WO2023273119A1 - 一种Ru基催化剂的制备方法及其应用 - Google Patents

一种Ru基催化剂的制备方法及其应用 Download PDF

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WO2023273119A1
WO2023273119A1 PCT/CN2021/132714 CN2021132714W WO2023273119A1 WO 2023273119 A1 WO2023273119 A1 WO 2023273119A1 CN 2021132714 W CN2021132714 W CN 2021132714W WO 2023273119 A1 WO2023273119 A1 WO 2023273119A1
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based catalyst
alkali metal
ammonium
preparation
catalyst
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郑南峰
邹子金
刘圣杰
陈洁
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厦门大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the technical field of catalysts, and relates to a preparation method and application of a Ru-based catalyst, in particular to a method for hydrogenation and reduction of dimethyl terephthalate into dimethyl 1,4-cyclohexanedicarboxylate Ru-based catalysts.
  • Dimethyl 1,4-cyclohexanedicarboxylate is an important organic chemical raw material, mainly used to prepare 1,4-cyclohexanedimethanol (CHDM).
  • CHDM is an important organic monomer used in the production of polyester in industry.
  • the polyester synthesized by it has very good performance and can be widely used in various aspects of society.
  • Hydrogenation reduction from dimethyl terephthalate is an important method to prepare dimethyl 1,4-cyclohexanedicarboxylate, and precious metal catalysts, such as Ru catalysts, are commonly used.
  • the noble metal catalysts currently used have problems such as low conversion rate, poor selectivity, and poor reusability.
  • DMT dimethyl terephthalate
  • An object of the present invention is to provide a method for preparing Ru-based catalysts, using ammonia or ammonium salts to treat Ru precursors, and then adding alkali metal alkalis or alkali metal salts as auxiliary agents to achieve highly dispersed Ru-based catalysts on the carrier. catalyst.
  • Another object of the present invention is to provide an application of a Ru-based catalyst for catalyzing the hydrogenation reduction of dimethyl terephthalate to generate dimethyl 1,4-cyclohexanedicarboxylate.
  • a preparation method of a Ru-based catalyst carried out according to the following steps, adding ammonia water or ammonium salt to the Ru precursor aqueous solution, stirring evenly, then adding alkali metal alkali or alkali metal salt, stirring evenly, adding the carrier dispersion liquid dropwise, adding dropwise Continue to stir and react for 3-12 hours, filter with suction, wash and dry to obtain Ru-based catalyst.
  • the Ru-based catalyst of the present invention can also be prepared according to the following method, adding ammonia water or ammonium salt to the Ru precursor aqueous solution, stirring evenly, adding the carrier dispersion liquid dropwise, stirring evenly after the dropwise addition, and then adding alkali metal alkali or alkali metal salt , stirred and reacted for 3-12 hours, suction filtered, washed and dried to obtain a Ru-based catalyst.
  • washing can use deionized water or alcoholic aqueous solution (such as absolute ethanol, deionized water by volume ratio 5:5, 6:4, 7:3, 8:2 or 9:1 preparation) ;Drying temperature can be 40-80 °C, can be normal pressure drying, can also be negative pressure drying.
  • deionized water or alcoholic aqueous solution such as absolute ethanol, deionized water by volume ratio 5:5, 6:4, 7:3, 8:2 or 9:1 preparation
  • the Ru precursor is selected from one or more of ruthenium trichloride, ruthenium acetate, ruthenium nitrate and ruthenium sulfate; the concentration of the Ru precursor aqueous solution is 0.01-1mol/l .
  • the Ru precursor is selected from ruthenium trichloride or ruthenium acetate, and the concentration of the Ru precursor aqueous solution is 0.05-0.5mol/l, which can be 0.05mol/l, 0.1mol/l, 0.15mol /l, 0.2mol/l, 0.25mol/l, 0.3mol/l, 0.35mol/l, 0.4mol/l, 0.45mol/l or 0.5mol/l.
  • the ammonium salt is selected from ammonium salts other than ammonium chloride, and is selected from one or more of ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate and ammonium bisulfate.
  • the molar ratio of NH 4+ in the ammonia in the ammonia or ammonium salt to the Ru precursor is 6-30:1.
  • the molar ratio of NH in ammonia or ammonium salt to Ru precursor is 10-30:1, more specifically, the molar ratio can be 10:1, 15:1, 20 :1, 25:1 or 30:1.
  • the alkali metal alkali is selected from potassium hydroxide or sodium hydroxide; the alkali metal salt is selected from potassium salt or sodium salt, and the potassium salt is selected from potassium salts other than potassium chloride, and One or more of potassium nitrate, potassium sulfate, potassium carbonate and potassium bicarbonate, the sodium salt is selected from sodium salts other than sodium chloride, and can be selected from sodium nitrate, sodium sulfate, sodium carbonate, sodium bicarbonate and phosphoric acid One or more of sodium.
  • the molar ratio of the alkali metal alkali or alkali metal salt to the Ru precursor is 1-10:1, more specifically, the molar ratio can be 1:1, 2:1, 3 :1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.
  • the carrier in the carrier dispersion is selected from one or more of ⁇ -alumina, ⁇ -alumina, silicon dioxide and titanium dioxide; the solvent of the carrier dispersion is selected from water One or more of , methanol and ethanol; the concentration of the carrier dispersion is 1-100 mg/ml; the weight ratio of the carrier to the Ru precursor in the carrier dispersion is 10-1000:1.
  • R is a substituent on the benzene ring, which can be one substitution, two substitutions or three substitutions.
  • R substituents include but are not limited to: halogen-substituted organic groups, ester-substituted organic groups, oxoorganic groups , thia organic groups, carbonyl substituted organic groups.
  • the R group is an ester group substituted organic group
  • the general structural formula is -R 1 COOR 2 or -COOR 3 , wherein, the general structural formula of R 1 is -C n H 2n -, n is a positive integer, R 2 and R 3 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or isopentyl.
  • the aromatic compound is selected from one or more of dimethyl terephthalate, dimethyl isophthalate and dimethyl phthalate.
  • aromatic compound is dimethyl terephthalate, dimethyl isophthalate or dimethyl phthalate, each of them is hydrogenated and reduced to dimethyl 1,4-cyclohexanedicarboxylate, 1 , dimethyl 3-cyclohexanedicarboxylate and dimethyl 1,2-cyclohexanedicarboxylate.
  • the present invention processes the Ru precursor with ammonia or NH 4+ to form a complex loaded on the carrier, which can realize the strong adsorption between the carrier and Ru (elementary state or ionic state), and improve the Ru (elemental state or ionic state). ionic state) on the dispersion of the carrier;
  • the method of the present invention can also reduce the poisoning effect of chloride ions on the catalyst, so that the obtained catalyst can have higher catalytic activity;
  • the present invention uses alkali metal ions (derived from alkali metal alkalis or alkali metal salts) as auxiliary agents in the preparation method to play an anti-agglomeration effect on dispersed Ru, which can realize high stability of the catalyst, and Not deactivated by use;
  • the catalyst of the present invention has a good catalytic effect on the hydrogenation reduction of dimethyl terephthalate to dimethyl 1,4-cyclohexanedicarboxylate, high conversion rate, high selectivity, and repeated use
  • the number of times is more than 10 times.
  • Fig. 1 is the catalytic activity that catalyst A applies mechanically repeatedly in embodiment 1;
  • Fig. 2 is the XRD comparison before and after carrier loading in embodiment 2;
  • Fig. 3 is the TEM figure of catalyst B in embodiment 2;
  • Figure 4 is a TEM image of catalyst B in Example 2 after being reused 7 times.
  • catalyst A can be expressed as 0.202%Ru-0.138%Na + / ⁇ -Al 2 O 3 .
  • Catalytic performance test Take 0.5g of catalyst A, 0.5g of dimethyl terephthalate (DMT), the mass ratio Ru/DMT is approximately 1:500, and 15ml of ethyl acetate as a solvent.
  • Catalyst A, DMT and ethyl acetate are put into 50ml autoclave inner liner, replace the air in the reactor with nitrogen, pass into hydrogen, hydrogen pressure is kept at 3MPa, at different temperatures (80 °C, 100 °C, 120 °C, 150° C.) to carry out hydrogenation reaction until no hydrogen consumption was taken and gas chromatography was taken.
  • the reaction results are shown in Table 1.
  • temperature reflex Conversion rate/% selectivity/% 80°C 100 (DMT not detected) 98.5 100°C 100 (DMT not detected) 99.4 120°C 100 (DMT not detected) 99.8 150°C 100 (DMT not detected) 99.3
  • the catalyst B can be expressed as 1%Ru-1.15%Na + / ⁇ -Al 2 O 3 .
  • Catalyst C was tested according to the catalytic activity test method in Example 1, the reaction temperature was 120° C., the conversion rate of DMT was 100%, and the selectivity was 99.5%.
  • Catalyst D was tested according to the catalytic activity test method in Example 1, the reaction temperature was 120° C., the conversion rate of DMT was 100%, and the selectivity was 99.3%.
  • Catalyst E was tested according to the catalytic activity test method in Example 1, the reaction temperature was 120° C., the conversion rate of DMT was 100%, and the selectivity was 99.5%.
  • Example 6 KHCO 3 was replaced by KNO 3 , and the rest of the steps remained unchanged to obtain Ru-based catalyst G.
  • Ru-based catalyst H Take 2ml 0.1mol/l RuCl 3 solution, slowly drop 2ml 1mol/l ammonium sulfate solution into it, stir for 7 minutes after the dropwise addition; add 0.4ml 1mol/l sodium nitrate solution, slowly drop into the above carrier dispersion after stirring , continued to stir for 6 h after the dropwise addition, filtered with suction, washed twice with deionized water, and dried in a vacuum oven at 60°C for 6 h to obtain Ru-based catalyst H.
  • Example 8 sodium nitrate was replaced by NaOH, and the rest of the steps remained unchanged to obtain Ru-based catalyst I.
  • Example 6 ammonium nitrate was replaced by ammonium chloride, and the rest of the steps remained unchanged to obtain Ru-based catalyst N.
  • Example 6 KHCO3 was replaced by KCl, and the rest of the steps remained unchanged to obtain Ru-based catalyst O.
  • Example 2 According to the catalytic performance test method of Example 1, the Ru-based catalysts F to O of Examples 6-9 and Comparative Examples 1-6 were tested, and repeated tests were performed. The results are shown in Table 2.
  • the Ru-based catalyst of the present invention is due to the use of alkali metal alkalis such as sodium hydroxide and potassium hydroxide or non-sodium chloride, potassium salts of chlorinating agents, and alkali metal salts of sodium salts as The additive plays a better role in stabilizing Ru in a highly dispersed state, so even after repeated application, it can still maintain the highly dispersed state of Ru in the catalyst, thus maintaining a good catalytic activity.
  • alkali metal alkalis such as sodium hydroxide and potassium hydroxide or non-sodium chloride
  • potassium salts of chlorinating agents potassium salts of chlorinating agents
  • alkali metal salts of sodium salts alkali metal salts of sodium salts

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Abstract

本发明属于催化剂技术领域，涉及一种Ru基催化剂的制备方法及其应用。在Ru前驱体水溶液中加入氨水或铵盐，搅拌均匀，再加入碱金属碱或碱金属盐，搅拌均匀，滴加载体分散液，滴加完继续搅拌反应，抽滤、洗涤、干燥，即获得本发明的Ru基催化剂。本发明的Ru基催化剂对于催化对苯二甲酸二甲酯加氢还原为1,4-环己烷二甲酸二甲酯具有很高的转化率、选择性，可多次重复使用，而且催化剂的制备方法简单，可大规模化生产。

Description

一种Ru基催化剂的制备方法及其应用 技术领域
本发明属于催化剂技术领域，涉及一种Ru基催化剂的制备方法及其应用，尤其是涉及一种用于对苯二甲酸二甲酯加氢还原为1,4-环己烷二甲酸二甲酯的Ru基催化剂。
背景技术
1,4-环己烷二甲酸二甲酯(DMCD)是重要的有机化工原料，主要用于制备1,4-环己烷二甲醇(CHDM)。CHDM是工业上用于聚酯生产的重要有机单体，其合成的聚酯有着非常优良的性能，能广泛用于社会的各个方面。由对苯二甲酸二甲酯加氢还原是制备1,4-环己烷二甲酸二甲酯的重要方法，常用贵金属催化剂，比如Ru催化剂。而现在所用的贵金属催化剂存在转化率低、选择性差、重复使用性差等问题。
因此，有必要开发一种应用于催化对苯二甲酸二甲酯(DMT)加氢还原制备DMCD的催化剂，具有转化率高、选择性高、能多次重复使用的特点，而且基于现在环保的要求，要求制备方法简单、污染少等。
发明内容
本发明的一个目的是提供一种Ru基催化剂的制备方法，利用氨水或铵盐对Ru前驱体进行处理，再加入碱金属碱或碱金属盐作为助剂，实现在载体上高分散的Ru基催化剂。
本发明的另一个目的是提供一种Ru基催化剂的应用，应用于催化对苯二甲酸二甲酯的加氢还原，生成1,4-环己烷二甲酸二甲酯。
为了达到上述目的，本发明采用以下的技术方案，
一种Ru基催化剂的制备方法，按以下步骤进行，在Ru前驱体水溶液中加入氨水或铵盐，搅拌均匀，再加入碱金属碱或碱金属盐，搅拌均匀，滴加载体分散液，滴加完继续搅拌反应3-12小时，抽滤、洗涤、干燥，获得Ru基催化剂。
本发明的Ru基催化剂也可以按以下方法进行制备，在Ru前驱体水溶液中加入氨水或铵盐，搅拌均匀，滴加载体分散液，滴加完搅拌均匀，再加入碱金属碱或碱金属盐，搅拌反应3-12小时，抽滤、洗涤、干燥，获得Ru基催化剂。
本发明的上述制备方法中，洗涤可以用去离子水或醇水溶液(比如无水乙醇、去离子水按体积比5:5、6:4、7:3、8:2或9:1配制)；干燥的温度可以是40-80℃，可以是常压干燥，也可以是负压干燥。
在本发明优选的方案中，所述Ru前驱体选自三氯化钌、醋酸钌、硝酸钌和硫酸钌中的一 种或几种；所述Ru前驱体水溶液的浓度为0.01-1mol/l。在本发明更优选的方案中，Ru前驱体选自三氯化钌或醋酸钌，Ru前驱体水溶液的浓度为0.05-0.5mol/l，可以是0.05mol/l、0.1mol/l、0.15mol/l、0.2mol/l、0.25mol/l、0.3mol/l、0.35mol/l、0.4mol/l、0.45mol/l或0.5mol/l。
在本发明优选的方案中，所述铵盐选自非氯化铵的铵盐，选自硝酸铵、硫酸铵、碳酸铵、碳酸氢铵和硫酸氢铵中的一种或几种。
在本发明优选的方案中，所述氨水中氨或铵盐中NH 4+与所述Ru前驱体的摩尔比为6-30:1。在本发明更优选的方案中，氨水中氨或铵盐中NH 4+与Ru前驱体的摩尔比为10-30:1，更具体的，摩尔比可以是10:1、15:1、20:1、25:1或30:1。
在本发明优选的方案中，所述碱金属碱选自氢氧化钾或氢氧化钠；所述碱金属盐选自钾盐或钠盐，钾盐选自非氯化钾的钾盐，可以选自硝酸钾、硫酸钾、碳酸钾和碳酸氢钾中的一种或几种，钠盐选自非氯化钠的钠盐，可以选自硝酸钠、硫酸钠、碳酸钠、碳酸氢钠和磷酸钠中的一种或几种。
在本发明优选的方案中，所述碱金属碱或碱金属盐与所述Ru前驱体的摩尔比为1-10:1，更具体的，摩尔比可以是1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1或10:1。
在本发明优选的方案中，所述载体分散液中载体选自α-氧化铝、γ-氧化铝、二氧化硅和二氧化钛中的一种或几种；所述载体分散液的溶剂选自水、甲醇和乙醇中的一种或几种；所述载体分散液的浓度为1-100mg/ml；所述载体分散液中载体与所述Ru前驱体的重量比为10-1000:1。
一种上述任一实施方案所述的制备方法获得的催化剂的应用，应用于芳香族化合物中苯环的加氢还原。
本发明中，芳香族化合物的结构通式如式(1)所示，
Figure PCTCN2021132714-appb-000001
其中，R为苯环上的取代基，可以是一个取代、两个取代或三个取代，R取代基包括但不限于：卤素取代有机基团、酯基取代有机基团、氧杂有机基团、硫杂有机基团、羰基取代有机基团。在本发明更优选的方案中，R基团为酯基取代有机基团，结构通式为-R 1COOR 2或-COOR 3，其中，R 1的结构通式为-C nH 2n-，n为正整数，R 2、R 3各自独自的选自甲基、乙基、丙基、异丙基、正丁基、异丁基或异戊基。在本发明进一步优选的方案中，芳香族化合物选自对苯二甲酸二甲酯、间苯二甲酸二甲酯和邻苯二甲酸二甲酯中的一种或几种。
上述芳香族化合物加氢还原后的结构通式如式(2)所示，
Figure PCTCN2021132714-appb-000002
如果上述芳香族化合物为对苯二甲酸二甲酯、间苯二甲酸二甲酯或邻苯二甲酸二甲酯，则各自加氢还原为1,4-环己烷二甲酸二甲酯、1,3-环己烷二甲酸二甲酯和1,2-环己烷二甲酸二甲酯。
本发明的有益效果：
(1)本发明用氨水或NH 4+对Ru前驱体进行处理，形成络合物负载在载体上，能实现载体与Ru(单质状态或离子状态)的强吸附作用，提高Ru(单质状态或离子状态)在载体上的分散性；
(2)如果Ru前驱体为三氯化钌，本发明的方法还可以减少氯离子对催化剂的毒化作用，使得获得的催化剂能有较高的催化活性；
(3)本发明在制备方法中用碱金属离子(来源于碱金属碱或碱金属盐)作为助剂，起到对已分散的Ru的抗团聚作用，能实现催化剂的高稳定性，多次使用不失活；
(4)本发明的制备过程简单、成本较低，能实现大规模的工业化生产；
(5)本发明的催化剂对对苯二甲酸二甲酯加氢还原为1,4-环己烷二甲酸二甲酯的反应具有较好的催化效果，转化率高、选择性高、重复使用次数达10次以上。
附图说明
图1为实施例1中催化剂A多次套用的催化活性；
图2为实施例2中载体负载前后的XRD对比；
图3为实施例2中催化剂B的TEM图；
图4为实施例2中催化剂B重复使用7次后的TEM图。
具体实施方式
以下藉由特定的具体实施例说明本发明的实施方式，熟悉此技艺的人士可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。
须知，本说明书所附图式所绘示的结构、比例、大小等，均仅用以配合说明书所揭示的内容，以供熟悉此技艺的人士的了解与阅读，并非用以限定本发明可实施的限定条件，故不具技术上的实质意义，任何结构的修饰、比例关系的改变或大小的调整，在不影响本发明所能产生 的功效及所能达成的目的下，均应落在本发明所揭示的技术内容得能涵盖的范围内。同时，本说明书中所引用的如「上」、「内」、「外」、「底」、「一」、「中」等用语，也仅为便于叙述的明了，而非用以限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容下，当也视为本发明可实施的范畴，事先予以叙明。
实施例1
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l RuCl 3溶液，向里面缓慢滴加2.5ml 1mol/l碳酸铵溶液，滴加完再搅拌10分钟；加入0.3ml 1mol/l碳酸钠溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥8h，得Ru基催化剂A。根据上述各原料的重量比，催化剂A可表示为0.202％Ru-0.138％Na +/γ-Al 2O 3。
催化性能测试。取0.5g催化剂A，对苯二甲酸二甲酯(DMT)0.5g，质量比Ru/DMT近似为1：500，15ml乙酸乙酯作溶剂。催化剂A、DMT和乙酸乙酯放入50ml高压反应釜内衬中，用氮气置换反应釜里的空气，通入氢气，氢气压力保持在3MPa，在不同温度(80℃、100℃、120℃、150℃)下进行加氢反应，直到不耗氢取样打气相色谱，反应结果如表1所示。
表1催化反应测试结果
反应温度 转化率/％ 选择性/％
80℃ 100(未检测到DMT) 98.5
100℃ 100(未检测到DMT) 99.4
120℃ 100(未检测到DMT) 99.8
150℃ 100(未检测到DMT) 99.3
选择上述120℃的反应，反应结束后产物离心过滤，收取催化剂A，70℃真空干燥后按上述催化性能测试方法继续进行催化反应(由于离心过滤会损失少量的催化剂A，因此需要进行补充)，反应温度为120℃。结果如附图1所示。可以看出，实施例1中的催化剂A重复使用了10次，转化率仍然为100％，选择性(即附图1中的产率)也是维持非常高的水平，而且不随着重复使用而有明显的下降，仍然保持较为良好的催化活性。
实施例2
取1gγ-Al 2O 3分散在30ml超纯水中，获得载体分散液；
取1ml 0.1mol/l RuCl 3溶液，向里面缓慢滴加1.5ml 1mol/l碳酸铵溶液，滴加完搅拌10分钟，再加入0.25ml 1mol/l碳酸钠溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌5h， 抽滤、洗涤，放入60℃真空干燥箱中干燥8h，获得Ru基催化剂B。根据上述各原料的重量比，催化剂B可表示为1％Ru-1.15％Na +/γ-Al 2O 3。
分别采用XRD测试γ-Al 2O 3载体和催化剂B，结果如附图2所示，其中Ru/Al 2O 3代表催化剂B。可以看出，即使催化剂B中Ru的负载量较高，γ-Al 2O 3载体和催化剂B的特征峰基本上完全一样，并未检测出Ru的特征峰。
催化剂B的TEM图如附图3所示，可以看出基本上观察不到Ru的金属颗粒。
因此，上述附图2和附图3证明了本发明的催化剂中，Ru在载体上的分散度高。
附图4是催化剂B重复使用7次后的TEM图，可以看出仍然维持着很高的分散性，团聚现象少。因此，本发明的催化剂能多次重复使用。
实施例3
取10gα-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加5ml 1mol/l氨水，滴加完再搅拌10分钟；加入1ml 1mol/l碳酸氢钠溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥7h，得Ru基催化剂C。
催化剂C按照实施例1中的催化活性测试方法进行测试，反应温度为120℃，DMT的转化率为100％，选择性为99.5％。
实施例4
取10g二氧化硅载体分散在300ml超纯水中，获得载体分散液；
取1ml 0.2mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l硝酸铵溶液，滴加完再搅拌10分钟；加入0.4ml 1mol/l NaOH溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入70℃真空干燥箱中干燥5h，得Ru基催化剂D。
催化剂D按照实施例1中的催化活性测试方法进行测试，反应温度为120℃，DMT的转化率为100％，选择性为99.3％。
实施例5
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l氨水，滴加完再搅拌10分钟；加入0.8ml 1mol/l NaOH溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入70℃真空干燥箱中干燥8h，得Ru基催化剂E。
催化剂E按照实施例1中的催化活性测试方法进行测试，反应温度为120℃，DMT的转化率为100％，选择性为99.5％。
实施例6
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l硝酸铵溶液，滴加完再搅拌7分钟；加入0.6ml 1mol/l KHCO 3溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌4h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥6h，得Ru基催化剂F。
实施例7
实施例6中KHCO 3替换为KNO 3，其余步骤保持不变，获得Ru基催化剂G。
实施例8
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l RuCl 3溶液，向里面缓慢滴加2ml 1mol/l硫酸铵溶液，滴加完再搅拌7分钟；加入0.4ml 1mol/l硝酸钠溶液，搅拌后缓慢滴入上述载体分散液，滴加完继续搅拌6h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥6h，得Ru基催化剂H。
实施例9
实施例8中硝酸钠替换为NaOH，其余步骤保持不变，获得Ru基催化剂I。
对比例1
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l氨水，滴加完搅拌10分钟，缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥6h，得Ru基催化剂J。
对比例2
对比例1中氨水从4ml替换为6ml，其余步骤保持不变，获得Ru基催化剂K。
对比例3
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l氨水，滴加完搅拌10分钟，缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入60℃真空干燥箱中干燥6h，再置于220℃下加热3小时，得Ru基催化剂L。
对比例4
取10gγ-氧化铝分散在300ml超纯水中，获得载体分散液；
取2ml 0.1mol/l醋酸钌溶液，向里面缓慢滴加4ml 1mol/l硝酸铵，滴加完搅拌10分钟，缓慢滴入上述载体分散液，滴加完继续搅拌5h，抽滤、去离子水洗涤2次，放入60℃真空干 燥箱中干燥6h，再置于220℃下加热3小时，得Ru基催化剂M。
对比例5
实施例6中硝酸铵替换为氯化铵，其余步骤保持不变，获得Ru基催化剂N。
对比例6
实施例6中KHCO 3替换为KCl，其余步骤保持不变，获得Ru基催化剂O。
按照实施例1的催化性能测试方法，对实施例6-9和对比例1-6的Ru基催化剂F～O进行测试，并进行重复套用测试，结果如表2所示。
表2实施例6-9和对比例1-6的Ru基催化剂F～M性能测试结果
Figure PCTCN2021132714-appb-000003
Figure PCTCN2021132714-appb-000004
由表2的结果可以看出，本发明的Ru基催化剂由于采用了氢氧化钠、氢氧化钾等碱金属碱或者非氯化钠、氯化剂等的钾盐、钠盐的碱金属盐作为助剂，起到了较好的稳定高分散状态的Ru的作用，因此即使多次套用后仍能维持催化剂中Ru的高分散状态，因此维持较好的催化活性。

Claims (10)

  1. 一种Ru基催化剂的制备方法，其特征在于，按以下步骤进行，在Ru前驱体水溶液中加入氨水或铵盐，搅拌均匀，再加入碱金属碱或碱金属盐，搅拌均匀，滴加载体分散液，滴加完继续搅拌反应3-12小时，抽滤、洗涤、干燥，获得所述Ru基催化剂。
  2. 一种Ru基催化剂的制备方法，其特征在于，按以下步骤进行，在Ru前驱体水溶液中加入氨水或铵盐，搅拌均匀，滴加载体分散液，滴加完搅拌均匀，再加入碱金属碱或碱金属盐，搅拌反应3-12小时，抽滤、洗涤、干燥，获得所述Ru基催化剂。
  3. 根据权利要求1或2所述的制备方法，所述Ru前驱体选自三氯化钌、醋酸钌、硝酸钌和硫酸钌中的一种或几种；所述Ru前驱体水溶液的浓度为0.01-1mol/l。
  4. 根据权利要求1或2所述的制备方法，所述铵盐选自硝酸铵、硫酸铵、碳酸铵、碳酸氢铵和硫酸氢铵中的一种或几种。
  5. 根据权利要求1或2所述的制备方法，所述氨水中氨或铵盐中NH 4+与所述Ru前驱体的摩尔比为6-30:1。
  6. 根据权利要求1或2所述的制备方法，所述碱金属碱选自氢氧化钾或氢氧化钠；所述碱金属盐选自硝酸钾、硫酸钾、碳酸钾、碳酸氢钾、硝酸钠、硫酸钠、碳酸钠、碳酸氢钠和磷酸钠中的一种或几种。
  7. 根据权利要求1或2所述的制备方法，所述碱金属碱或碱金属盐与所述Ru前驱体的摩尔比为1-10:1。
  8. 根据权利要求1或2所述的制备方法，所述载体分散液中载体选自α-氧化铝、γ-氧化铝、二氧化硅和二氧化钛中的一种或几种；所述载体分散液的溶剂选自水、甲醇和乙醇中的一种或几种；所述载体分散液的浓度为1-100mg/ml；所述载体分散液中载体与所述Ru前驱体的重量比为10-1000:1。
  9. 一种权利要求1-8任一项所述的制备方法获得的Ru基催化剂的应用，其特征在于，应用于芳香族化合物中苯环的加氢还原。
  10. 根据权利要求9所述的应用，所述芳香族化合物选自对苯二甲酸二甲酯、间苯二甲酸二甲酯和邻苯二甲酸二甲酯中的一种或几种。
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