WO2010054552A1 - 一种负载型金属钯催化剂的制备方法 - Google Patents

一种负载型金属钯催化剂的制备方法 Download PDF

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WO2010054552A1
WO2010054552A1 PCT/CN2009/072453 CN2009072453W WO2010054552A1 WO 2010054552 A1 WO2010054552 A1 WO 2010054552A1 CN 2009072453 W CN2009072453 W CN 2009072453W WO 2010054552 A1 WO2010054552 A1 WO 2010054552A1
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carrier
catalyst
solution
hours
palladium
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French (fr)
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张法智
陈鹏
侯荣
陈加利
高超
张慧
李殿卿
李峰
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • B01J23/007—Mixed salts
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J23/892—Nickel and noble 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
    • B01J23/70—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
    • B01J23/8926—Copper and noble 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • 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
    • 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
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • 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

Definitions

  • the invention belongs to the technical field of catalysts, and in particular provides a preparation method of a supported metal palladium catalyst. Background technique
  • Supported catalysts are obtained in petrochemical processes, especially in hydrocarbon processes, especially in hydrocarbon conversion, olefin selective oxidation, and selective hydrogenation, due to their excellent heat and mass transfer properties and easy realization of continuous reactions. Widely used, it accounts for more than 70% of the total amount of catalyst.
  • the additive metal is added to the catalyst by a dipping method, a spray method or a coating method.
  • the auxiliary metal supported by these methods is easily affected by the solvation effect and the clustering effect of the metal component in the preparation process, and is liable to cause micro-coagulation of the metal component in the subsequent high-temperature baking process, thereby causing assistance.
  • the dispersibility of the metal component of the agent is poor, the structure of the catalyst is unstable, the dispersion of the active metal is low, the energy consumption in the preparation process is high, and the consumption of the precious metal is large.
  • Hydrotalcite-like compounds include hydrotalcite and hydrotalcite-like compounds, and the main body thereof is generally composed of hydroxides of two metals, so it is also called layered double-hydroxy composite metal oxide (Layered Double Hydroxide). , abbreviated as LDH).
  • LDH layered double-hydroxy composite metal oxide
  • the intercalated compound of LDH is called intercalated hydrotalcite.
  • Hydrotalcite, hydrotalcite-like, and intercalated hydrotalcite are collectively referred to as hydrotalcite-like intercalation materials (LDHs:).
  • the material is a hexagonal sheet structure, and the sheet itself has extremely high rigidity, and it is extremely difficult to prepare a sheet-like structure with controllable morphology.
  • This type of material is an inorganic material with unique structural properties: such as tunable denaturation of elemental composition over a wide range, tunable denaturation of pore structure, and designability of interlayer anion species, etc. It is likely to be the basis for industrial catalysts or catalyst precursors with potential applications.
  • a method for preparing a supported hydrotalcite is disclosed in the patent CN 1269260A, which is The monolithic or double-drip method utilizes the reaction of an alkaline earth metal salt and a soluble trivalent metal salt to assemble a hydrotalcite precursor containing a divalent metal on the surface and inner pores of the A1 2 0 3 carrier, and then calcined to form a catalyst.
  • the method will have better performance in improving the catalytic performance of the catalyst, enhancing the stability of the catalyst and reducing the consumption of precious metals. effect. Summary of the invention
  • the method of the present invention first forms a hydrotalcite precursor containing a catalyst auxiliary metal element and an aluminum element on the surface of the A1 2 0 3 microsphere (carrier). Using the lattice localization effect of the hydrotalcite crystal, the metal atom and the aluminum atom of the auxiliary agent are highly dispersed with each other and firmly bonded to the carrier; in the subsequent drying and calcination, the hydrotalcite precursor obtained above is converted into highly dispersed assistance.
  • the method can improve the overall catalytic performance of the catalyst and enhance the stability of the catalyst. In addition, the method of the invention can also reduce the consumption of precious metal palladium.
  • A1 2 0 3 carrier with a certain geometry of 26 ⁇ 100 mesh is added to the above solution.
  • the A1 2 0 3 carrier is added in an amount of 1 to 6 g of A1 2 0 3 per 100 ml of the above solution, and stirred at 80 to 150 ° C for 3 to 15 hours to obtain a mixed solution.
  • M 2+ represents a divalent metal cation
  • the M 2+ may be any one or more of Mg 2+ , Ni 2+ , Ca 2+ , Pt 2+ , and Cu 2+ . More preferably, it is one or more of Mg 2+ , Ni 2+ or Ca 2+ .
  • the concentration of the M 2+ ion in the 0.1 to 1 mol/L means that the concentration of the M 2+ ion in the system when the M 2+ salt solution is added to the mixed solution is 0.1 to 1 mol. /L.
  • A1 2 0 3 wherein the shape of the carrier may be spherical, and sheet-like cloverleaf shape of one or more,
  • A1 2 0 3 crystalline form may be any vector ⁇ , ⁇ , ⁇ , ⁇ , and the ⁇ One or more.
  • the M 2+ Al-LDHs/Al 2 0 3 precursor obtained by the method of the present invention was confirmed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and the like.
  • the medium M 2+ Al-LDHs are located on the surface layer and the inner pore surface of the A1 2 0 3 carrier.
  • the amount of Pd in the catalyst was measured by inductively coupled plasma emission spectroscopy to be 0.1% by weight to 5% by weight.
  • the aluminum talc precursor is provided with an aluminum element.
  • the method of the present invention uses a layered precursor method, which refers to a process of preparing a substance having a layered structure on the surface of the material, and the layered structure gradually disappears in the subsequent treatment.
  • the present invention is characterized in that
  • the layered precursor of M 2+ Al-LDHs can be grown on the surface of the A1 2 0 3 carrier and the surface of the inner pore by the method of the invention, due to the LDHs Lattice localization effect, the metal elements and aluminum elements distributed on the surface of the support are bound by the lattice and are separated and evenly distributed, and the migration of ions is not easy in the subsequent calcination process, and can be made next
  • the supported Pd elements are better separated and dispersed from each other, so that the auxiliary metal element and the main active metal can be uniformly and stably distributed on the surface of the carrier, thereby improving the overall stability and catalytic performance of the catalyst, and also reducing the precious metal.
  • the amount of catalyst used is characterized in that the layered precursor of M 2+ Al-LDHs can be grown on the surface of the A1 2 0 3 carrier and the surface of the inner pore by the method of the invention, due to the LDHs Lattice localization
  • the catalyst prepared by the invention passes through a fixed-bed catalytic hydrogenation micro-reactor, and the catalytic hydrogenation of dimethyl terephthalate to produce dimethyl 1,4-cyclohexanedicarboxylate is evaluated, and the reactant conversion rate is 90%. ⁇ 97%, product selectivity is between 90% and 98%.
  • Pd/Al 2 0 3 prepared by the traditional impregnation method was subjected to catalytic hydrogenation of dimethyl terephthalate to form dimethyl 1,4-cyclohexanedicarboxylate under the same conditions, and the reactant conversion rate was 85. % ⁇ 95%, product selectivity is 75% ⁇ 88%. Therefore, the catalyst prepared according to the process of the present invention has higher catalytic hydrogenation activity and selectivity than the conventional palladium catalyst which is co-impregnated or stepwise impregnated with the introduction aid.
  • Figure 1 is a schematic illustration of a fixed bed catalytic hydrogenation microreactor apparatus used in Examples 1-3 of the process of the present invention.
  • Example 2 is an XRD spectrum of MgAl-LDHs/Al 2 0 3 prepared in Example 1 of the method according to the present invention.
  • NiAl-LDHs/Al 2 0 3 is a nitrogen gas absorption and desorption isotherm diagram of NiAl-LDHs/Al 2 0 3 prepared according to Example 2 of the method of the present invention, wherein P is a partial pressure of nitrogen, P. Is the saturated vapor pressure of the material to be tested.
  • Example 1 The structure was analyzed by the American Cota AS-1C-VP type surface-aperture distribution tester, and degassed at 373K for 2 hours, and then subjected to nitrogen adsorption and desorption test under liquid nitrogen atmosphere.
  • Example 1 The structure was analyzed by the American Cota AS-1C-VP type surface-aperture distribution tester, and degassed at 373K for 2 hours, and then subjected to nitrogen adsorption and desorption test under liquid nitrogen atmosphere.
  • Catalyst performance test Catalytic hydrogenation of dimethyl terephthalate to 1,4-cyclohexyl dimethane by a fixed-bed catalytic hydrogenation microreactor (MRCS-2000DR micro-reverse chromatography system) using the prepared supported catalyst Dimethyl formate, reaction conditions include: reaction temperature 220 ° C, 3 ⁇ 4 pressure is 80 atm, hydrogen to oil ratio of 80, using ethyl acetate as solvent, solvent amount of 100 ml / 3 g of dimethyl terephthalate The reaction time was 6 h. As a result, the conversion of dimethyl terephthalate was 91%, and the selectivity of dimethyl 1,4-cyclohexanedicarboxylate was 98%.
  • Example 3 6 g of urea was weighed and dissolved in deionized water to prepare a solution of 60 ml, and 3 g of a spherical ⁇ - ⁇ 1 2 3 having a particle size of 40 mesh was added to the above solution, and stirred at 100 ° C for 15 hours. Weigh 9 g of calcium chloride dissolved in deionized water to prepare a solution of 60 ml, add to the mixture obtained above, stir at 120 ° C for 10 hours, filter by cooling, wash with deionized water, at 90 Drying at ° C gave CaAl-LDHs/Al 2 0 3 .
  • FIG learned by XRD prepared as CaAl-LDHs / Al 2 0 3 .

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Description

一种负载型金属钯催化剂的制备方法
技术领域
本发明属于催化剂技术领域，特别是提供了一种负载型金属钯催化剂的 制备方法。 背景技术
负载型催化剂以其优良的传热传质性能， 以及容易实现连续化反应等特 点， 在石油化工过程， 特别是在烃类转化、 烯烃选择性氧化、 以及选择性加 氢等重要反应过程中获得了广泛使用， 其使用量占催化剂总量的 70%以上。
而常见的重要石油化工过程中所用的负载型催化剂的制备过程中，多采 用浸渍法、 喷淋法或者涂覆法等方法将助剂金属添加到催化剂中。 对于用这 些方法负载的助剂金属，在制备过程中容易受到溶剂化效应和金属组分的团 簇效应影响， 而且在后续高温焙烧过程中易产生金属组分微晶凝并现象， 从 而导致助剂金属组分分散性差， 催化剂结构不稳定， 活性金属分散度较低， 制备过程能耗高和贵重金属消耗量大的结果。
水滑石类化合物包括水滑石 (Hydrotalcite)和类水滑石 (Hydrotalcite-like compound), 其主体一般由两种金属的氢氧化物构成， 因此又称为层状双羟 基复合金属氧化物 (Layered Double Hydroxide,简写为 LDH)。 LDH的插层化 合物称为插层水滑石。 水滑石、 类水滑石和插层水滑石统称为水滑石类插层 材料 (LDHs：)。 该材料为六方片层结构， 片层本身具有极强的刚性， 极难制备 出形貌可控的片状结构。 该类材料是一种具有独特结构特性的无机材料： 如 元素组成在较宽范围内的可调变性、孔结构的可调变性以及层间插层阴离子 种类的可设计性等奠定了这类材料有可能成为具有潜在应用前景的工业催 化剂或催化剂前驱体的基础。
专利 CN 1269260A中公开了一种制备负载型水滑石的方法， 该方法通 过单滴法或双滴法利用碱土金属盐和可溶性三价金属盐的反应在 A1203载体 表面及内孔组装含有二价金属的水滑石前体， 再经过焙烧成为的催化剂在生 成醇醚醋酸酯的反应中有很好的活性；在 Journal of catalysis 231(2005)92-104 中提到过在镁铝复合氧化物表面负载有 Ni作为催化剂， 这对提高 Ni的活性 起到了良好的效果； 另外由于水滑石层板金属离子间的相互作用对金属原子 有很好的隔离作用， 该方法在提高催化剂的催化性能， 增强催化剂的稳定性 和减少贵重金属消耗量方面将有较好的效果。 发明内容
本发明的方法首先在 A1203微球 （载体） 表面上形成含有催化剂助剂金 属元素和铝元素的水滑石前体。利用水滑石晶体的晶格定位效应使助剂金属 原子和铝原子相互高度分散并与载体牢固结合；在随后进行的干燥和焙烧过 程中， 上述得到的水滑石前体转变为相互高度分散的助剂金属和铝的复合氧 化物， 并且能够对随后要负载上的催化剂主活性金属钯元素起到隔离和分散 作用。 本方法能够提高催化剂整体催化性能， 增强催化剂稳定性， 此外， 本 发明的方法还能减少贵金属钯消耗量。
本发明的具体制备步骤如下：
1、 M2+Al-LDHs/Al203前体的制备
称取一定量的尿素溶于去离子水中配置成溶液，使得到的溶液中尿素的 浓度为 0.2~2mol/L; 将粒度为 26~100 目的具有一定几何形状的 A1203载体 加入上述溶液中， 所述 A1203载体加入的量为每 100 ml的上述溶液中加入 l~6g的 A1203， 在 80~150°C下搅拌 3~15小时， 得到混合溶液。 称取一定量 的可溶性 M2+盐溶于去离子水配置成 M2+盐溶液， 按照一定比例加入到上述 混合溶液中， 使其中 M2+离子的浓度保持在 0.1~1 mol/L, 在 80~160°C下搅 拌 3~15 小时， 冷却过滤， 用去离子水洗涤， 于 80~120°C下干燥， 得到 M2+Al-LDHs/Al203前体。
其中， M2+表示二价金属阳离子， 优选地， 所述 M2+可以是 Mg2+、 Ni2+、 Ca2+、 Pt2+和 Cu2+中的任意一种或者是多种， 更优选为 Mg2+、 Ni2+或 Ca2+中 的一种或多种。
所述使其中 M2+离子的浓度保持在 0.1~l mol/L指的是将 M2+盐溶液加入 混合溶液中还未发生反应时体系中的 M2+离子的浓度为 0.1~1 mol/L。
其中 A1203载体的形状可以是球型、 三叶草型和片状等形状中的一种或 者是多种， A1203载体的晶形可以是 δ、 β、 γ、 Θ和 η中的任意一种或多种。
通过 X射线衍射（XRD)、傅立叶变换红外（FT-IR)、X光电子能谱（XPS ) 等表征方法证实， 根据本发明的方法所得到的 M2+Al-LDHs/Al203前体中 M2+Al-LDHs位于 A1203载体的表层及内孔表面上。
2、 负载型催化剂的制备
称取一定质量的氯化钯配置成氯化钯水溶液，使得到的氯化钯水溶液中 氯化钯的浓度保持在 0.03~0.3 mol/L, 将步骤 1中得到的 M2+Al-LDHs/Al203 前体加入到上述氯化钯水溶液中， 在 50~90°C的水浴摇床中放置 1~24小时 后过滤， 将得到的固体用去离子水洗涤， 于 80~120°C下干燥， 然后在 300~900°C的温度下焙烧 2~24小时，将焙烧过的样品放置于固定床还原装置 中， 用 ¾在200~600 的温度下还原处理 2~24小时， 得到负载型催化剂。
通过电感耦合等离子发射光谱可测得该催化剂中 Pd的量为 0.1重量％~5 重量％。
由于在尿素作用下， 载体三氧化二铝的表面可以形成铝的活化层， 从而 为水滑石前体提供铝元素。 本发明的方法使用了层状前体法， 该方法是指先 在材料表面制备形成具有层状结构的物质， 而在后续处理过程中该层状结构 逐渐消失的过程， 因此， 本发明的特点在于， 通过本发明的方法能够使 M2+Al-LDHs层状前体生长在 A1203载体的表面及内孔表面， 由于 LDHs的 晶格定位效应， 分布在载体表面的助剂金属元素和铝元素受到晶格的束缚而 被定向间隔分离且均匀分布， 在随后的焙烧过程中也不容易发生离子的迁 移， 并且能够使接下来负载的 Pd元素得到更好地相互隔离和分散， 因此助 剂金属元素和主活性金属都能均匀稳定的分布在载体的表面，从而提高了催 化剂整体的稳定性和催化性能， 并且还减少了贵金属催化剂的使用量。
将本发明制备的催化剂通过固定床催化加氢微反应装置，进行对苯二甲 酸二甲酯催化加氢生成 1,4-环己垸二甲酸二甲酯反应评价， 反应物转化率为 90%~97%， 产物选择性在 90%~98%。 用传统的浸渍法制备的 Pd/Al203在相 同条件下进行对苯二甲酸二甲酯催化加氢生成 1 ,4-环己垸二甲酸二甲酯反应 评价， 反应物转化率为 85%~95%， 产物选择性在 75%~88%。 因此， 与传统 共浸渍或者分步浸渍引入助剂的金属钯催化剂相比，根据本发明的方法制备 的催化剂具有更高的催化加氢反应活性和选择性。 附图说明
图 1是根据本发明的方法的实施例 1-3所使用的固定床催化加氢微反应 装置示意图。
图 2是根据本发明的方法的实施例 1制得的 MgAl-LDHs/Al203的 XRD 谱图。
图 3是根据本发明的方法的实施例 2制得的 NiAl-LDHs/Al203的氮气吸 脱附等温线图， 其中， P为氮气的分压， P。为待测材料的饱和蒸汽压。 具体实施方式
通过下面实施例对本发明予以具体说明。
在以下实施例中，使用如下方法测定各实施例中制得的根据本发明的产 p 以日本岛津 XRD-6000型 X射线衍射仪进行结构分析， Cu Ka光源（λ = 0.154 nm)， 电压 40 Kv， 电流 30 mA， 连续扫描， 扫描速度 2 min。
以美国康塔公司 AS-1C-VP型比表面 -孔径分布测试仪进行结构分析，在 373K温度下脱气处理 2h后在液氮气氛下进行氮气吸脱附测试。 实施例 1：
称取 4 g的尿素溶于去离子水配置成 80 ml的溶液， 将 2 g粒度为 60目 球形 η-Α1203加入上述溶液中， 在 130°C条件下搅拌 12小时。 称取 12 g的 Mg(N03)2 · 6H20溶于去离子水配置成 20 ml溶液， 加入到按上述得到的混 合物中， 130°C温度下搅拌 12小时， 冷却过滤， 用去离子水洗涤， 于 80°C下 干燥， 得到 MgAl-LDHs/Al203。
称取 0.04 g的氯化钯配置成氯化钯水溶液，将得到的 MgAl-LDHs/Al203 加入氯化钯水溶液中， 在 50°C的水浴摇床中放置 24小时， 过滤， 将得到的 固体用去离子水洗涤， 于 80°C下干燥， 然后在 450°C的温度下焙烧 8小时， 将焙烧过的样品放置于固定床还原装置中，用 1¾在 300 °C的温度下还原处理 3小时， 得到本发明的负载型催化剂。
通过 XRD图得知， 制得的为 MgAl-LDHs/Al203。
催化剂性能测试： 通过固定床催化加氢微反应装置 （MRCS-2000DR微 反色谱系统）， 用制得的负载型催化剂进行对苯二甲酸二甲酯催化加氢生成 1,4-环己垸二甲酸二甲酯， 反应条件包括： 反应温度 220°C， ¾压为 80 atm， 氢油比为 80， 采用乙酸乙酯做溶剂， 溶剂用量为 100 ml/3 g的对苯二甲酸二 甲酯， 反应时间为 6h， 结果对苯二甲酸二甲酯转化率为 91%, 1,4-环己垸二 甲酸二甲酯选择性为 98 %。
对比例 1
作为比较，称取 12 g的 Mg(N03)2 · 6Η20和 0.04 g氯化钯通过共浸渍法 在 A1203载体上进行制备得到催化剂， 按照与实施例 1相同的方法进行催化 剂性能测试， 得到结果为对苯二甲酸二甲酯转化率为 88%, 1,4-环己垸二甲 酸二甲酯选择性为 80%。 实施例 2:
称取 8 g的尿素溶于去离子水配置成 70 ml的溶液，将 3 g的粒度为 100 目球形 Θ-Α1203加入上述溶液中， 在 100°C条件下搅拌 15小时。称取 16 g的 Ni(N03)2 · 6¾0溶于去离子水配置成 30 ml的溶液， 加入到按上述得到的混 合物中， 在 110°C的温度下搅拌 14小时， 冷却过滤， 用去离子水洗涤， 于 100 V下干燥， 得到 NiAl-LDHs/Al203。
称取 0.3 g的氯化钯配置成水溶液， 将得到的 NiAl-LDHs/Al203加入氯 化钯水溶液中， 在 80°C的水浴摇床中放置 12小时， 过滤， 将得到的固体用 去离子水洗涤， 于 120°C下干燥， 然后在 500 °C的温度下焙烧 6小时， 将焙 烧过的样品放置于固定床还原装置中， 用 ¾在 400°C的温度下还原处理 2.5 小时， 得到本发明的负载型催化剂。
通过 XRD图得知， 制得的为 NiAl-LDHs/Al203。
按照与实施例 1相同的方法对所制得的催化剂进行催化剂性能测试，结 果对苯二甲酸二甲酯转化率为 90%, 1,4-环己垸二甲酸二甲酯选择性为 94%。 对比例 2
作为比较， 称取 16 g的 Ni(N03)2 · 6H20和 0.3g的氯化钯通过共浸渍法 在 A1203载体上进行制备得到催化剂， 按照与实施例 1相同的方法进行催化 剂性能测试， 得到结果为对苯二甲酸二甲酯转化率为 92%, 1,4-环己垸二甲 酸二甲酯选择性为 88%。 实施例 3： 称取 6 g的尿素溶于去离子水配置成 60 ml的溶液， 将 3 g的粒度为 40 目球形 γ-Α1203加入上述溶液中， 在 100°C条件下搅拌 15小时。 称取 9 g的 氯化钙溶于去离子水配置成 60 ml的溶液， 加入到按上述得到的混合物中， 在 120°C温度下搅拌 10小时， 冷却过滤， 用去离子水洗涤， 于 90°C下干燥， 得到 CaAl-LDHs/Al203。
称取 0.3 g的氯化钯配置成水溶液， 将得到的 CaAl-LDHs/Al203加入氯 化钯水溶液中， 在 90°C的水浴摇床中放置 14小时， 过滤， 将得到的固体用 去离子水洗涤， 于 100°C下干燥， 然后在 400 °C的温度下焙烧 9小时， 将焙 烧过的样品放置于固定床还原装置中， 用 ¾在 300°C的温度下还原处理 4 小时， 得到本发明的负载型催化剂。
通过 XRD图得知， 制得的为 CaAl-LDHs/Al203。
按照与实施例 1相同的方法对所制得的催化剂进行催化剂性能测试，结 果对苯二甲酸二甲酯转化率为 92%, 1,4-环己垸二甲酸二甲酯选择性为 90%。 对比例 3
作为比较，， 称取 18 g的氯化钙和 0.3 g的氯化钯通过共浸渍法在 A1203 载体上进行制备得到催化剂，按照与实施例 1相同的方法进行催化剂性能测 试， 得到结果为对苯二甲酸二甲酯转化率为 85%, 1,4-环己垸二甲酸二甲酯 选择性为 78%。

Claims

权利要求书
1、 一种负载型金属钯催化剂的制备方法， 其特征在于， 该方法包括以 下步骤：
( 1 ) M2+Al-LDHs/Al203前体的制备
称取一定量的尿素溶于去离子水配置成溶液，使得到的溶液中尿素的浓 度为 0.2〜2mol/L;将粒度为 26〜100目的具有一定几何形状的 A1203载体加 入上述溶液中， 所述 A1203载体加入的量为每 100 ml的上述溶液中加入 1〜 6g的 A1203， 在 80〜150°C下搅拌 3〜15小时， 得到混合溶液； 称取一定量 的可溶性 M2+盐溶于去离子水配置成 M2+盐溶液， 按照比例加入到所述混合 溶液中，使其中 M2+离子的浓度保持在 0.1〜lmol/L，在 80〜160°C下搅拌 3〜 15 小时， 冷却过滤， 用去离子水洗涤， 于 80〜120°C下干燥， 得到 M2+ Al-LDHs/Al203前体；
(2) 负载型催化剂的制备
称取一定质量的氯化钯配置成氯化钯水溶液，使所述氯化钯水溶液中氯 化钯的浓度保持在 0.03〜0.3 mol/L,将步骤（ 1 )中得到的 M2+Al-LDHs/Al203 前体加入到所述氯化钯水溶液中，在 50〜90°C的水浴摇床中放置 1〜24小时 后过滤，将得到的固体用去离子水洗涤，于 80〜120°C下干燥，然后在 300〜 900°C的温度下焙烧 2〜24小时，将焙烧过的样品放置于固定床还原装置中， 用 ¾在 200〜600°C的温度下还原处理 2〜24小时， 得到所述负载型金属钯 催化剂。
2、根据权利要求 1所述的方法， 其特征在于， 所述 A1203载体的形状为 球型、 三叶草型和片状中的一种或者多种， 所述 A1203载体的晶形为 δ、 β、 γ、 Θ和 η中的任意一种或多种。
3、 根据权利要求 1或 2所述的方法， 其特征在于， 所述的 Μ2+离子为 Mg2+、 Ni2+、 Ca2+、 Pt2+和 Cu2+中的任意一种或者多种。
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CN113600157A (zh) * 2021-09-06 2021-11-05 北京化工大学 一种稀土掺杂的球形氧化铝Pd基催化剂及其制备方法和应用
CN113600157B (zh) * 2021-09-06 2024-04-09 北京化工大学 一种稀土掺杂的球形氧化铝Pd基催化剂及其制备方法和应用
CN113786844A (zh) * 2021-10-13 2021-12-14 北京化工大学 石墨烯基纳米片阵列复合物负载钯簇催化剂及制备方法

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