应器里面，只有生成的产物沸点较低，在抽真空条件下经冷却进入收集装置，产物与催化剂得到很好地分离，对产物进行气相色谱-质谱联用仪（GC-MS）分析后，发现产物中主要含有丙酮酸、乙酸等产物，还有少量二氧化碳、乙醛等其他小分子物质，此时丙酮酸的选择性为81%。Tartaric acid is prepared pyruvic acid: add 5g tartaric acid, 60ml heat-conducting oil in reactor, after both are stirred evenly, be warmed up slowly to 186 ℃, then add 2.5g Mo0.61 V0.31 Nb0.08 O2.81 catalyzer to reactor, pass into after stirring Air, the air flow rate is 40ml/min, the reaction is carried out under low negative pressure (about -0.06MPa), and a certain liquid product is obtained after 40 minutes of reaction. The boiling point of the product is low, and it enters the collection device after cooling under vacuum conditions, and the product and the catalyst are well separated. After analyzing the product by gas chromatography-mass spectrometry (GC-MS), it is found that the product mainly contains pyruvic acid , acetic acid and other products, and a small amount of carbon dioxide, acetaldehyde and other small molecular substances, the selectivity of pyruvic acid is 81%.
反应2h后对产物进行GC-MS分析，结果发现丙酮酸选择性在80%左右，几乎没有变化。对产物混合物按照常规方式进行减压精馏，得到较高纯度的丙酮酸，此时丙酮酸纯度在96%以上。After 2 hours of reaction, the product was analyzed by GC-MS, and it was found that the selectivity of pyruvate was about 80%, almost unchanged. The product mixture is subjected to vacuum rectification in a conventional manner to obtain pyruvic acid with higher purity, and the purity of pyruvic acid is above 96%.
将反应器里面的固体催化剂经离心、过滤回收到另一个反应器中，加入与上述实验相同量的酒石酸，在相同的反应条件反应40min收集产物，得到丙酮酸的选择性在80%左右,几乎没有降低。The solid catalyst in the reactor was recycled to another reactor by centrifugation and filtration, and the same amount of tartaric acid as in the above experiment was added, and the product was collected after reacting for 40 minutes under the same reaction conditions, and the selectivity of pyruvic acid was about 80%, almost No lowering.
实施例2：Example 2:
钼钒铌复合金属氧化物Mo0.61V0.31Nb0.08O2.81的制备：将7.2g草酸（C2H2O4·2H2O），3.63g偏钒酸铵（NH4VO3）溶于25ml超纯水中，10.77g仲钼酸铵（(NH4)6Mo7O24·4H2O）溶于25ml超纯水中，将完全溶解的上述两种溶液在40-60°C温度下混合均匀，取2.42g铌酸铵草酸盐水合物（C4H4NNbO9·xH2O）溶于25ml超纯水中，然后将该溶液逐滴加入含钼、钒的混合溶液中，在90°C温度真空搅拌下至溶剂几乎完全挥发，得到半固体状催化剂，将该催化剂置于120°C温度下烘干过夜，之后将烘干后的催化剂在400°C温度、足量空气气氛下焙烧4h左右，即得催化剂Mo0.61V0.31Nb0.08O2.81。Preparation of molybdenum vanadium niobium composite metal oxide Mo0.61 V0.31 Nb0.08 O2.81 : 7.2g oxalic acid (C2 H2 O4 2H2 O), 3.63g ammonium metavanadate (NH4 VO3 ) were dissolved in 25ml In ultrapure water, 10.77g of ammonium paramolybdate ((NH4 )6 Mo7 O24 4H2 O) was dissolved in 25ml of ultrapure water. Mix well, take 2.42g of ammonium niobate oxalate hydrate (C4 H4 NNbO9 xH2 O) and dissolve it in 25ml of ultrapure water, then add the solution dropwise into the mixed solution containing molybdenum and vanadium, Stir under vacuum at a temperature of 90°C until the solvent is almost completely volatilized to obtain a semi-solid catalyst, which is dried overnight at a temperature of 120°C, and then dried at a temperature of 400°C in a sufficient amount of air Calcined under the atmosphere for about 4h to obtain the catalyst Mo0.61 V0.31 Nb0.08 O2.81 .
酒石酸制备丙酮酸：在反应器中加入5g酒石酸，60ml导热油缓慢加热至200°C，然后加入2.5g Mo0.61V0.31Nb0.08O2.81催化剂，搅拌均匀后通入空气，空气流量80ml/min，反应在低负压（约-0.08MPa）下进行，反应1h后得到一定的液体产物，此时几乎全部的酒石酸原料及钼钒铌催化剂都留在反应器里面，只有生成的产物沸点较低，在抽真空条件下经冷却进入收集装置，产物与催化剂得到很好地分离，对产物进行气相色谱-质谱联用仪（GC-MS）分析后，产物中主要含有丙酮酸、乙酸等产物，还有少量二氧化碳，乙醛等，丙酮酸的选择性为76%。Tartaric acid is prepared pyruvic acid: in reactor, add 5g tartaric acid, 60ml heat-conducting oil is slowly heated to 200 ℃, then adds 2.5g Mo0.61 V0.31 Nb0.08 O2.81 catalyzer, feeds air after stirring, air flow 80ml/min, The reaction is carried out under low negative pressure (about -0.08MPa), and a certain liquid product is obtained after the reaction for 1 hour. At this time, almost all the tartaric acid raw materials and the molybdenum vanadium niobium catalyst are left in the reactor, and only the generated product has a lower boiling point. After cooling under vacuum conditions, it enters the collection device, and the product and the catalyst are well separated. After the product is analyzed by gas chromatography-mass spectrometry (GC-MS), the product mainly contains pyruvic acid, acetic acid and other products, as well as A small amount of carbon dioxide, acetaldehyde, etc., the selectivity of pyruvic acid is 76%.
反应2h后对产物进行GC-MS分析，结果发现丙酮酸选择性在72%左右，对产物混合物按照常规方式进行减压精馏，得到较高纯度的丙酮酸，此时丙酮酸的纯度在95%左右。After 2 hours of reaction, the product was analyzed by GC-MS, and it was found that the selectivity of pyruvic acid was about 72%. The product mixture was subjected to vacuum distillation in a conventional manner to obtain pyruvic acid with a higher purity. At this time, the purity of pyruvic acid was 95%. %about.
将反应器里面的固体催化剂经离心、过滤回收到另一个反应器中，加入与上述实验相同量的酒石酸，在相同的反应条件反应1h收集产物，得到的丙酮酸选择性几乎没有变化，仍在76%左右。The solid catalyst in the reactor was recycled to another reactor through centrifugation and filtration, and the same amount of tartaric acid as in the above experiment was added, and the product was collected after reacting for 1 hour under the same reaction conditions. About 76%.
实施例3：Example 3:
酒石酸制备丙酮酸：在反应器中加入5g酒石酸，60ml导热油，二者搅拌均匀后缓慢升温至200℃，然后通入空气，空气流量80ml/min，反应在低负压下（约-0.08MPa）进行，反应1h后得到一定的液体产物，经气相色谱-质谱联用仪（GC-MS）分析后，产物混合物中含有少量乙醛、乙酸等，几乎检测不到丙酮酸的存在。Preparation of pyruvic acid from tartaric acid: Add 5g tartaric acid and 60ml heat transfer oil into the reactor, stir the two evenly and then slowly raise the temperature to 200°C, then pass in air, the air flow rate is 80ml/min, and the reaction is under low negative pressure (about -0.08MPa ), and a certain liquid product was obtained after 1 hour of reaction. After analysis by gas chromatography-mass spectrometry (GC-MS), the product mixture contained a small amount of acetaldehyde, acetic acid, etc., and almost no pyruvic acid was detected.
实施例4：Example 4:
钼钒铌复合金属氧化物Mo0.61V0.31Nb0.08O2.81/TiO2的制备：Preparation of molybdenum vanadium niobium composite metal oxide Mo0.61 V0.31 Nb0.08 O2.81 /TiO2 :
纳米二氧化钛（P25）预处理：向烧杯中加入80g纳米二氧化钛（P25）和250g水，将二氧化钛润湿，然后在120℃温度下烘干过夜，即得颗粒状二氧化钛。Nano-titanium dioxide (P25) pretreatment: Add 80g nano-titanium dioxide (P25) and 250g water into a beaker to wet the titanium dioxide, and then dry it at 120°C overnight to obtain granular titanium dioxide.
将2.52g草酸（C2H2O4·2H2O），0.91g偏钒酸铵（NH4VO3），10g预处理后的二氧化钛溶于25ml超纯水中（二氧化钛不溶），2.7g仲钼酸铵（(NH4)6Mo7O24·4H2O）溶于20ml超纯水中，将完全溶解的上述两种溶液在40-60℃温度下混合均匀，取0.61g铌酸铵草酸盐水合物（C4H4NNbO9·xH2O）溶于20ml超纯水中，然后将该溶液逐滴加入含钼、钒的混合溶液中，在90℃温度真空搅拌下至溶剂几乎完全挥发，得到半固体状催化剂，将该催化剂置于120℃温度下烘干过夜，之后将烘干后的催化剂在400℃温度、足量空气气氛下焙烧4h左右，即得24%的催化剂Mo0.61V0.31Nb0.08O2.81/TiO2。Dissolve 2.52goxalic acid (C2H2O42H2O ), 0.91g ammonium metavanadate (NH4VO3 ), 10g pretreated titanium dioxide in25mlultrapure water (titanium dioxide is insoluble), 2.7g Ammonium paramolybdate ((NH4 )6 Mo7 O24 4H2O) was dissolved in 20ml of ultrapure water, and the above two solutions that were completely dissolved were mixed evenly at a temperature of 40-60°C, and 0.61g of ammonium niobate was taken Salt hydrate (C4 H4 NNbO9 ·xH2 O) was dissolved in 20ml of ultrapure water, and then the solution was added dropwise to the mixed solution containing molybdenum and vanadium, and stirred under vacuum at 90°C until the solvent was almost Completely volatilize to obtain a semi-solid catalyst, dry the catalyst at 120°C overnight, and then roast the dried catalyst at 400°C in a sufficient air atmosphere for about 4 hours to obtain a 24% catalyst Mo0.61 V0.31 Nb0.08 O2.81 /TiO2 .
酒石酸制备丙酮酸：在反应器中加入5g酒石酸，60ml导热油，搅拌均匀后缓慢升温至160℃，然后加入1.0g Mo0.61V0.31Nb0.08O2.81/TiO2催化剂，搅拌均匀后通入空气，空气流量80ml/min，反应在低负压（约-0.08MPa）下进行，反应1h后得到一定的液体产物，此时几乎全部的酒石酸原料及钼钒铌催化剂都留在反应器里面，只有生成的产物沸点较低，在抽真空条件下经冷却进入收集装置，产物与催化剂得到很好地分离，对产物冷却收集后进行气相色谱-质谱联用仪（GC-MS）分析，产物中主要含有丙酮酸、乙酸等产物，还有少量二氧化碳，丙酮酸的选择性为73%左右。Preparation of pyruvic acid from tartaric acid: Add 5g tartaric acid and 60ml heat transfer oil into the reactor, stir well and then slowly heat up to 160°C, then add 1.0g Mo0.61 V0.31 Nb0.08 O2.81 /TiO2 catalyst, stir well and then feed air, The air flow rate is 80ml/min, and the reaction is carried out under low negative pressure (about -0.08MPa). After 1 hour of reaction, a certain liquid product is obtained. At this time, almost all the tartaric acid raw materials and the molybdenum vanadium niobium catalyst are left in the reactor, and only the generated The boiling point of the product is low, and it enters the collection device after cooling under vacuum conditions. The product and the catalyst are well separated. After the product is cooled and collected, it is analyzed by gas chromatography-mass spectrometry (GC-MS). The product mainly contains acetone Acid, acetic acid and other products, and a small amount of carbon dioxide, the selectivity of pyruvic acid is about 73%.
反应3h后对产物进行GC-MS分析，结果发现丙酮酸选择性在70%左右，对产物混合物进行减压精馏，得到较高纯度的丙酮酸，丙酮酸的纯度在95%左右。After reacting for 3 hours, the product was analyzed by GC-MS, and it was found that the selectivity of pyruvic acid was about 70%. The product mixture was subjected to vacuum distillation to obtain pyruvic acid with a higher purity, and the purity of pyruvic acid was about 95%.
将反应器里面的固体催化剂经离心、过滤回收到另一个反应器中，加入与上述实验相同量的酒石酸，在相同的反应条件反应1h后收集产物，丙酮酸的选择性几乎没有降低。The solid catalyst in the reactor was recycled to another reactor through centrifugation and filtration, and the same amount of tartaric acid as in the above experiment was added, and the product was collected after reacting for 1 h under the same reaction conditions, and the selectivity of pyruvic acid was hardly reduced.
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| CN201410033428.6ACN104803841B (en) | 2014-01-24 | 2014-01-24 | A kind of method preparing acetone acid |
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| CN201410033428.6ACN104803841B (en) | 2014-01-24 | 2014-01-24 | A kind of method preparing acetone acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111971270A (en)* | 2018-04-13 | 2020-11-20 | 阿彻丹尼尔斯米德兰德公司 | Dehydration and amination of alpha, beta-dihydroxycarbonyl compounds to alpha amino acids |
| RU2785876C2 (en)* | 2018-04-13 | 2022-12-14 | Арчер Дэниелс Мидлэнд Компани | Dehydration and amination of alpha-, beta-dihydroxycarbonyl compounds to alpha-amino acids |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164997A (en)* | 1990-01-30 | 1992-11-17 | Ezel, Inc. | Method and apparatus for aligning images using pixels of closed contours |
| US5412120A (en)* | 1991-12-13 | 1995-05-02 | Basf Aktiengesellschaft | Preparation of carboxylic esters |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164997A (en)* | 1990-01-30 | 1992-11-17 | Ezel, Inc. | Method and apparatus for aligning images using pixels of closed contours |
| US5412120A (en)* | 1991-12-13 | 1995-05-02 | Basf Aktiengesellschaft | Preparation of carboxylic esters |
| Title |
|---|
| 邱方利: "丙酮酸钠合成工艺的研究", 《化学工程师》* |
| 青岛技术转移中心: "关于召开"生物能源与过程高端技术产业化对接会"的通知", 《HTTP://WWW.QINGDAOTSE.COM/DETAIL.ASPX?ARTICLE_ID=2533》* |
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11414376B2 (en)* | 2018-04-13 | 2022-08-16 | Archer Daniels Midland Company | Dehydration and amination of alpha-, beta-dihydroxy carbonyl compounds to alpha-amino acids |
| RU2785876C2 (en)* | 2018-04-13 | 2022-12-14 | Арчер Дэниелс Мидлэнд Компани | Dehydration and amination of alpha-, beta-dihydroxycarbonyl compounds to alpha-amino acids |
| CN111971270B (en)* | 2018-04-13 | 2024-02-02 | 阿彻丹尼尔斯米德兰德公司 | Dehydration and amination of alpha, beta-dihydroxycarbonyl compounds to alpha amino acids |
| Publication number | Publication date |
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| Publication | Publication Date | Title |
|---|---|---|
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