CN115947653A - Method and catalyst for simultaneously producing 1, 4-cyclohexanedicarboxylic acid as byproduct in hydrofining of crude terephthalic acid - Google Patents
Method and catalyst for simultaneously producing 1, 4-cyclohexanedicarboxylic acid as byproduct in hydrofining of crude terephthalic acid Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及粗对苯二甲酸加氢精制技术,特别是粗对苯二甲酸加氢精制同时副产1,4-环己烷二甲酸的方法及其催化剂。The invention relates to a crude terephthalic acid hydrogenation refining technology, in particular to a method for the crude terephthalic acid hydrogenation refining while by-producing 1,4-cyclohexanedicarboxylic acid and a catalyst thereof.
背景技术Background technique
精对苯二甲酸(PTA)是一种重要的有机化工原料。通常是以对二甲苯(PX)液相氧化制得粗对苯二甲酸(CTA),再由CTA加氢精制而得到。CTA中一般含有较高含量的对羧基苯甲醛(4-CBA),精制过程主要是为了除去4-CBA,一般工业要求PTA中4-CBA的含量要低于25ppm。Purified terephthalic acid (PTA) is an important organic chemical raw material. Usually, crude terephthalic acid (CTA) is obtained by liquid-phase oxidation of p-xylene (PX), and then obtained by hydrogenation of CTA. Generally, CTA contains higher content of p-carboxybenzaldehyde (4-CBA). The refining process is mainly to remove 4-CBA. The general industry requires that the content of 4-CBA in PTA be lower than 25ppm.
1,4-环己烷二甲酸(CHDA)是脂肪族二元酸,其主要用途是作为改性单体,用于生产粉末涂料用的树脂、高固含量密胺(三聚氰胺)聚酯烘烤瓷漆、卷材涂料用树脂、水性聚酯树脂、胶衣涂料用不饱和聚酯树脂、凝胶土层用不饱和聚酯树脂以及聚氨酯涂料用聚酯多元醇。1,4-cyclohexanedicarboxylic acid (CHDA) is an aliphatic dibasic acid, its main use is as a modified monomer for the production of resins for powder coatings, high solid content melamine (melamine) polyester baking Enamel paints, resins for coil coatings, water-based polyester resins, unsaturated polyester resins for gel coat coatings, unsaturated polyester resins for gel coats, and polyester polyols for polyurethane coatings.
除了作为改性单体外,CHDA还可以是生产1,4-环己烷二甲醇(CHDM)的中间体,而CHDM是工业上重要的聚酯生产原料,主要用于聚酯纤维的生产。用CHDM生产的聚酯纤维与乙二醇合成的聚酯相比.不仅更具低密度、高熔点等特性,且其水解稳定性和电气性能也更优异,特别适用于制作电器设备。目前全球实现CHDA工业化生产的企业主要以美国Eastman化学公司为代表,另外美国Amoco公司和日本Towa化学工业有限公司也都有进行CHDA相关技术的研发。In addition to being a modified monomer, CHDA can also be an intermediate in the production of 1,4-cyclohexanedimethanol (CHDM), and CHDM is an industrially important raw material for polyester production, mainly used in the production of polyester fibers. Compared with the polyester synthesized by ethylene glycol, the polyester fiber produced by CHDM not only has the characteristics of low density and high melting point, but also has better hydrolysis stability and electrical properties, and is especially suitable for making electrical equipment. At present, the world's enterprises that realize the industrialized production of CHDA are mainly represented by Eastman Chemical Company of the United States. In addition, Amoco Company of the United States and Towa Chemical Industry Co., Ltd. of Japan also have research and development of CHDA related technologies.
以对苯二甲酸为原料制备CHDA是目前最具前景的方法,早在1959年,美国专利US2888484就提出了采用钯系催化剂进行对苯二甲酸加氢制CHDA,在其实施例中,以5wt%Pd/C为催化剂,在反应温度为195℃,反应压力大于34MPa,反应2h后对苯二甲酸的转化率达到了100%,1,4-环己烷二甲酸的收率也达到了98.5%,取得了不错的效果,但其反应压力过高,实施起来比较困难。US5430184公开了1,4-环己烷二甲酸的制备过程,但以乙醇和水为溶剂,提高了对苯二甲酸溶液的进料浓度,同样采用钯系催化剂,钯负载量为5%~10%,载体选用抗酸性物质如铝、硅或炭等。在氢化反应温度120~160℃,压力0.19~0.95MPa条件下,反应时间30~120min,滤掉催化剂后分析CHDA产物纯度达到98%,副产物主要为4-甲基环己烷甲酸和环己烷甲酸。虽然降低了反应温度和反应压力,但由于体系中引入了乙醇,副产物较多,分离困难。Using terephthalic acid as a raw material to prepare CHDA is currently the most promising method. As early as 1959, U.S. Patent No. 2,888,484 proposed the use of palladium catalysts to hydrogenate terephthalic acid to prepare CHDA. In its examples, 5 wt %Pd/C as the catalyst, at a reaction temperature of 195°C and a reaction pressure greater than 34MPa, the conversion rate of terephthalic acid reached 100% after 2 hours of reaction, and the yield of 1,4-cyclohexanedicarboxylic acid also reached 98.5 %, achieved good results, but its reaction pressure is too high, and it is difficult to implement. US5430184 discloses the preparation process of 1,4-cyclohexanedicarboxylic acid, but ethanol and water are used as solvents to increase the feed concentration of terephthalic acid solution, and palladium series catalysts are also used, and the palladium loading capacity is 5% to 10% %, the carrier is selected from acid-resistant substances such as aluminum, silicon or carbon. Under the condition of hydrogenation reaction temperature of 120-160℃, pressure of 0.19-0.95MPa, reaction time of 30-120min, the purity of CHDA product can reach 98% after filtering off the catalyst, and the by-products are mainly 4-methylcyclohexanecarboxylic acid and cyclohexane Alkanoic acid. Although the reaction temperature and reaction pressure are reduced, due to the introduction of ethanol in the system, there are many by-products and separation is difficult.
US6291706公开了氢化对苯二甲酸制备1,4-环己烷二甲酸的方法,在其提供的实施例中采用0.5wt%Pd/C催化剂,苯二甲酸在水溶液中的质量分数为5%,在温度200~230℃范围内,氢压4.48MPa,加氢反应产物CHDA纯度最高达到98%,但对苯二甲酸(TA)的转化率只有66.5%。US6291706 discloses a method for preparing 1,4-cyclohexanedicarboxylic acid by hydrogenating terephthalic acid. In the examples provided, 0.5wt% Pd/C catalyst is used, and the mass fraction of phthalic acid in aqueous solution is 5%. In the temperature range of 200-230° C. and the hydrogen pressure of 4.48 MPa, the purity of the hydrogenation reaction product CHDA reaches up to 98%, but the conversion rate of terephthalic acid (TA) is only 66.5%.
由于工业上对CHDA的需求量并不太高,因此,以单独的装置来制备CHDA在工业生产中则不够经济。如果能够在CTA精制制备PTA的过程中副产CHDA则将是一种比较经济有效的手段。但由于CTA精制制备PTA的过程与CTA制备CHDA的过程存在明显的矛盾之处,CTA加氢精制的反应温度为280℃以上,而如果要在这个温度下使TA加氢生成CHDA则会发生严重的脱羧反应而又会生成大量环己甲酸,影响了CHDA产率。但若在250℃下反应,则由于TA的溶解度很低,又会大大降低CTA加氢精制的效率,使得装置的产能得不到有效利用。Since the industrial demand for CHDA is not too high, it is not economical to prepare CHDA with a separate device in industrial production. It will be a more economical and effective means if CHDA can be produced by-product in the process of refining CTA to prepare PTA. However, due to the obvious contradiction between the process of refining CTA to prepare PTA and the process of preparing CHDA from CTA, the reaction temperature of CTA hydrogenation refining is above 280 ° C, and if TA is hydrogenated to generate CHDA at this temperature, serious problems will occur. The decarboxylation reaction will generate a large amount of cyclohexanecarboxylic acid, which affects the CHDA yield. However, if the reaction is performed at 250°C, the efficiency of CTA hydrofining will be greatly reduced due to the low solubility of TA, so that the production capacity of the device will not be effectively utilized.
发明内容Contents of the invention
本发明的目的在于提供一种粗对苯二甲酸(CTA)加氢精制制备精对苯二甲酸(PTA)的过程中可以副产1,4-环己烷二甲酸(CHDA)的方法及催化剂。以实现在CTA精制制备PTA的过程中副产CHDA。The object of the present invention is to provide a kind of method and catalyst that can by-produce 1,4-cyclohexanedicarboxylic acid (CHDA) in the process of preparing purified terephthalic acid (PTA) by hydrogenation of crude terephthalic acid (CTA) . To realize by-product CHDA in the process of refining CTA to prepare PTA.
本发明第一方面在于提供一种粗对苯二甲酸加氢精制同时副产1,4-环己烷二甲酸的方法,包括如下步骤:The first aspect of the present invention is to provide a method for crude terephthalic acid hydrogenation refining while by-producing 1,4-cyclohexanedicarboxylic acid, comprising the following steps:
(1)将粗对苯二甲酸、催化剂及溶剂混合;(1) crude terephthalic acid, catalyst and solvent are mixed;
(2)在温度为250-285℃、压力为6-10MPa的条件下进行加氢精制反应得到精对苯二甲酸和1,4-环己烷二甲酸;(2) Under the conditions of a temperature of 250-285°C and a pressure of 6-10MPa, hydrogenation refining reaction is carried out to obtain purified terephthalic acid and 1,4-cyclohexanedicarboxylic acid;
其中所述催化剂包括载体和负载于载体上的Pd和Rh。Wherein the catalyst comprises a carrier and Pd and Rh loaded on the carrier.
进一步地,以催化剂为基准,所述催化剂中Pd的负载量为0.5wt%-1wt%,Rh的负载量为0.1wt%-0.5wt%。Further, based on the catalyst, the loading amount of Pd in the catalyst is 0.5wt%-1wt%, and the loading amount of Rh is 0.1wt%-0.5wt%.
进一步地,所述载体为活性炭,优选椰壳活性炭,更优选所述椰壳活性炭的比表面积为800-1200m2/g,活性炭中的Na、K、Ca的含量之和为不高于300ppm。Further, the carrier is activated carbon, preferably coconut shell activated carbon, more preferably the specific surface area of the coconut shell activated carbon is 800-1200m 2 /g, and the sum of Na, K and Ca contents in the activated carbon is not higher than 300ppm.
进一步地,步骤(1)中粗对苯二甲酸与溶剂的质量比为1:99-30:70,粗对苯二甲酸与催化剂的质量比为100:(1-10)。Further, the mass ratio of crude terephthalic acid to solvent in step (1) is 1:99-30:70, and the mass ratio of crude terephthalic acid to catalyst is 100:(1-10).
进一步地,步骤(1)中所述溶剂优选为水。Further, the solvent described in step (1) is preferably water.
进一步地,步骤(1)中粗对苯二甲酸中含有0.1wt%-0.35wt%的4-醛基-苯甲酸。Further, the crude terephthalic acid in step (1) contains 0.1wt%-0.35wt% 4-formyl-benzoic acid.
进一步地,步骤(2)中反应时间控制在15-90min。Further, the reaction time in step (2) is controlled at 15-90min.
进一步地,步骤(2)之后还包括分离步骤,所述分离步骤包括将反应混合物在80-160℃下过滤,得到精对苯二甲酸,所得滤液冷却至5-20℃后过滤,得到1,4-环己烷二甲酸。Further, after step (2), a separation step is also included, the separation step includes filtering the reaction mixture at 80-160°C to obtain purified terephthalic acid, cooling the obtained filtrate to 5-20°C and then filtering to obtain 1, 4-Cyclohexanedicarboxylic acid.
本发明第二方面在于提供一种粗对苯二甲酸加氢精制同时副产1,4-环己烷二甲酸的催化剂,所述催化剂包括载体和负载于载体上的Pd和Rh。The second aspect of the present invention is to provide a catalyst for hydrofinishing crude terephthalic acid while by-producing 1,4-cyclohexanedicarboxylic acid. The catalyst includes a carrier and Pd and Rh loaded on the carrier.
进一步地,以催化剂为基准,所述催化剂中Pd的负载量为0.5wt%-1wt%,Rh的负载量为0.1wt%-0.5wt%。Further, based on the catalyst, the loading amount of Pd in the catalyst is 0.5wt%-1wt%, and the loading amount of Rh is 0.1wt%-0.5wt%.
进一步地,所述载体为活性炭,优选椰壳活性炭,更优选所述椰壳活性炭的比表面积为800-1200m2/g,活性炭中的Na、K、Ca的含量之和为不高于300ppm。Further, the carrier is activated carbon, preferably coconut shell activated carbon, more preferably the specific surface area of the coconut shell activated carbon is 800-1200m 2 /g, and the sum of Na, K and Ca contents in the activated carbon is not higher than 300ppm.
本发明实现了在粗对苯二甲酸(CTA)加氢精制制备精对苯二甲酸(PTA)的过程中副产1,4-环己烷二甲酸(CHDA)。本发明所说的副产CHDA是指产物中CHDA的含量至少达到5wt%以上。特别是选择特定催化剂与适宜反应条件相匹配,这样不仅不用新建CHDA生产装置,而且可以最大程度的提高装置的经济效益。The invention realizes the by-production of 1,4-cyclohexanedicarboxylic acid (CHDA) in the process of preparing purified terephthalic acid (PTA) through hydrogenation refining of crude terephthalic acid (CTA). The by-product CHDA mentioned in the present invention means that the content of CHDA in the product reaches at least 5wt%. In particular, the selection of a specific catalyst to match the appropriate reaction conditions will not only eliminate the need to build a new CHDA production unit, but also maximize the economic benefits of the unit.
具体实施方式Detailed ways
下面结合具体实施方式对本发明进行示例性阐述,但应当理解本发明的保护范围并不受具体实施方式的限制。The present invention will be illustrated below in conjunction with specific embodiments, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.
本发明对金属含量的分析,采用ICP-AES进行。The analysis of the metal content in the present invention is carried out by ICP-AES.
对于反应产物的分析则主要通过外标法用液相色谱进行分析。The analysis of the reaction products is mainly carried out by liquid chromatography with external standard method.
【实施例1】【Example 1】
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例2】[Example 2]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.25g,含铑0.175g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.5wt%,Rh含量为0.35wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.25g of palladium and 0.175g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging at 80°C for 4h, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.5wt%. The Rh content is 0.35 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例3】[Example 3]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.5g,含铑0.05g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为1.0wt%,Rh含量为0.1wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.5g of palladium and 0.05g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80° C. for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 1.0 wt%. The Rh content is 0.1 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例4】【Example 4】
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.35g,含铑0.25g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.7wt%,Rh含量为0.5wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.35g of palladium and 0.25g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, it is aged at 80°C for 4h, aged After the completion, the reducing agent hydrazine hydrate was added for reduction. After the reduction, the catalyst was washed with deionized water until no chloride ions were detected. Finally, the catalyst was dried at 80°C for 2 hours. The Pd content of the catalyst was analyzed by ICP-AES to be 0.7wt%. The Rh content is 0.5 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例5】【Example 5】
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将125g粗对苯二甲酸(含4-CBA的量为0.375g)和2375g水加入反应釜中,然后开启搅拌并升温至265℃,反应釜压力控制在10MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为60min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalysts are placed in the hanging basket in the reactor, 125g of crude terephthalic acid (the amount containing 4-CBA is 0.375g) and 2375g of water are added in the reactor, and then Start stirring and raise the temperature to 265°C. The pressure of the reactor is controlled at 10MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time pass in hydrogen to react. The reaction time is 60min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例6】[Example 6]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将100g粗对苯二甲酸(含4-CBA的量为0.3g)和900g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 100g of crude terephthalic acid (the amount containing 4-CBA is 0.3g) and 900g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例7】[Example 7]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging at 80°C for 4h, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将200g粗对苯二甲酸(含4-CBA的量为0.6g)和800g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 200g of crude terephthalic acid (the amount containing 4-CBA is 0.6g) and 800g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例8】[Embodiment 8]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至250℃,反应釜压力控制在6MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为90min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 250°C. The pressure of the reactor is controlled at 6MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time pass in hydrogen to react. The reaction time is 90min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【实施例9】[Example 9]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1135m2/g,Na含量207ppm,K含量为132ppm,Ca含量18ppm)作为载体,氯钯酸和氯铑酸混合溶液50g,其中含钯0.375g,含铑0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯铑酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Rh含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1135m 2 /g, Na content 207ppm, K content is 132ppm, Ca content 18ppm) as carrier, chloropalladic acid and chlororhodium acid mixed solution 50g, containing 0.375g of palladium and 0.075g of rhodium as the impregnating solution, impregnating 100g of activated carbon in it and stirring continuously, after the mixed solution of chloropalladic acid and chlororhodium acid is completely absorbed by the activated carbon, aging for 4 hours at a temperature of 80°C, aging After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Rh content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For the convenience of comparison, the analysis results are listed in Table 1.
【比较例1】[Comparative Example 1]
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸溶液50g,其中含钯0.45g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.9wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladium acid solution 50g, wherein contains palladium 0.45g was used as the impregnating solution, impregnated 100g activated carbon in it and kept stirring, after the chloropalladium acid solution was completely absorbed by the activated carbon, aged for 4 hours at a temperature of 80°C, after the aging was completed, the reducing agent hydrazine hydrate was added for reduction, after the reduction was completed, use The catalyst was washed with ionized water until no chlorine ions were detected, and finally the catalyst was dried at 80° C. for 2 hours. The Pd content of the catalyst was analyzed by ICP-AES to be 0.9 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量、CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了方便比较,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and after being fully dissolved with ammonia water, a sample was taken for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content therein. For the convenience of comparison, the analysis results are listed in Table 1.
【比较例2】【Comparative example 2】
催化剂的制备:取100g椰壳活性炭(南京木林森活性炭有限公司提供,比表面积为1108m2/g,Na含量138ppm,K含量为53ppm,Ca含量73ppm)作为载体,氯钯酸和氯钌酸混合溶液50g,其中含钯0.375g,含钌0.075g作为浸渍液,将100g活性炭浸渍其中并不断搅拌,待氯钯酸和氯钌酸混合溶液被活性炭完全吸收后,在温度80℃下老化4h,老化完成后加入还原剂水合肼进行还原,还原完成后用去离子水清洗催化剂直至无氯离子检测出,最后催化剂在80℃干燥2h即可,采用ICP-AES分析催化剂的Pd含量为0.75wt%,Ru含量为0.15wt%。The preparation of catalyst: get 100g coconut shell activated carbon (Nanjing Mulinsen Activated Carbon Co., Ltd. provides, specific surface area is 1108m 2 /g, Na content 138ppm, K content is 53ppm, Ca content 73ppm) as carrier, chloropalladic acid and chlororuthenic acid mixed solution 50g, containing 0.375g of palladium and 0.075g of ruthenium as the impregnating solution, impregnated 100g of activated carbon in it and kept stirring, after the mixed solution of chloropalladic acid and chlororuthenic acid was completely absorbed by the activated carbon, aged at 80°C for 4h, aged After completion, add reducing agent hydrazine hydrate for reduction. After reduction, clean the catalyst with deionized water until no chloride ion is detected. Finally, the catalyst can be dried at 80°C for 2 hours. The Pd content of the catalyst is analyzed by ICP-AES to be 0.75wt%. The Ru content is 0.15 wt%.
粗对苯二甲酸的加氢:将10g上述催化剂置于反应釜中的挂篮中,将300g粗对苯二甲酸(含4-CBA的量为0.9g)和700g水加入反应釜中,然后开启搅拌并升温至280℃,反应釜压力控制在8MPa,当温度和压力都达到要求后,将催化剂挂篮放入反应溶液中,同时通入氢气进行反应,反应时间为25min,反应结束后,将反应釜温度降至室温,取出反应产物,采用氨水全溶解后取样进行液相色谱分析其中的4-CBA含量CHDA含量及脱羧产物(苯甲酸+环己甲酸)含量。为了比较方便,将分析结果列于表1中。The hydrogenation of crude terephthalic acid: 10g of the above-mentioned catalyst is placed in the hanging basket in the reactor, 300g of crude terephthalic acid (containing 4-CBA is 0.9g) and 700g of water are added in the reactor, and then Start stirring and raise the temperature to 280°C. The pressure of the reactor is controlled at 8MPa. When the temperature and pressure meet the requirements, put the catalyst hanging basket into the reaction solution, and at the same time feed hydrogen to react. The reaction time is 25min. After the reaction, The temperature of the reaction kettle was lowered to room temperature, and the reaction product was taken out, and a sample was taken after fully dissolving with ammonia water for liquid chromatography analysis of 4-CBA content, CHDA content and decarboxylation product (benzoic acid+cyclohexanecarboxylic acid) content. For convenience, the analysis results are listed in Table 1.
表1Table 1
以上详细描述了本发明的具体实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。The specific embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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