WO2020107539A1 - 一种生产甲基丙烯酸甲酯的催化剂的制备方法及其应用 - Google Patents

一种生产甲基丙烯酸甲酯的催化剂的制备方法及其应用 Download PDF

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WO2020107539A1
WO2020107539A1 PCT/CN2018/120758 CN2018120758W WO2020107539A1 WO 2020107539 A1 WO2020107539 A1 WO 2020107539A1 CN 2018120758 W CN2018120758 W CN 2018120758W WO 2020107539 A1 WO2020107539 A1 WO 2020107539A1
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catalyst
methyl methacrylate
gold
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metal
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黄家辉
吕强
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
    • 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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a catalyst for producing methyl methacrylate.
  • Methyl methacrylate is an important organic chemical raw material. It is a colorless and transparent liquid with ether flavor at room temperature.
  • MMA was mainly produced by the acetone cyanohydrin method in industry.
  • the one-step preparation of MMA by methacrolein is a green process route with great development potential, because there is no methacrylic acid formation in the middle, and there is no subsequent esterification process of methacrylic acid and methanol, which will greatly save production costs.
  • the by-product of the process is water, which is green and environmentally friendly.
  • the difficulty of this process lies in the preparation of the catalyst. Therefore, many efforts have been made to solve this problem.
  • the core-shell nanogold catalyst (Au@NiOx) can efficiently catalyze the co-oxidation of methacrolein and methanol to produce MMA.
  • the process is simple and the catalyst shows excellent stability.
  • the catalyst preparation technology requires high, and when the conversion rate of methacrolein is 65%, the selectivity of MMA is about 95%, and in actual application process, it is often necessary to ensure high activity (usually based on high conversion rate) At the same time, it can maintain a high selectivity of the target product; in addition, the cost of the catalyst is also high, the cost is about 6 million/ton, which will also limit its industrial application to a certain extent.
  • Chinese Patent Publication No. CN107107034A discloses a gold-based catalyst for the oxidative esterification of aldehydes to obtain carboxylic acid esters, with gold as the active component, and silicon, aluminum and other elements in the oxidized state as carriers, and other elements are selected from Alkali metal, alkaline earth metal, rare earth metal, Ti, Zr, Cu, Mn, Pb, Sn or Bi, form a particle form of the catalyst, the catalyst can be used for a long time to oxidize aldehyde to carboxylic acid ester, especially in the water And mixtures containing carboxylic acid.
  • this catalyst catalyzes the conversion of methacrolein to MMA, the catalytic conditions are harsh, and the conversion rate of methacrolein and the selectivity of MMA are not ideal, especially in the industrial expansion test, the selectivity to MMA is not high, affecting product quality.
  • the present invention provides a preparation method and application of a catalyst for producing methyl methacrylate.
  • the catalyst preparation process is simple, the operation is convenient, has excellent activity and good stability, and the choice of MMA High performance, suitable for industrial production.
  • the catalyst includes a carrier and an active center supported on the carrier; the active center includes gold, transition metal, and lanthanide metal; and the carrier includes SiO 2 , Al 2 O 3 and alkali metals or alkaline earth metals; in the catalyst, the loading of gold is 0.05wt%-0.98wt%, the loading of lanthanide metal is 1wt%-2.5wt%, the transition metal The loading is 1wt%-2.5wt%.
  • the alkali metal or alkaline earth metal is Na, K, Rb, Cs, Be, Mg, Ca, Sr;
  • the lanthanide metal is one of La, Ce, Pr, Nd,
  • the transition metal is one of Cu, Co, Fe, Mn, and Cr.
  • the mass fraction of alkali metal and alkaline earth metal ranges from 1 to 25%; the molar ratio of alkali metal or alkaline earth metal to SiO 2 in the carrier is 1 to 6: 0.5 ⁇ 4.
  • Another aspect of the present invention provides a method for preparing the above-mentioned catalyst for producing methyl methacrylate, which is special in that: the catalyst is prepared by a polymer protection method, and the precursor of gold and the reducing agent are removed under stirring conditions. Ion water is fully mixed to obtain a stable, uniform and high-dispersed gold sol. In the presence of a polymer protective agent, the lanthanide metal precursor and the transition metal precursor are added to the gold sol in sequence, and then the carrier is added , Slowly raise the temperature to 65-85°C and continue to stir for 2-20h. After stirring, return to room temperature, let stand and filter, wash with deionized water until no chloride ion can be detected, dry it and roast in air to obtain the catalyst
  • the preparation process of the carrier is: adding an alumina precursor, an alkali metal or an alkaline earth metal precursor to the silica precursor solution under stirring conditions, and after fully stirring and mixing, adding an acid Adjust the PH value to 0.5-5.5, and continue to stir for 1-24h to obtain a mixture.
  • the mixture is spray-dried to form spherical particles with a particle size of 50-100 ⁇ m, and the carrier is obtained by calcination under an air atmosphere.
  • the precursor of Au is gold cyanide (Au(CN) 3 ), potassium gold cyanide, gold chloride (AuC1), gold chloride (AuC1 3 ), gold chloride One or more of acid, chloroaurate, sodium gold sulfite or thunder gold.
  • the polymer protective agent is polyvinyl alcohol, polyvinylpyrrolidone, tetramethylolphosphonium chloride, polydimethyldipropylene ammonium chloride, sodium citrate, and thiol.
  • the reducing agent is sodium citrate, tetramethylolphosphonium chloride, oxalic acid, and sodium borohydride.
  • the lanthanide metal precursor and the transition metal precursor are sulfates, nitrates, phosphates, carbonates, and acetates of corresponding metals.
  • the amount of lanthanide metal precursor, transition metal precursor, gold precursor, reducing agent, polymer protective agent and carrier added is: lanthanide metal element: transition metal element : Gold element: reducing agent: polymer protective agent: carrier: water mass ratio is 1: (0.4-2.5): (0.02-0.98): (0.2-0.5): (0.2-0.5): (50-200) : (200-400).
  • the alumina precursor is added to the silica precursor solution and dissolved.
  • the precursor of the alkali metal or alkaline earth metal is a simple substance, oxide, hydroxide, other compound or composite of the corresponding metal
  • the precursor of the silica is a silica sol, solid state One of silica gel and white carbon black
  • the precursor of alumina is one of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum carbonate, or alumina powder.
  • the acid is one of nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid.
  • the present invention provides a method for producing methyl methacrylate, which uses the above-mentioned catalyst to synthesize methyl methacrylate by a one-step oxidation method using methacrolein and methanol as reaction raw materials.
  • the synthesis method of methyl methacrylate is as follows: the reaction raw material A is added to the reactor to be fully mixed, and then the catalyst is added to the reactor; the reactor is sealed, stirring is started, and the bottom of the reactor is Air and inert gas are fed at the rate of 0.8-1.3L/min and 2.5-3.2L/min, and the reaction raw materials are added to the reaction kettle at a rate of 8-12ml/min using a liquid constant flow sampling pump.
  • the same rate as the reaction material feed rate is stored in the storage tank; the mass concentration of methanol in the reaction mixture is 50-70%, the reaction raw material and the catalyst constitute a reaction system; the mass concentration of the catalyst in the reaction system 15-20%; the reaction index obtained after the reaction is carried out for 150-200h is: the conversion rate of methacrolein ⁇ 97%, and the selectivity of methyl methacrylate ⁇ 98%.
  • the present invention adopts the polymer protection method, and the active center Au obtained has a small and uniform particle size, high activity, and excellent stability.
  • the method for preparing the supported catalyst does not have high requirements on the carrier, and can be used in a range wide.
  • a supported catalyst having a trimetallic active center is composed of a lanthanide metal, a transition metal, and gold.
  • the lanthanide and transition metal in the catalyst exist in elemental form and cooperate with Au to catalyze, so that the selectivity and conversion rate of the catalyst high.
  • the load of Au is low, which greatly reduces the cost of the catalyst.
  • the preparation process is easy to operate.
  • the catalyst is applied to the preparation of methyl methacrylate.
  • the conversion rate of methacrolein is greater than 97% when running on a small evaluation device for 4000h.
  • a The selectivity of methyl acrylate is greater than 97%.
  • the active sites Au, lanthanides and transition metals on the catalyst are still stable without loss.
  • Figure 1 is an electron micrograph of the catalyst prepared in Example 2.
  • the lower precipitate was washed with deionized water until no chloride ion was detected in the solution. After drying at 100°C for 24h, it was calcined in air at 300°C for 24h to obtain the catalyst Cu-La- Au/SiO 2 -Al 2 O 3 -MgO.
  • the mass percentages of La, Ce, and Au in the catalyst are 1%, 1%, and 0.48%, respectively.
  • the carrier molding conditions are the same as Comparative Example 1, in which magnesium nitrate is replaced with rubidium nitrate to obtain a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m, which is then calcined at 700°C in an air atmosphere for 6 hours and cooled to room temperature Later to spare.
  • the catalyst preparation conditions are the same as in Example 1, and the catalyst Cu-La-Au/SiO 2 -Al 2 O 3 -RbO is obtained, in which the mass percentages of La, Ce, and Au in the catalyst are 1%, 1%, and 0.48%, respectively .
  • the electron micrograph of the catalyst prepared in this example it can be seen that the particles of Au are uniform and highly dispersed on the surface of the carrier, and the particle size is 2nm; the particles of La and Ce are slightly larger than Au, but uniformly distributed, The particle size is around 4 nm.
  • the carrier molding conditions are the same as Comparative Example 1, in which magnesium nitrate is replaced with cesium nitrate to obtain spherical SiO 2 -Al 2 O 3 -CsO powder with a particle size of about 70 ⁇ m, and then the powder is calcined in an air atmosphere at 700° C. for 6 hours and cooled to room temperature. Later to spare.
  • the catalyst preparation conditions were the same as in Example 1, and the catalyst Cu-La-Au/SiO 2 -Al 2 O 3 -CsO was obtained, in which the mass percentages of Cu, La, and Au in the catalyst were 1%, 1%, and 0.48%, respectively. .
  • the carrier molding conditions are the same as in Comparative Example 1, in which magnesium nitrate is replaced with strontium nitrate to obtain spherical SiO 2 -Al 2 O 3 -SrO powder with a particle size of about 70 ⁇ m, and then the powder is calcined in an air atmosphere at 700° C. for 6 h and cooled to room temperature Later to spare.
  • the catalyst preparation conditions were the same as in Example 1, and the catalyst Cu-La-Au/SiO 2 -Al 2 O 3 -SrO was obtained, in which the mass percentages of La, Ce, and Au in the catalyst were 1%, 1%, and 0.48%, respectively. .
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions are the same as in Example 2, in which copper nitrate is replaced with cobalt nitrate to obtain the catalyst Co-La-Au/SiO 2 -Al 2 O 3 -RbO, wherein the mass percentages of Co, La and Au in the catalyst are: 1%, 1%, 0.48%.
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions are the same as in Example 2, in which copper nitrate is replaced with chromium nitrate to obtain the catalyst Cr-La-Au/SiO 2 -Al 2 O 3 -RbO, in which the mass percentages of Cr, La and Au in the catalyst are: 1%, 1%, 0.48%.
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions are the same as in Example 2, in which copper nitrate is replaced with manganese nitrate to obtain the catalyst Mn-La-Au/SiO 2 -Al 2 O 3 -RbO, in which the mass percentages of Mn, La and Au in the catalyst are: 1%, 1%, 0.48%.
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions are the same as in Example 2, in which lanthanum nitrate is replaced with praseodymium nitrate to obtain the catalyst Cu-Ce-Au/SiO 2 -Al 2 O 3 -RbO, in which the mass percentages of Cu, Ce and Au in the catalyst are: 1%, 1%, 0.48%.
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions were the same as in Example 2, in which lanthanum nitrate was replaced with neodymium nitrate to obtain the catalyst Cu-Nd-Au/SiO 2 -Al 2 O 3 -RbO, in which the mass percentages of Cu, Nd and Au in the catalyst were: 1%, 1%, 0.48%.
  • the carrier molding conditions were the same as in Example 2.
  • a spherical SiO 2 -Al 2 O 3 -RbO powder with a particle size of about 70 ⁇ m was obtained, and then the powder was fired at 700° C. in an air atmosphere for 6 hours, and then lowered to room temperature for use.
  • the catalyst preparation conditions are the same as in Example 2, in which lanthanum nitrate is replaced with praseodymium nitrate to obtain the catalyst Cu-Pr-Au/SiO 2 -Al 2 O 3 -RbO, in which the mass percentages of Cu, Pr and Au in the catalyst are: 1%, 1%, 0.48%.
  • the lower precipitate was washed with deionized water until no chloride ion was detected in the solution. After drying at 100°C for 24h, it was calcined in air at 300°C for 24h to obtain the catalyst Cu-La- Au/SiO 2 -Al 2 O 3 -MgO.
  • the mass percentages of La, Ce, and Au in the catalyst are 1%, 1%, and 1.4%, respectively.
  • the catalysts of Comparative Examples and Examples 1-10 were applied to the synthesis of methyl methacrylate under the same conditions.
  • the reaction conditions were:
  • Examples 11 and 12 are as follows: From the table, it can be seen that the addition of transition metals and lanthanide metals improves the activity of the catalyst, and the conversion and selectivity of the reaction are both improved; after increasing the loading of Au, the catalysis of the catalyst Performance is reduced.

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Abstract

一种生产甲基丙烯酸甲酯的催化剂及其制备方法和应用，该催化剂包括载体和负载在载体上的活性中心；所述活性中心包括金、过渡金属和镧系金属；所述载体包括SiO 2、Al 2O 3和碱金属或碱土金属中一种；金的负载量为0.05wt％-0.98wt％，镧系金属的负载量为1wt％-2.5wt％，过渡金属的负载量为1wt％-2.5wt％。制备方法采用高分子保护法，将金的前驱体与还原剂和去离子水充分混合得到金溶胶，依次加入镧系金属和过渡金属，然后加入载体，继续搅拌2-20h并缓慢升温至65-85℃，搅拌结束后降至室温，经静置过滤、洗涤、烘干、焙烧得到催化剂。该催化剂应用在生产甲基丙烯酸甲酯的反应中，具有优异的活性和稳定性而且催化剂价格低廉，甲基丙烯醛的转化率和MMA的选择性高，适合工业化生产。

Description

一种生产甲基丙烯酸甲酯的催化剂的制备方法及其应用 技术领域
本发明属于催化剂制备技术领域，具体涉及一种生产甲基丙烯酸甲酯的催化剂的制备方法及其应用。
背景技术
甲基丙烯酸甲酯(methyl methacrylate，MMA)是一种重要的有机化工原料，常温下为无色透明、带有醚类香味的液体，过去工业上MMA主要采用丙酮氰醇法进行生产，近年来，甲基丙烯醛一步法制备MMA是一种极有发展潜力的绿色工艺路线，因为中间没有甲基丙烯酸的生成，也没有后续的甲基丙酸和甲醇的酯化过程，会大大节约生产成本，同时该过程副产物是水，绿色环保。但是该工艺的难点在于催化剂的制备，因此，人们付出诸多努力试图解决这一难题。比如日本旭化成开发了异丁烯氧化为甲基丙烯醛，甲基丙烯醛在Pd-Pb催化剂作用下再与甲醇氧化酯化制备MMA。该工艺不涉及腐蚀性较强的甲基丙烯酸，对反应设备要求不高。此外，该工艺非常简单，只需两步反应。副产物只有水，绿色环保。相比原来的MMA制备工艺，该工艺所需原料费用较低，产品纯度高，设备紧凑，建设费用明显降低，但对催化剂的设计、制备要求很高。第一代的Pd-Pb催化剂对MMA的选择性不高，约为84％，将会增大后续分离成本并影响产品的质量。
随后，日本旭化成在后续研究中发现核壳结构的纳米金催化剂(Au@NiOx)能够高效催化甲基丙烯醛和甲醇共氧化制MMA，该工艺过程简单、并且催化剂表现出了优异的稳定性。但是该催化剂制备技术要求高，并且在甲基丙烯醛转化率为65％时，MMA的选择性为95％左右，而在实际应用过程中往往需要保证高活性(通常是以高转化率计)的同时，又能够保持高的目标产物的选择性；另外该催化剂成本也较高，成本约为600万/吨，这也会在一定程度限制其工业化应用。
中国专利公开号CN107107034A公开了一种用于将醛氧化酯化以获得羧酸酯的金基催化剂，以金作为活性组分，以氧化态的硅、铝和其他元素作为载体，其他元素选自碱金属、碱土金属、稀土金属、Ti、Zr、Cu、Mn、Pb、Sn或Bi，形成粒子形式的催化剂，该催化剂能够长时间内用于将醛氧化酯化成羧酸酯，尤其在含有水和含有羧酸的混合物中。但是，该催化剂催化甲基丙烯醛转化成MMA反应中，催化条件苛刻，且甲基丙烯醛的转化率和MMA的选择性不够理想，尤其在工业化扩大试验中对MMA的选择性不高，影响产品质量。
发明内容
为弥补现有技术的不足，本发明提供一种生产甲基丙烯酸甲酯的催化剂的制备方法及其应用，催化剂制备过程简单、操作方便、具有优异的活性和很好的稳定性，MMA的选择性高，适合工业化生产。
本发明是通过如下技术方案实现的：
本发明一方面提供一种生产甲基丙烯酸甲酯的催化剂，所述催化剂包括载体和负载在载体上的活性中心；所述活性中心包括金、过渡金属和镧系金属；所述载体包括SiO 2、Al 2O 3和碱金属或碱土金属中一种；所述催化剂中，金的负载量为0.05wt％-0.98wt％，镧系金属的负载量为1wt％-2.5wt％，过渡金属的负载量为1wt％-2.5wt％。
基于以上技术方案，优选的，所述碱金属或碱土金属为Na、K、Rb、Cs、Be、Mg、Ca、Sr；所述镧系金属为La、Ce、Pr、Nd中的一种，所述过渡金属为Cu、Co、Fe、Mn、Cr中的一种。
基于以上技术方案，优选的，以载体质量为100％计，碱金属与碱土金属的质量分数范围1-25％；所述载体中碱金属或碱土金属与SiO 2的摩尔比为1～6:0.5～4。
本发明再一方面提供一种上述生产甲基丙烯酸甲酯的催化剂的制备方法，其特殊之处在于：采用高分子保护法制备催化剂，在搅拌条件下，将金的前驱体与还原剂与去离子水充分混合，得到稳定、均匀单一并具较高分散状态的金溶胶，在高分子保护剂存在的条件下，依次向金溶胶中加入镧系金属前驱体和过渡金属前驱体，然后加入载体，缓慢升温至65-85℃继续搅拌2-20h，搅拌结束后降至室温，静置过滤，用去离子水洗涤至检测不到氯离子，烘干后于空气中焙烧得到所述催化剂
基于以上技术方案，优选的，所述载体制备过程为：在搅拌条件下，向二氧化硅前驱体溶液中加入氧化铝前驱体、碱金属或碱土金属的前体，充分搅拌混合后，加入酸调节PH值至0.5-5.5，继续搅拌1-24h后得到混合物，将所述混合物进行喷雾干燥成型，得到颗粒尺寸为50-100μm的球状颗粒物，在空气气氛下焙烧得到所述载体。
基于以上技术方案，优选的，所述Au的前躯体为氰化金(Au(CN) 3)、氰化亚金钾、氯化亚金(AuC1)、氯化金(AuC1 3)、氯金酸、氯金酸盐、亚硫酸金钠或雷金中的一种或两种以上。
基于以上技术方案，优选的，所述高分子保护剂为聚乙烯醇、聚乙烯吡咯烷酮、四羟甲基氯化磷、聚二甲基二丙烯氯化铵、柠檬酸钠、硫醇类物质。
基于以上技术方案，优选的，所述还原剂为柠檬酸钠、四羟甲基氯化磷、草酸和硼氢化钠。
基于以上技术方案，优选的，所述镧系金属前驱体和过渡金属前驱体为相应金属的硫酸盐、硝酸盐、磷酸盐、碳酸盐、醋酸盐。
基于以上技术方案，优选的，所述方法中，镧系金属前驱体、过渡金属前驱体、金前驱体、还原剂、高分子保护剂和载体的加入量为：镧系金属元素：过渡金属元素：金元素：还原剂：高分子保护剂：载体：水的质量比为1：(0.4-2.5)：(0.02-0.98)：(0.2-0.5)：(0.2-0.5)：(50-200)：(200-400)。
基于以上技术方案，优选的，在向二氧化硅前驱体溶液中加入碱金属或碱土金属之前，先向二氧化硅前驱体溶液中加入氧化铝的前驱体并溶解。
基于以上技术方案，优选的，所述碱金属或碱土金属的前驱体为相应金属的单质、氧化物、氢氧化物、其他化合物或复合物；所述二氧化硅的前驱体为硅溶胶、固态硅胶和白炭黑中的一种；所述氧化铝的前驱体为硝酸铝、硫酸铝、磷酸铝、碳酸铝或者氧化铝粉末中的一种。
基于以上技术方案，优选的，所述酸为硝酸、硫酸、盐酸、磷酸中的一种。
本发明再一方面提供一种生产甲基丙烯酸甲酯的方法，采用上述的催化剂以甲基丙烯醛和甲醇为反应原料，通过一步氧化法催化合成甲基丙烯酸甲酯。
基于以上技术方案，优选的，甲基丙烯酸甲酯的合成方法为：将反应原料甲加入反应器中充分混合，然后向反应器中加入催化剂；密封反应器，开启搅拌，在反应器底部分别以0.8-1.3L/min和2.5-3.2L/min的速率通入空气和惰性气体，采用液体恒流进样泵以8-12ml/min的速率向反应釜中加入反应原料，反应后的产物以与反应原料进去速率相同的速度存储在储料罐中；所述反应混合物中甲醇的质量浓度为50-70％，所述反应原料与催化剂组成反应体系；所述催化剂在反应体系中的质量浓度为15-20％；所述反应进行150-200h后得到的反应指标为：甲基丙烯醛的转化率≥97％，甲基丙烯酸甲酯的选择性≥98％。
有益效果
本发明的有益效果是：本发明采用高分子保护法，制得的活性中心Au的粒度小且均一、活性高、稳定性优异，该方法制备负载型催化剂对载体的要求不高，可选用范围广。本发明通过镧系金属、过渡金属与金组成具有三金属活性中心的负载型催化剂，该催化剂中的镧系与过渡金属以单质形式存在、协同Au共同催化，使得催化剂的选择性 与转化率更高。Au的负载量低，大大降低催化剂的成本，制备过程操作方便，将该催化剂应用于甲基丙烯酸甲酯的制备，在小型评价装置上运行4000h时甲基丙烯醛的转化率大于97％，甲基丙烯酸甲酯的选择性大于97％，此时催化剂上的活性中心Au、镧系和过渡金属依然稳定存在没有流失。
附图说明
附图1是实施例2制备的催化剂的电镜图。
具体实施方式
下面结合具体实施方式对本发明作进一步详细的说明，以帮助本领域的技术人员对本发明的发明构思、技术方案有更完整、准确和深入的理解，本发明的保护范围包括但不限于以下实施例，在不偏离本申请的精神和范围的前提下任何对本发明的技术方案的细节和形式所做出的修改均落入本发明的保护范围内。
对比例1
称取50kg硅溶胶(30wt％)，搅拌过程中加入9kg硝酸铝，待溶解后加入7kg硝酸镁，加入250ml浓硝酸调节PH值，50℃下继续搅拌24h，降温至室温后进行喷雾干燥，喷雾条件为：10ml/min进料量，进口温度200-220℃，出口温度80-100℃，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-MgO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
在搅拌条件下，将250g氯金酸与250g柠檬酸钠与60L去离子水充分混合，得到稳定、均匀单一并具较高分散状态的金溶胶，在搅拌条件下加入260g聚乙烯吡咯烷酮(PVP，分子量8000-10000)，完全溶解后加入30kg上述制备的SiO 2-Al 2O 3-MgO粉末，继续搅拌并缓慢升温至75℃，该温度下继续搅拌14h后降至室温，静置后倾倒出上层液体，去离子水洗涤下层沉淀物直至溶液中检测不到氯离子，100℃烘干24h后再于300℃空气中焙烧24h得到催化剂Au/SiO 2-Al 2O 3-MgO。其中Au在催化剂中的质量百分含量为0.48％。
实施例1
载体的制备成型条件同对比例1。
在搅拌条件下，将250g氯金酸与250g柠檬酸钠与60L去离子水充分混合，得到稳定、均匀单一并具较高分散状态的金溶胶，在搅拌条件下加入260g聚乙烯吡咯烷酮(PVP，分子量8000-10000)，然后依次加入935g硝酸镧、1170g硝酸铜，完全溶解后加入30kg上述制备的SiO 2-Al 2O 3-MgO粉末，继续搅拌并缓慢升温至75℃，该温度下 继续搅拌14h后降至室温，静置后倾倒出上层液体，去离子水洗涤下层沉淀物直至溶液中检测不到氯离子，100℃烘干24h后再于300℃空气中焙烧24h得到催化剂Cu-La-Au/SiO 2-Al 2O 3-MgO。其中La、Ce、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例2
载体成型条件同对比例1，其中硝酸镁用硝酸铷替换，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例1，得到催化剂Cu-La-Au/SiO 2-Al 2O 3-RbO，其中La、Ce、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
如图1，为本实施例制备的催化剂的电镜图，从图中可以看出Au的颗粒均匀，高度分散于载体表面，颗粒尺寸为2nm；La与Ce的颗粒略大于Au，但均匀分布，颗粒尺寸为4nm左右。
实施例3
载体成型条件同对比例1，其中硝酸镁用硝酸铯替换，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-CsO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例1，得到催化剂Cu-La-Au/SiO 2-Al 2O 3-CsO，其中Cu、La、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例4
载体成型条件同对比例1，其中硝酸镁用硝酸锶替换，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-SrO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例1，得到催化剂Cu-La-Au/SiO 2-Al 2O 3-SrO，其中La、Ce、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例5
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸铜用硝酸钴替换，得到催化剂Co-La-Au/SiO 2-Al 2O 3-RbO，其中Co、La、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例6
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再 将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸铜用硝酸铬替换，得到催化剂Cr-La-Au/SiO 2-Al 2O 3-RbO，其中Cr、La、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例7
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸铜用硝酸锰替换，得到催化剂Mn-La-Au/SiO 2-Al 2O 3-RbO，其中Mn、La、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例8
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸镧用硝酸镨替换，得到催化剂Cu-Ce-Au/SiO 2-Al 2O 3-RbO，其中Cu、Ce、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例9
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸镧用硝酸钕替换，得到催化剂Cu-Nd-Au/SiO 2-Al 2O 3-RbO，其中Cu、Nd、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
实施例10
载体成型条件同实施例2，得到颗粒尺寸约70μm的球形SiO 2-Al 2O 3-RbO粉末，再将该粉末在700℃空气气氛下焙烧6h，降至室温后以备用。
催化剂制备条件同实施例2，其中硝酸镧用硝酸镨替换，得到催化剂Cu-Pr-Au/SiO 2-Al 2O 3-RbO，其中Cu、Pr、Au在催化剂中的质量百分含量分别为1％、1％、0.48％。
对比例2
在搅拌条件下，将750g氯金酸与750g柠檬酸钠与60L去离子水充分混合，得到 稳定、均匀单一并具较高分散状态的金溶胶，在搅拌条件下加入760g聚乙烯吡咯烷酮(PVP，分子量8000-10000)，然后依次加入935g硝酸镧、1170g硝酸铜，完全溶解后加入30kg上述制备的SiO 2-Al 2O 3-MgO粉末，继续搅拌并缓慢升温至75℃，该温度下继续搅拌14h后降至室温，静置后倾倒出上层液体，去离子水洗涤下层沉淀物直至溶液中检测不到氯离子，100℃烘干24h后再于300℃空气中焙烧24h得到催化剂Cu-La-Au/SiO 2-Al 2O 3-MgO。其中La、Ce、Au在催化剂中的质量百分含量分别为1％、1％、1.4％。
实施例11
分别将对比例与实施例1-10所述催化剂在同样条件下应用于甲基丙烯酸甲酯的合成反应，反应条件为：
将2000mL甲基丙烯醛与甲醇在3L不锈钢高压反应釜充分混合，加入500g催化剂，充分混合，其中甲基丙烯醛的浓度为30wt％，密封反应釜，开启搅拌，浴温80℃开始反应，在反应釜底部分别以1L/min和3L/min的速率通入空气和氮气，采用液体恒流进样泵向体系中以10ml/min的速率向反应釜中加入反应原料，生成产物连续取出至储料罐，每隔一定时间取出料液，使用气相色谱对出料液进行分析，使用正癸烷作为内标物，计算出甲基丙烯醛的转化率和甲基丙烯酸甲酯的选择性，反应200h。
实施例12
将2000mL甲基丙烯醛与甲醇在3L不锈钢高压反应釜充分混合，加入500g实施例1中的催化剂，充分混合，其中甲基丙烯醛的浓度为30wt％，密封反应釜，开启搅拌，浴温80℃开始反应，在反应釜底部分别以1L/min和3L/min的速率通入空气和氮气，采用液体恒流进样泵向体系中以10ml/min的速率向反应釜中加入反应原料，生成产物连续取出至储料罐，每隔一定时间取出料液，使用气相色谱对出料液进行分析，使用正癸烷作为内标物，计算出甲基丙烯醛的转化率和甲基丙烯酸甲酯的选择性，反应4000h。
实施例11与12的结果如下表：从表中可以看出过渡金属和镧系金属的加入提高了催化剂的活性，反应的转化率和选择性均有提高；提高Au的负载量后催化剂的催化性能降低。
Figure PCTCN2018120758-appb-000001
Figure PCTCN2018120758-appb-000002

Claims (17)

  1. 一种生产甲基丙烯酸甲酯的催化剂，其特征在于，所述催化剂包括载体和负载在载体上的活性中心；所述活性中心包括金、过渡金属和镧系金属；所述载体包括SiO 2、Al 2O 3和碱金属或碱土金属中一种；所述催化剂中，金的负载量为0.05wt％-0.98wt％，镧系金属的负载量为1wt％-2.5wt％，过渡金属的负载量为1wt％-2.5wt％。
  2. 根据权利要求1所述生产甲基丙烯酸甲酯的催化剂，其特征在于，所述碱金属或碱土金属为Na、K、Rb、Cs、Be、Mg、Ca、Sr；所述镧系金属为La、Ce、Pr、Nd中的一种，所述过渡金属为Cu、Co、Fe、Mn、Cr中的一种。
  3. 根据权利要求1所述生产甲基丙烯酸甲酯的催化剂，其特征在于，以载体质量为100％计，碱金属与碱土金属的质量分数范围1-25％；所述载体中碱金属或碱土金属与SiO 2的摩尔比为1～6:0.5～4。
  4. 一种权利要求1-4任意一项所述生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：在搅拌条件下，将金的前驱体和还原剂与去离子水充分混合，得到金溶胶，在高分子保护剂存在的条件下，向金溶胶依次加入镧系金属前驱体和过渡金属前驱体，然后加入载体，升温至65-85℃，继续搅拌2-20h，搅拌结束后降至室温，静置过滤，用去离子水洗涤，烘干后于空气中焙烧得到所述催化剂。
  5. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述载体制备过程为：在搅拌条件下，向二氧化硅的前驱体溶液中加入氧化铝前驱体、碱金属或碱土金属的前驱体，充分搅拌混合后，加入酸调节PH值至0.5-5.5，继续搅拌1-24h后得到混合物，将所述混合物进行喷雾干燥成型，得到颗粒尺寸为50-100μm的球状颗粒物，在空气气氛下焙烧得到所述载体。
  6. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述Au的前躯体为氰化金(Au(CN) 3)、氰化亚金钾、氯化亚金(AuC1)、氯化金(AuC1 3)、氯金酸、氯金酸盐、亚硫酸金钠或雷金中的一种或两种以上。
  7. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述高分子保护剂为聚乙烯醇、聚乙烯吡咯烷酮、四羟甲基氯化磷、聚二甲基二丙烯氯化铵、柠檬酸钠、硫醇类物质。
  8. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述还原剂为柠檬酸钠、四羟甲基氯化磷、草酸和硼氢化钠。
  9. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述镧系金属前驱体和过渡金属的前驱体为相应金属的硫酸盐、硝酸盐、磷酸盐、碳酸盐、醋酸盐。
  10. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述方法中，镧系金属前驱体、过渡金属前驱体、金前驱体、还原剂、高分子保护剂和载体的加入量为：镧系金属元素:过渡金属元素:金元素:还原剂:高分子保护剂:载体:水的质量比为1:0.4～2.5:0.02～0.98:0.2～0.5:0.2～0.5:50～200:200～400。
  11. 根据权利要求4所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：在二氧化硅前驱体溶液中加入碱金属或碱土金属前驱体之前，先加入氧化铝前驱体并溶解。
  12. 根据权利要求5所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述碱金属或碱土金属的前驱体为相应金属的单质、氧化物、氢氧化物、化合物或复合物。
  13. 根据权利要求5所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述酸为硝酸、硫酸、盐酸、磷酸中的一种。
  14. 根据权利要求5所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述二氧化硅的前驱体为硅溶胶、固体硅胶、白炭黑中的一种。
  15. 根据权利要求5所述的生产甲基丙烯酸甲酯催化剂的制备方法，其特征在于：所述氧化铝的前驱体为硝酸铝、硫酸铝、磷酸铝、醋酸铝、醋酸铝或者氧化铝粉末中的一种。
  16. 一种甲基丙烯酸甲酯的合成方法，其特征在于：采用权利要求1-3任意一项中所述的催化剂，以甲基丙烯醛和甲醇为反应原料，通过一步氧化法催化合成甲基丙烯酸甲酯。
  17. 根据权利要求16所述的甲基丙烯酸甲酯的合成方法，其特征在于：将反应原料加入反应器中充分混合，然后向反应器中加入所述催化剂；密封反应器，开启搅拌，在反应器底部分别以0.8-1.3L/min和2.5-3.2L/min的速率通入空气和惰性气体，采用液体恒流泵以8-12ml/min的速率加入反应原料，反应后的产物以与反应原料加入速率相同的速率存储；反应混合物中甲醇的质量浓度为50-70％，所述反应原料与催化剂组成反应体系；所述催化剂在反应体系中的质量浓度为15-20％。
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