WO2003090927A1 - Catalyseur acide solide surfin magnetique a structure a double coque et son procede de preparation - Google Patents

Catalyseur acide solide surfin magnetique a structure a double coque et son procede de preparation 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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WIPO (PCT)
Prior art keywords
magnetic
solid acid
carrier
double
shell structure
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PCT/CN2002/000756
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English (en)
Chinese (zh)
Inventor
Xue Duan
Zheng Chang
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Beijing University Of Chemical Technology
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Publication of WO2003090927A1 publication Critical patent/WO2003090927A1/fr

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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
    • 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
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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

Definitions

  • 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)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur acide solide surfin magnétique à structure à double coque et son procédé de préparation. Ledit catalyseur est caractérisé en ce que la surface du noyau magnétique est recouverte par un support présentant une aire spécifique et forme ainsi, avec le noyau magnétique, un support sur lequel est déposée une couche d'acide solide puissant. Ledit catalyseur est préparé par application du support présentant une aire spécifique, tel que SiO2, ZrO2, Al2O3, TiO2, etc., sur la surface du noyau magnétique constitué de Fe3O4, CO-Fe3O4, Mn-Fe3O4, ou NI-Fe3O4 ; mise en oeuvre du procédé sol-gel, puis dispersion de l'acide solide puissant Zr(SO4)2, SO42--ZrO2, etc., dans la surface du support avec induction de magnétisme, au moyen d'un procédé d'imprégnation. Ce type de catalyseur acide solide à structure à double coque s'utilise principalement pour des réactions catalysées par un acide, offrant l'avantage de présenter un magnétisme et une forte activité.
PCT/CN2002/000756 2002-04-24 2002-10-25 Catalyseur acide solide surfin magnetique a structure a double coque et son procede de preparation WO2003090927A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB02117136XA CN1167504C (zh) 2002-04-24 2002-04-24 一种双壳式结构磁性超细固体酸催化剂及其制备方法
CN02117136.X 2002-04-24

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698756A (zh) * 2012-06-19 2012-10-03 华南理工大学 一种Fe3O4/TiO2纳米磁性复合体及其制备方法
EP2522426A1 (fr) * 2011-05-12 2012-11-14 King Saud University Heterogeneous catalyst for preparing carboxylic acids and method for preparing carboxylic acids
CN103464126A (zh) * 2013-06-20 2013-12-25 江南大学 二氧化锆四氧化三铁纳米颗粒的制备及其富集磷酸肽的方法
CN104815678A (zh) * 2015-04-01 2015-08-05 哈尔滨工业大学 一种具有高比表面积和强酸催化活性的硫化二氧化钛的制备方法
CN105642315A (zh) * 2015-12-29 2016-06-08 龙建新 一种固体酸催化剂的工业制备方法及其应用
CN104437566B (zh) * 2014-12-04 2016-09-07 江南大学 一种核壳结构的Fe3O4@SiO2纳米粒子负载型Cu催化剂及其制备方法和应用
CN109092370A (zh) * 2018-08-03 2018-12-28 华南农业大学 一种水稻硅源磁性固体酸催化剂及其制备方法和在催化玉米芯制备还原糖中的应用
CN109879327A (zh) * 2019-01-25 2019-06-14 重庆科技学院 一种利用金属氧化物催化制备Fe3O4的方法
CN111569912A (zh) * 2020-06-22 2020-08-25 南通百川新材料有限公司 一种乙酸正丁酯生产用催化剂的改进方法
CN112958129A (zh) * 2021-02-03 2021-06-15 中国科学院兰州化学物理研究所 一种固体酸催化剂及其制备方法与应用

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CN101543786B (zh) * 2008-03-27 2012-05-30 中国石油化工股份有限公司 一种磁性固体酸催化剂及其制备方法和应用
CN102380402A (zh) * 2011-08-25 2012-03-21 华北电力大学 钛基磁性固体超强酸催化剂及其制备及其催化热解纤维素或生物质制备左旋葡萄糖酮的方法
CN102532206B (zh) * 2011-12-20 2015-04-15 华北电力大学 利用固体磷酸催化热解纤维素制备左旋葡萄糖酮的方法
CN102516322B (zh) * 2011-12-20 2015-06-10 华北电力大学 利用磁性固体磷酸催化剂制备左旋葡萄糖酮的方法
CN104209124A (zh) * 2013-05-29 2014-12-17 华东理工大学 一种酯化催化剂制备及其应用
CN103288607A (zh) * 2013-06-26 2013-09-11 苏州奥索特新材料有限公司 一种聚甲氧基二甲醚的合成方法
CN105921157A (zh) * 2016-04-28 2016-09-07 中国林业科学研究院亚热带林业研究所 一种固体酸催化剂及其制备方法和应用
CN107353202A (zh) * 2017-07-07 2017-11-17 中国矿业大学 一种固体酸催化剂催化糖转化制备乙酰丙酸酯的方法
CN109621964B (zh) * 2018-12-20 2020-07-14 华中科技大学 一种纳米Na/Fe复合型固体酸催化剂及其制备方法和应用
CN110787801B (zh) * 2019-11-05 2021-10-01 江南大学 一种磁性固体酸催化剂的合成方法及其应用
CN111167452B (zh) * 2020-01-08 2023-03-17 山东交通学院 一种船用柴油机尾气用催化剂载体的制造方法

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2522426A1 (fr) * 2011-05-12 2012-11-14 King Saud University Heterogeneous catalyst for preparing carboxylic acids and method for preparing carboxylic acids
CN102698756A (zh) * 2012-06-19 2012-10-03 华南理工大学 一种Fe3O4/TiO2纳米磁性复合体及其制备方法
CN103464126A (zh) * 2013-06-20 2013-12-25 江南大学 二氧化锆四氧化三铁纳米颗粒的制备及其富集磷酸肽的方法
CN104437566B (zh) * 2014-12-04 2016-09-07 江南大学 一种核壳结构的Fe3O4@SiO2纳米粒子负载型Cu催化剂及其制备方法和应用
CN104815678A (zh) * 2015-04-01 2015-08-05 哈尔滨工业大学 一种具有高比表面积和强酸催化活性的硫化二氧化钛的制备方法
CN105642315A (zh) * 2015-12-29 2016-06-08 龙建新 一种固体酸催化剂的工业制备方法及其应用
CN105642315B (zh) * 2015-12-29 2018-01-05 龙建新 一种固体酸催化剂的工业制备方法及其应用
CN109092370A (zh) * 2018-08-03 2018-12-28 华南农业大学 一种水稻硅源磁性固体酸催化剂及其制备方法和在催化玉米芯制备还原糖中的应用
CN109879327A (zh) * 2019-01-25 2019-06-14 重庆科技学院 一种利用金属氧化物催化制备Fe3O4的方法
CN111569912A (zh) * 2020-06-22 2020-08-25 南通百川新材料有限公司 一种乙酸正丁酯生产用催化剂的改进方法
CN112958129A (zh) * 2021-02-03 2021-06-15 中国科学院兰州化学物理研究所 一种固体酸催化剂及其制备方法与应用

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CN1167504C (zh) 2004-09-22

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