WO2003090927A1 - Magnetic superfine solid acid catalyst with double shell structure and process for preparing - Google Patents

Magnetic superfine solid acid catalyst with double shell structure and process for preparing Download PDF

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Publication number
WO2003090927A1
WO2003090927A1 PCT/CN2002/000756 CN0200756W WO03090927A1 WO 2003090927 A1 WO2003090927 A1 WO 2003090927A1 CN 0200756 W CN0200756 W CN 0200756W WO 03090927 A1 WO03090927 A1 WO 03090927A1
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magnetic
solid acid
carrier
double
shell structure
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PCT/CN2002/000756
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French (fr)
Chinese (zh)
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Xue Duan
Zheng Chang
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J35/33—
    • B01J35/51—
    • 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
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles

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  • the invention relates to a double-shell structure magnetic solid acid catalyst and a preparation method thereof. Background technique
  • the purpose of the present invention is to overcome the shortcomings that the active center of the catalyst cannot fully function, and to prepare a magnetic solid acid catalyst with a double shell structure, that is, to select a carrier with a large surface area as a transition layer, and first encapsulate the magnetic core.
  • the magnetic solid acid catalyst with a double-layer coating structure is prepared by mono-dispersing the active component on its surface, greatly increasing the number of acid centers. According to the monodispersity mechanism, many solids can spontaneously disperse on the surface of another solid (carrier) to form a monolayer (monolayer) or a submonolayer (not covered). Select some active components to disperse them on a porous, high specific surface area support.
  • the active components are in a single layer as a whole, which greatly increases the number of acidic centers and interacts strongly with the support.
  • the acidic centers on the inner and outer layers of the layer play different roles respectively.
  • the acidic centers on the inner surface layer may lose or reduce the catalyst activity due to the interaction with the support, while the acidic centers on the outer surface are completely exposed on the support surface.
  • the formed catalyst has excellent catalytic performance. It acts as a bridge with a high specific surface area.
  • the magnetic core can be coated by the sol-gel method.
  • the inner layer interacts with the magnetic core to give the catalyst magnetism, and the outer layer can interact with active components.
  • the specific surface area of the catalyst gives the catalyst excellent catalytic activity. This double-layered catalyst can better meet the requirements of simple separation and great activity. It is a further improvement of the magnetic catalyst with a single-layer coating structure.
  • the present invention has developed a magnetic superfine solid acid catalyst with a double shell structure, and its structure is shown in FIG. 1: in the magnetic core Fe 3 0 4 , Co-Fe 3 0 4 , Mn- Fe 3 0 4 or Ni-Fe 3 0 4 is coated with a high specific surface area material that is easy to be hydrolyzed to form a magnetic carrier.
  • the carrier is coated with a strong acid solid acid.
  • the solid acid catalyst with double shell structure has high magnetic activity and high catalytic activity. Performance characteristics.
  • the double-shell magnetic solid acid catalyst is prepared by the following method:
  • the magnetic core is prepared by the method in patent application 00133474.3, and the surface of the magnetic core is coated with a carrier having a high specific surface area by a sol-gel method to form a magnetic carrier.
  • the coated support should be a high specific surface area support that can be prepared by hydrolysis of raw materials.
  • the preferred hydrolyzable support is: high specific surface area materials such as Si0 2 , Zr0 2 , AI 2 0 3 , and Ti0 2 .
  • Strong acid solid acids are preferably Zr (S0 4 ) 2 , SO /--Zr0 2 , and F_Zr0 2 .
  • the specific preparation method is as follows:
  • the magnetic core is prepared according to the method in patent application 00133474.3.
  • the preferred magnetic cores are iron-based magnetic cores Fe 3 0 4 , cobalt-based magnetic cores Co-Fe 3 0 4 , manganese-based magnetic cores Mn-Fe 3 0 4 and nickel-based magnetics.
  • the strong acid solid acid solution is immersed in the strong acid solid acid solution at a constant temperature under a mass ratio of 0.25 to 1: 1 with the magnetic core carrier under constant temperature conditions. After immersing for 2 to 6 hours, it is separated by filtration and dried at 110 ° C. That is, a magnetic catalyst having a strong acid solid acid supported thereon is obtained.
  • Figure 1 Schematic diagram of a double-shell magnetic ultrafine solid acid catalyst.
  • Figure 1 is a schematic diagram of the structure of a double-shell magnetic ultra-fine solid acid catalyst, 1 is a magnetic core, 2 is a carrier shell with a high specific surface area, and 3 is a strong acid solid acid shell.
  • Example 1 The following further describes the present invention in detail with reference to several examples: Example 1
  • the FeCl 2 4H 2 0 solution (0.1mol / l) and FeCl 3 '6H 2 0 solution (0.1mol / l) 5: 1 was added to a three-necked flask, placed in a constant temperature water bath at 65 ° C, and 0.1 mol / l NaOH was added dropwise while stirring until the pH of the solution reached 12, and the mixture was aged at constant temperature for 30 min. A magnetic field is used to separate the magnetic matrix from the supernatant. Wash with deionized water until the pH of the solution is close to 7, and a black magnetic core Fe 3 0 4 can be obtained.
  • the esterification conversion activity of the catalyst was measured in the butyl acetate synthesis reaction system.
  • the test method was to weigh 0.6 g of the above catalyst, and add glacial acetic acid (29 ml, 0.5 mol) and n-butanol (53 ml, 0.55 mol) to the distillation.
  • glacial acetic acid 29 ml, 0.5 mol
  • n-butanol 53 ml, 0.55 mol
  • Zr0 with a molar ratio of ⁇ 2 and Fe 3 0 4 of 5: 1 can be prepared by using 50 ml Fe 3 0 4 (0.0025mol) and 100 ml ZrOCl 2. 8H 2 0 (0.0125mol) as raw materials. 2 / Fe 3 0 4 magnetic carrier, immersed in Zr (S0 4 ) 2 4H 2 0 solution at room temperature for 6h at 25% wt load, and then obtained Zr (S0 2 ) 2 / Zr0 2 by filtration and drying / Fe 3 0 4 catalyst.
  • Example 3 0.6g of the above catalyst was weighed into the reaction system as in Example 1, and the esterification conversion activity of the catalyst was measured to be 98%.
  • Example 3 0.6g of the above catalyst was weighed into the reaction system as in Example 1, and the esterification conversion activity of the catalyst was measured to be 98%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to the magnetic superfine solid acid catalyst with double shell structure and the process for preparing it. The properties of structure for catalyst is that the magnetic nucleus surface is covered by carrier with high specific surface area and hence forms carrier with magnetic nucleus on which there is a layer of strong acid solid acid. This catalyst is prepared by coating the surface of magnetic nucleus Fe3O4, Co-Fe3O4, Mn-Fe3O4 or Ni-Fe3O4 with carrier having high specific surface area, such as SiO2, ZrO2, Al2O3, TiO2, etc. by using sol-gel method, followed by dispersing strong acid solid acid Zr(SO4)2, SO42- -ZrO2, etc. into the surface of carrier with magnetism by using impregnation method. Such solid acid catalyst with double shell structure is mainly used to acid catalystic reaction, which has the advantage of having magnetism and high activity.

Description

一种双壳式结构磁性超细固体酸催化剂及其制备方法 技术领域  Magnetic superfine solid acid catalyst with double shell structure and preparation method thereof
本发明涉及一种双壳式结构磁性固体酸催化剂及其制备方法。 背景技术  The invention relates to a double-shell structure magnetic solid acid catalyst and a preparation method thereof. Background technique
目前国内外在研究固体酸催化剂时经常遇到超细催化剂粒子难以分 离和回收的问题， 针对这种情况， 本室及哈尔滨工程大学共同提出了赋 予催化剂磁性并利用外加磁场分离的思路。 在中国专利申请 00133474.3 中利用溶胶一凝胶法将 Zr02包覆在 Fe304外部制备了 Zr02/Fe304磁性固 体酸催化剂， 在 2001 年第 3 期的 《无机化学学报》 中利用更为简便的 超声波法将 Zr(S04)2 · 4H20 与 Fe304形成了具备更高酸强度的 Zr(S04)2/Fe304磁性固体酸催化剂， 但这两种制备方法， 都是将活性组分 直接包覆到磁性核表面， 其缺点在于表面活性组份受磁性核的影响损害 了部分活性中心的酸催化作用， 使得该类催化剂的活性受到局限。 发明内容 At present, when researching solid acid catalysts at home and abroad, it is often encountered that it is difficult to separate and recover ultrafine catalyst particles. In response to this situation, our laboratory and Harbin Engineering University have jointly proposed the idea of making the catalyst magnetic and using an external magnetic field for separation. In Chinese patent application 00133474.3, a Zr0 2 / Fe 3 0 4 magnetic solid acid catalyst was prepared by coating Zr0 2 on the outside of Fe 3 0 4 by a sol-gel method. In the Journal of Inorganic Chemistry, No. 3, 2001 using an ultrasonic method more convenient Zr (S0 4) 2 · 4H 2 0 and Fe 3 0 4 forms a Z r with a higher acid strength (S0 4) 2 Fe 3 0 4 magnetic solid acid catalyst /, but In the two preparation methods, the active component is directly coated on the surface of the magnetic core. The disadvantage is that the surface active component is affected by the magnetic core to damage the acid catalysis of some active centers, so that the activity of this type of catalyst is limited. Summary of the Invention
本发明的目的是克服以上的催化剂活性中心不能够完全发挥作用的 缺点， 制备一种双壳式结构的磁性固体酸催化剂， 即选择一种表面积大 的载体作为过渡层， 先对磁性核进行包覆， 再让活性组分在其表面进行 单分散， 极大提高酸性中心的数量， 制备出双层包覆结构的磁性固体酸 催化剂。 ' . 根据单分散机理可知， 许多固体能自发分散在另一种固体 (载体) 表面形成单层 （单分子层） 或亚单层 （未敷满）。 选择一些活性组分使 其分散到多孔、 高比表面积的载体上， 活性组分整体处于一种单层状态， 极大地提高了酸性中心的数量， 并与载体发生较强的相互作用， 这样单 层内外表面的酸性中心分别发挥着不同的作用， 处于内表层的酸性中心 由于与载体发生了相互作用， 可能失去或降低了催化剂活性， 而位于外 表面的酸性中心完全暴露在载体表面， 因此所形成的催化剂具备较优异 的催化性能。 充当桥梁连接作用的高比表面积载体， 可以利用溶胶一凝 胶法对磁性核进行包覆， 其内层与磁性核作用， 赋予催化剂以磁性， 外 层又可与活性组分相互作用， 提高了催化剂的比表面积， 赋予催化剂优 异的催化活性。 这种双层结构的催化剂能够更好的满足即可简单分离又 具备极大活性的要求， 是对单层包覆结构的磁性催化剂的进一步改进。 The purpose of the present invention is to overcome the shortcomings that the active center of the catalyst cannot fully function, and to prepare a magnetic solid acid catalyst with a double shell structure, that is, to select a carrier with a large surface area as a transition layer, and first encapsulate the magnetic core. The magnetic solid acid catalyst with a double-layer coating structure is prepared by mono-dispersing the active component on its surface, greatly increasing the number of acid centers. According to the monodispersity mechanism, many solids can spontaneously disperse on the surface of another solid (carrier) to form a monolayer (monolayer) or a submonolayer (not covered). Select some active components to disperse them on a porous, high specific surface area support. The active components are in a single layer as a whole, which greatly increases the number of acidic centers and interacts strongly with the support. The acidic centers on the inner and outer layers of the layer play different roles respectively. The acidic centers on the inner surface layer may lose or reduce the catalyst activity due to the interaction with the support, while the acidic centers on the outer surface are completely exposed on the support surface. The formed catalyst has excellent catalytic performance. It acts as a bridge with a high specific surface area. The magnetic core can be coated by the sol-gel method. The inner layer interacts with the magnetic core to give the catalyst magnetism, and the outer layer can interact with active components. The specific surface area of the catalyst gives the catalyst excellent catalytic activity. This double-layered catalyst can better meet the requirements of simple separation and great activity. It is a further improvement of the magnetic catalyst with a single-layer coating structure.
基于以上设想， 本发明研制出了双壳式结构磁性超细固体酸催化 剂，其结构如图 1所示：在磁性核 Fe304 、 Co-Fe304、Mn- Fe304或 Ni-Fe304 上包覆一层易于水解制备的高比表面积物质形成带磁性的载体， 载体外 面是一层强酸固体酸， 这种双壳式结构的固体酸催化剂具备磁性及催化 活性高的性能特点。 Based on the above assumptions, the present invention has developed a magnetic superfine solid acid catalyst with a double shell structure, and its structure is shown in FIG. 1: in the magnetic core Fe 3 0 4 , Co-Fe 3 0 4 , Mn- Fe 3 0 4 or Ni-Fe 3 0 4 is coated with a high specific surface area material that is easy to be hydrolyzed to form a magnetic carrier. The carrier is coated with a strong acid solid acid. The solid acid catalyst with double shell structure has high magnetic activity and high catalytic activity. Performance characteristics.
该双壳式结构磁性固体酸催化剂通过如下方法制备：  The double-shell magnetic solid acid catalyst is prepared by the following method:
用专利申请 00133474.3中的方法制得磁性核， 利用溶胶一凝胶法在 磁性核表面包覆上具有高比表面积的载体， 形成带磁性的载体。 所包覆 的载体应是能用原料水解制备出的高比表面积载体， 优选的可水解制备 的载体是： Si02、 Zr02、 AI203、 Ti02等高比表面积物质。 The magnetic core is prepared by the method in patent application 00133474.3, and the surface of the magnetic core is coated with a carrier having a high specific surface area by a sol-gel method to form a magnetic carrier. The coated support should be a high specific surface area support that can be prepared by hydrolysis of raw materials. The preferred hydrolyzable support is: high specific surface area materials such as Si0 2 , Zr0 2 , AI 2 0 3 , and Ti0 2 .
然后利用浸渍法将强酸固体酸分散到带磁性的载体表面， 沉淀物经 干燥处理后， 即可得到具备磁性及高活性中心的双壳式结构磁性固体酸 催化剂。 强酸固体酸较好的是 Zr(S04)2、 SO/- -Zr02、 F_Zr02。 Then, a strong acid solid acid is dispersed on the surface of the magnetic carrier by a dipping method, and the precipitate is dried to obtain a double-shell structure magnetic solid acid catalyst having magnetic properties and a high active center. Strong acid solid acids are preferably Zr (S0 4 ) 2 , SO /--Zr0 2 , and F_Zr0 2 .
其具体制备方法如下：  The specific preparation method is as follows:
A. 磁性核的制备：  A. Preparation of magnetic core:
按照专利申请 00133474.3中的方法制备磁性核， 优选的磁性核是铁 基磁性核 Fe304、 钴基磁性核 Co-Fe304、 锰基磁性核 Mn-Fe304和镍基磁 性核 Ni-Fe304； The magnetic core is prepared according to the method in patent application 00133474.3. The preferred magnetic cores are iron-based magnetic cores Fe 3 0 4 , cobalt-based magnetic cores Co-Fe 3 0 4 , manganese-based magnetic cores Mn-Fe 3 0 4 and nickel-based magnetics. Nuclear Ni-Fe 3 0 4 ;
B. 磁性核载体的制备 将一定量所选磁性核粉末与水配置成悬浮液加入三口烧瓶中， 置于B. Preparation of magnetic nuclear carriers Add a certain amount of selected magnetic core powder and water into a suspension to a three-necked flask and place
50〜80 Ό恒温水浴中搅拌， 将制备载体物质所用的原料配制成溶胶溶液， 将该溶胶按照与磁性核 0.2~10:1摩尔比例滴加到三口烧瓶中， 在原料水 解形成溶胶-凝胶的同时磁性核得到包覆， 在以上包覆过程中， 一直要均 勾加入 0.5-2mol/l NaOH溶液使溶液 pH值恒定保持在 9〜11范围内， 得 到的沉淀物经陈化、 洗涤、 分离， 在 110°C下干燥， 500°C焙烧 3〜5小时， 即得到带磁性的载体； 50 ~ 80 搅拌 Stir in a constant temperature water bath, prepare the raw materials used to prepare the carrier material into a sol solution, add this sol to a three-necked flask in a molar ratio of 0.2 to 10: 1 to the magnetic core, and hydrolyze the raw materials to form a sol-gel At the same time, the magnetic core is coated. In the above coating process, 0.5-2mol / l NaOH solution must be added uniformly to keep the solution pH constant within the range of 9-11. The obtained precipitate is aged, washed, Separated, dried at 110 ° C, and baked at 500 ° C for 3 ~ 5 hours to obtain a magnetic carrier;
C. 双壳式结构磁性固体酸催化剂的合成：  C. Synthesis of double-shell magnetic solid acid catalyst:
将强酸固体酸溶液按照与磁性核载体 0.25〜1 :1 的质量比， 在恒温条 件下将磁性核载体粉末浸渍入强酸固体酸溶液， 浸渍 2~6小时后， 过滤 分离， 110°C干燥后即得已负载强酸固体酸的磁性催化剂。  The strong acid solid acid solution is immersed in the strong acid solid acid solution at a constant temperature under a mass ratio of 0.25 to 1: 1 with the magnetic core carrier under constant temperature conditions. After immersing for 2 to 6 hours, it is separated by filtration and dried at 110 ° C. That is, a magnetic catalyst having a strong acid solid acid supported thereon is obtained.
从上述为本发明设计出的桥式磁性固体酸催化剂的制备方法， 可以 实现带有磁性并具备较高催化活性的固体酸催化剂， 充当桥梁作用的载 体减弱了磁性核对活性组分的影响， 且通过活性组分的单层分散原理极 大提高了催化剂的催化活性， 其对乙酸乙酯合成反应的转化率达到 9%， 进一步完善了磁性固体酸催化剂的性质。 附图说明  From the above-mentioned preparation method of the bridge-type magnetic solid acid catalyst designed for the present invention, a solid acid catalyst with magnetic properties and high catalytic activity can be realized, and the carrier acting as a bridge reduces the influence of the magnetic core on the active components, and The single-layer dispersion principle of the active component greatly improves the catalytic activity of the catalyst, and its conversion rate to the ethyl acetate synthesis reaction reaches 9%, which further improves the properties of the magnetic solid acid catalyst. BRIEF DESCRIPTION OF THE DRAWINGS
图 1 : 双壳式结构磁性超细固体酸催化剂结构示意图。  Figure 1: Schematic diagram of a double-shell magnetic ultrafine solid acid catalyst.
图 1 为双壳式结构磁性超细固体酸催化剂结构示意图， 1 为磁性核， 2为高比表面积载体壳， 3为强酸固体酸壳。 具体实施方式  Figure 1 is a schematic diagram of the structure of a double-shell magnetic ultra-fine solid acid catalyst, 1 is a magnetic core, 2 is a carrier shell with a high specific surface area, and 3 is a strong acid solid acid shell. detailed description
下面结合几个实施例对本发明作进一步的详细说明： 实施例 1  The following further describes the present invention in detail with reference to several examples: Example 1
将 FeCl24H20溶液 （0.1mol/l) 和 FeCl3'6H20溶液 （0.1mol/l) 按照 5： 1 比例加入到三口烧瓶中， 放置于 65 °C的恒温水浴中， 搅拌同时滴 加 0.1mol/l NaOH, 直至溶液 pH值达到 12， 继续恒温搅拌陈化 30min。 利用磁场分离磁基体与上层清液。 用去离子水进行洗涤， 至溶液的 pH 值接近 7， 即可得到黑色的磁性核 Fe304。 The FeCl 2 4H 2 0 solution (0.1mol / l) and FeCl 3 '6H 2 0 solution (0.1mol / l) 5: 1 was added to a three-necked flask, placed in a constant temperature water bath at 65 ° C, and 0.1 mol / l NaOH was added dropwise while stirring until the pH of the solution reached 12, and the mixture was aged at constant temperature for 30 min. A magnetic field is used to separate the magnetic matrix from the supernatant. Wash with deionized water until the pH of the solution is close to 7, and a black magnetic core Fe 3 0 4 can be obtained.
取配成 0.0025mol悬浮液的 Fe3O450ml加入三口烧瓶中， 置于 50± 1 °C恒温水浴中搅拌， 滴加 1 mol/1 NaOH使溶液 pH达到 9。滴入 0.025mol 的正硅酸乙酯的乙醇溶液 （1.9mol/l)， 同时滴加 lmol/1 NaOH以保持反 应液 pH始终为 9。 待正硅酸乙酯完全滴加完毕后， 继续恒温陈化 lh。 随后转移至烧杯中室温下放置陈化 10天， 过滤分离， 110Ό干燥 48h。 取出后在 500°C焙烧 5h。 按 25%wt负载量用 Zr(S04)24H20溶液在室温 下浸渍 6h，过滤分离， 110°C干燥 48h，即可得 8102与 Fe304摩尔比为 10: 1的 Zr(S04)2/ Si02/ Fe304磁性固体酸催化剂。 50 ml of Fe 3 O 4 prepared as 0.0025mol suspension was added to a three-necked flask, placed in a 50 ± 1 ° C constant temperature water bath and stirred, and 1 mol / 1 NaOH was added dropwise to bring the solution pH to 9. A 0.025 mol solution of ethyl orthosilicate in ethanol (1.9 mol / l) was added dropwise, while 1 mol / 1 NaOH was added dropwise to keep the pH of the reaction solution always at 9. After the ethyl orthosilicate was completely added dropwise, the solution was aged at constant temperature for 1 h. Then transferred to a beaker and aged at room temperature for 10 days, separated by filtration, and dried at 110 ° C for 48h. After taking out, it was baked at 500 ° C for 5h. Zr (S0 4 ) 2 4H 2 0 solution was immersed at room temperature for 6h at 25% wt load, separated by filtration, and dried at 110 ° C for 48h to obtain Zr with a molar ratio of 810 2 to Fe 3 0 4 of 10: 1. (S0 4 ) 2 / Si0 2 / Fe 3 0 4 magnetic solid acid catalyst.
在乙酸丁酯的合成反应体系中测催化剂的酯化转化活性， 测试方法 为称取 0.6g上述催化剂以及冰醋酸 （29ml、 0.5mol)、 正丁醇 （53ml、 0.55mol) 加入到带精馏塔和回流冷凝管及分水器的三口烧瓶中， 搅拌条 件下升温， 回流， 反应温度约 120°C， 待反应完毕， 以磁场分离催化剂 后得到的上层澄清液用酸值滴定法确定醋酸转化率， 计算得到该催化剂 的酯化转化活性为 99%。 实施例 2  The esterification conversion activity of the catalyst was measured in the butyl acetate synthesis reaction system. The test method was to weigh 0.6 g of the above catalyst, and add glacial acetic acid (29 ml, 0.5 mol) and n-butanol (53 ml, 0.55 mol) to the distillation. In the three-necked flask of the tower, the reflux condenser and the water separator, the temperature was increased under stirring and refluxed. The reaction temperature was about 120 ° C. After the reaction was completed, the upper clear solution obtained after separating the catalyst by magnetic field was determined by acid value titration. Ratio, the esterification conversion activity of the catalyst was calculated to be 99%. Example 2
按照实施例 1 的方法， 以 50ml Fe304 ( 0.0025mol ) 与 100ml ZrOCl2. 8H20 (0.0125mol) 为原料即可制得∑ 2与 Fe304摩尔比为 5: 1的 Zr02/ Fe304带磁性的载体， 按 25%wt负载量， 用 Zr(S04)24H20溶 液在室温下浸渍 6h， 经过滤、 干燥制得 Zr (S02) 2/Zr02/ Fe304催化剂。 According to the method of Example 1, Zr0 with a molar ratio of Σ 2 and Fe 3 0 4 of 5: 1 can be prepared by using 50 ml Fe 3 0 4 (0.0025mol) and 100 ml ZrOCl 2. 8H 2 0 (0.0125mol) as raw materials. 2 / Fe 3 0 4 magnetic carrier, immersed in Zr (S0 4 ) 2 4H 2 0 solution at room temperature for 6h at 25% wt load, and then obtained Zr (S0 2 ) 2 / Zr0 2 by filtration and drying / Fe 3 0 4 catalyst.
称取 0.6g上述催化剂投入到如实施例 1 的反应体系中， 测得该催化 剂的酯化转化活性为 98%。 实施例 3 0.6g of the above catalyst was weighed into the reaction system as in Example 1, and the esterification conversion activity of the catalyst was measured to be 98%. Example 3
按照实施例 1方法， 最后按 25%wt负载量， 用 S04 2--Zr02浸渍 Si02/ Fe304， 即可得 8][02与？6304摩尔比为 10: 1的 S04 2--Zr02/ Si02/ Fe304磁 性固体酸催化剂。 According to the procedure of Example 1, and finally by loading 25% wt, with S0 4 2 --Zr0 2 impregnated Si0 2 / Fe 3 0 4, to give 8] [0 2? 6 3 0 4 S0 4 2 --Zr0 2 / Si0 2 / Fe 3 0 4 magnetic solid acid catalyst with a molar ratio of 10: 1.
称取 0.6g上述催化剂投入到如实施例 1 的反应体系中， 测得该催化 剂的酯化转化活性为 98%。  0.6 g of the above catalyst was weighed into the reaction system as in Example 1, and the esterification conversion activity of the catalyst was measured to be 98%.

Claims

权 利 要 求 书 Claim
1 . 本发明涉及一种双壳式结构磁性超细固体酸催化剂， 其结构特 征是： 在磁性核表面包覆上具有高比表面积的载体， 形成带磁性核的载 体， 载体外面是一层强酸固体酸； 这种双壳式结构的固体酸催化剂具备 磁性及催化活性高的性能特点。 1. The invention relates to a magnetic superfine solid acid catalyst with a double-shell structure, which is characterized in that: a surface of a magnetic core is covered with a carrier having a high specific surface area to form a carrier with a magnetic core, and a strong acid is formed on the outside of the carrier. Solid acid; This double-shell solid acid catalyst has the characteristics of high magnetic and catalytic activity.
2. 本发明还涉及一种双壳式结构磁性超细固体酸催化剂的制备方 法， 采用改进的共沉淀法制备磁性核， 其特征是在该磁性核的表面利用 溶胶一凝胶法包覆上具有高比表面积的载体， 经过滤、 干燥、 焙烧处理 后得到带磁性核的载体， 再利用浸渍法将强酸固体酸分散到具备磁性的 载体表面， 经过滤、 干燥， 即可得到具备磁性及高活性的双壳式结构磁 性固体酸催化剂。 2. The present invention also relates to a method for preparing a magnetic superfine solid acid catalyst with a double shell structure. The magnetic core is prepared by an improved coprecipitation method, and is characterized in that the surface of the magnetic core is coated with a sol-gel method. A carrier with a high specific surface area can be filtered, dried, and roasted to obtain a carrier with a magnetic core, and then a strong acid solid acid is dispersed on the surface of the carrier with magnetic properties by the immersion method. After filtering and drying, a magnetic and high carrier can be obtained. Active double shell magnetic solid acid catalyst.
3. 权利要求 2 所述的双壳式结构磁性超细固体酸催化剂的制备方 法： 其具体制备步骤如下： 3. The method for preparing a double-shell structure magnetic ultra-fine solid acid catalyst according to claim 2: The specific preparation steps are as follows:
A. 按照专利申请 00133474.3中的方法制备磁性核载体  A. Preparation of magnetic core carrier according to the method in patent application 00133474.3
B . 将强酸固体酸溶液按照强酸固体酸比磁性核载体为 0.25~1 : 1 的 质量比， 在恒温条件下将磁性核载体粉末浸渍入强酸固体酸溶液， 浸渍 2-6小时后， 过滤分离， 110Ό干燥后即得已负载强酸固体酸的磁性催化 剂。  B. The strong acid solid acid solution is immersed in the strong acid solid acid solution at a constant temperature according to a mass ratio of the strong acid solid acid to the magnetic core carrier of 0.25 to 1: 1. After soaking for 2-6 hours, it is separated by filtration. After being dried at 110 ° C, a magnetic catalyst having a strong acid solid acid supported thereon was obtained.
4. 权利要求 1、 3所述的双壳式结构磁性超细固体酸催化剂及其制 备方法， 所包覆的具有高比表面积的载体应是能用原料水解制备出的载 体。 4. The magnetic superfine solid acid catalyst with double shell structure according to claim 1 and 3, and a method for preparing the same, wherein the support with a high specific surface area is a support that can be prepared by hydrolyzing raw materials.
5. 权利要求 4所述的双壳式结构磁性超细固体酸催化剂及其制备 法， 优选的可水解制备的载体是： Si02、 Zr02、 AI203、 Ti02。 5. The double-shell structure magnetic ultra-fine solid acid catalyst according to claim 4 and preparation thereof Method, the preferred hydrolyzable supports are: Si0 2 , Zr0 2 , AI 2 0 3 , Ti0 2 .
6. 权利要求 1、 3所述的双壳式结构磁性超细固体酸催化剂及其制 方法， 所用强酸固体酸优选 Zr(S04)2、 S04 2- -Zr02、 F-Zr02。 6. The double-shell structure magnetic ultra-fine solid acid catalyst according to claim 1 and 3, and a method for preparing the same, the strong acid solid acid used is preferably Zr (S0 4 ) 2 , S0 4 2 --Zr0 2 , F-Zr0 2 .
7. 权利要求 1、 3所述的双壳式结构磁性超细固体酸催化剂及其制 方法， 优选的磁性核是 Fe304、 Co-Fe304、 Mn-Fe304或 Ni-Fe304。 7. The double-shell structure magnetic ultra-fine solid acid catalyst according to claim 1 and 3, and a method for preparing the same, the preferred magnetic core is Fe 3 0 4 , Co-Fe 3 0 4 , Mn-Fe 3 0 4 or Ni -Fe 3 0 4 .
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