WO2004009233A1 - Magnetic nanometer solid base catalyst and its preparation method - Google Patents

Magnetic nanometer solid base catalyst and its preparation method Download PDF

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Publication number
WO2004009233A1
WO2004009233A1 PCT/CN2003/000592 CN0300592W WO2004009233A1 WO 2004009233 A1 WO2004009233 A1 WO 2004009233A1 CN 0300592 W CN0300592 W CN 0300592W WO 2004009233 A1 WO2004009233 A1 WO 2004009233A1
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magnetic
catalyst
mixed
salt
solution
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PCT/CN2003/000592
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French (fr)
Chinese (zh)
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Xue Duan
Hui Zhang
Rong Qi
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Beijing University Of Chemical Technology
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Priority to AU2003255081A priority Critical patent/AU2003255081A1/en
Publication of WO2004009233A1 publication Critical patent/WO2004009233A1/en
Priority to US11/040,408 priority patent/US7247598B2/en

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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
    • B01J23/002—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
    • B01J23/007—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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding

Definitions

  • the invention relates to a magnetic nano solid base catalyst and a preparation method thereof.
  • heterogeneous catalysis In the field of catalytic research, homogeneous catalysis has gradually transitioned to heterogeneous catalysis.
  • the use of solid bases instead of liquid bases for catalysis has the following advantages: (1) high activity, high selectivity, and high product purity; (2) the catalyst is easy to separate (3) less corrosive to equipment, less waste liquid generated, and reduce environmental pollution.
  • heterogeneous catalysis systems often have disadvantages such as small reaction interface and large mass transfer resistance, which make the catalytic performance significantly lower than that of homogeneous systems, or cannot be widely used for other reasons.
  • Hydrotalcite (LDH) compounds have shown good application prospects in the field of heterogeneous catalysis.
  • LDH Hydrotalcite
  • the nano-sized composite metal oxide particles are extremely small in size, have a large specific surface area, can be in full contact with the substrate, achieve efficient catalytic activity, and have good thermal stability.
  • the disadvantage is that the dispersion in the liquid-solid catalyst system is poor, and it is difficult to separate and recover.
  • the catalyst particles are small, resulting in large bed resistance, which brings difficulties to its industrial application.
  • EP0421677A1, EP0421678A1 describe alkaline hydrotalcite and calcined hydrotalcite as solid base catalysts for the synthesis of alcohol ethers.
  • the general formula of hydrotalcite is [M 2+ a N 3+ b (OH) ( 2a + 3b) ] [X ] b , where M is a divalent metal ion, N is a trivalent metal ion, and X is an equivalent anion, which becomes a Mg-Al-0 complex after firing.
  • the invention provides a nano-scale solid alkali catalyst with magnetic properties, that is, a catalyst coated with a solid alkali active component on the outside of a magnetic core.
  • the reaction can be achieved by controlling the intensity and direction of a magnetic field applied by an external magnetic field.
  • the preparation method of the catalyst is to firstly perform a rapid nucleation reaction using a liquid-liquid reaction all-reverse liquid film reactor (see patent application: 00132145.5) to prepare a nano-level magnetic core, and mix the magnetic core with a corresponding salt solution.
  • An all-reverse liquid film reactor is used to perform a rapid nucleation reaction to obtain a hydrotalcite containing a magnetic core.
  • the hydrotalcite is converted to a corresponding solid alkali composite oxide by high-temperature roasting, and the magnetic core is coated in the composite oxide.
  • the chemical formula of the magnetic nano solid base catalyst prepared by the present invention is:
  • M is any one of the divalent metal ions Mg 2+ , Ni 2+ , Zn 2+ , Ca 2+ or Co 2+ , and N is the trivalent metal ion Fe 3+ , V 3+ , Al 3+ or Gr ⁇ any one of them; M is any one of Mg "Cu 2+ , Ba 2 ⁇ Ni 2+ trivalent metal ion, M and M may be the same or different;
  • M, Fe 2 0 4 is a magnetic species
  • MN- (O) is a composite oxide formed by baking the corresponding hydrotalcite, which is coated on M, Fe 2 0 4 .
  • the preparation method of the catalyst is:
  • the soluble inorganic salt of M, and the soluble inorganic salt of ferric iron are formulated into a mixed solution, wherein the molar ratio of M7Fe 3+ is 0.5 2.0, the molar concentration of M is 0.1-2.5M, and the molar concentration of Fe 3+ is 0.2- 5.0M; a mixed alkali solution was prepared with NaOH and Na 2 C0 3 , wherein the molar concentration of NaOH is 0.1-5.0M, and the molar concentration of Na 2 C0 3 is 0.1 ⁇ 4.8M;
  • the above salt solution and alkaline solution are simultaneously poured into an all-reverse liquid film reactor (see patent application 00132145), the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the materials in the reactor is 1 to 8 minutes, which are dispersed by the liquid separator. After that, mix thoroughly in the gap between the rotor and the stator, discharge to the crystallization kettle through the discharge port, and crystallize at 80 ⁇ 120 ° C for 2 ⁇ 10h at a constant temperature. Repeat suction filtration, washing, and drying. It is dried and calcined at a high temperature of 800 ⁇ 1000 ° C to obtain M, Fe 2 0 4 powder with a particle size range of 20 ⁇ 80nm. The amount of alkali solution should be added so that the PH value of the mixed liquid is 8.5 ⁇ 11.0.
  • a mixed alkali solution was prepared with NaOH and Na 2 CO ⁇ e.
  • the molar concentration of NaOH is 0.1-5.0M, and the molar concentration of Na 2 C0 3 is 0.1-4.8M;
  • the salt solution and the alkaline solution are simultaneously poured into an all-reverse liquid film reactor, and the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the material in the reactor is 1 to 8 minutes, and the liquid is passed through the gap between the rotor and the stator Mix thoroughly at the place, drain to the crystallization kettle through the discharge port, and crystallize at 80 ⁇ 120 ° C for 4 ⁇ : LOh, repeatedly suction filtration, washing, and drying to obtain hydrotalcite MN- with magnetic core M, Fe 2 0 4 LDH IM, Fe 2 0 4 .
  • the amount of alkali solution should be added so that the PH value of the mixed liquid is 8.5-11.0.
  • MN-LDH / M and Fe204 are calcined at 400 ⁇ 600 ° C for 2 ⁇ 5 hours, and the heating rate is 10 ° C / min, to obtain a magnetic solid base catalyst MN- (O) / M with a particle size range of 30 ⁇ 100nm.
  • the trivalent salt of iron in step (1) may be: Fe 2 (S0 4 ) 3 , Fe Cl 3 ⁇ Fe (N0 3 ) 3 ; M, the salt may be: M, S0 4 , M, C1 2 , Any of M, (N0 3 ) 2 , M, preferably Zn 2+ , Mg 2+ or Ni 2+ .
  • the preparation of magnetic cores and solid base catalysts uses a fully reversed liquid film reactor for rapid nucleation reaction, the reactants can be fully contacted and collided instantaneously, the nucleation reaction is completed instantaneously, and the crystal nuclei are synchronized. Growth, so the resulting magnetic core and solid base catalyst are both nano-sized particles.
  • the particle size of the catalyst is 30 ⁇ 100 nm, and its magnetic properties are as follows: the coercive force He is 120 ⁇ 108A / m, and the specific saturation magnetization is 2 ⁇ 18 A / m.
  • the magnetic precursor MgAl-LDH / MgFe 2 0 4 was calcined in an air atmosphere at 600 ° C. for 2 hours, and the temperature rising rate was 10 ° C./minute to obtain a magnetic solid base catalyst MgAl (0) / MgFe 2 0 4 .
  • the measured grain size of the catalyst is in the range of 30-85 nm, and the maximum grain size is 62 nm.
  • the coercive force He value is 120.0A / m, and the specific saturation magnetization 6 * is 2.1A / m.
  • the gelatinous substance was poured into a crystallization kettle, and was crystallized at a constant temperature of 100 ° C for 6 hours, and then repeatedly filtered with suction and washed to a pH value of 7.
  • the filter cake was dried in an oven for 24 hours to obtain the magnetic precursor ZnAl-LDH / NiFe. 2 0 4 .
  • the magnetic precursor ZnAl-LDH / NiFe 2 0 4 was fired in an air atmosphere at 600 ° C. for 5 hours, and the temperature rising rate was 10. C / min to obtain a magnetic solid base catalyst ZnAl (0) / NiFe 2 0 4 .
  • the measured grain size is in the range of 30 ⁇ 80nm, and the maximum grain size is 58nm.
  • the coercive force He value is 110.5A / m, and the specific saturation magnetization 6 x is 3.5A / m.
  • the mixed solution stayed in the reactor for 2 minutes, and then the obtained slurry was poured into a crystallization kettle, and was crystallized at 100 ° C for 6 hours, and then repeatedly filtered and washed to a pH value of 7, and the filter cake was placed at 70 ° C. After drying in an oven for 24 hours, it was pulverized, and then calcined in an air atmosphere at 900 ° C for 2 hours. The heating rate was 10 ° C / min, and the magnetic core NiFe 2 0 4 was obtained .
  • magnesium-aluminum molar ratio of 4 1, weigh 41,03g Mg (N0 3 ) 2 -6H 2 0 and 15.01g ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 in 130ml deionized water to form a mixed salt Solution, and at a molar ratio of Mg (N0 3 ) 2 .6H 2 0 / NiFe 2 0 4 to 5.00, add the prepared NiFe 2 0 4 powder to the mixed salt solution, stir and mix uniformly; weigh 12.8 g NaOH and 8.48g Na 2 C0 3 were dissolved in BOml deionized water to prepare a mixed alkali solution; the two solutions were simultaneously poured into the opened all-reverse liquid film reactor.
  • the rotor speed was controlled at 7000 rpm, and the reaction mixture was Remain in the reactor for 2min, then pour the obtained gum into the crystallization kettle, crystallize at 100 ° C for 6h, and then repeat Suction filtration, washing until the pH is equal to 7, and drying the filter cake in an oven for 24 hours to obtain the magnetic precursor MgAl-LD Li iFe 2 0 4 .
  • the magnetic precursor MgAl-LDH / NiFe 2 0 4 was calcined in an air atmosphere at 550 ° C. for 2 hours, and the temperature rising rate was 10 ° C./minute to obtain a magnetic solid base catalyst MgAl (0) / NiFe 2 0 4 .
  • the measured grain size is in the range of 35 ⁇ 90nm.
  • the maximum grain size is 65nm.
  • the coercive force He value was 130.2 A / m, and the specific saturation magnetization 6 x was 2.6 A / m.

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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 a magnetic nanometer solid base catalyst and its preparation method. The magnetic core of the catalyst is wrapped by solid base active component Firstly utilize the method that all return mixing-liquid membrane reactor which is based on liquid-liquid reaction, is adopted to carry out qulick nucleation reaction to prepare the nanometer magnetic core, secondly mix it with relevant salt solution, use all return mixing-liquid membrane reactor to carry out qulick nucleation reaction, then get hydrotalcite which contains magnetic core, calcining it to transfer into solid base composite oxide, the magnetic core is wrapped into composite oxide. The characteristic of the catalyst is: nanometer size and high specific area, high activity and selectivity in catalytic reaction. Since the catalyst is magnetic it can be gathered to recover and highly dispersed in reaction system by extra magnetic field. The catalyst can be use in base-catalysed organic reaction, such as alcohol ether synthesis, ester exchange, aldehyde ketone condensation etal.

Description

一种磁性纳米固体碱催化剂及其制备方法 技术领域  Magnetic nano solid base catalyst and preparation method thereof
本发明涉及一种磁性纳米固体碱催化剂及其制备方法。 技术背景  The invention relates to a magnetic nano solid base catalyst and a preparation method thereof. technical background
在催化研究领域中， 均相催化已经逐步向多相催化过渡， 使用固体碱 代替液体碱进行催化具有下述优点： （1 ) 高活性、 高选择性、 产物纯度高； ( 2 )催化剂易于分离； （3 )对设备的腐蚀性小， 产生的废液少， 减少环境 污染。 但是多相催化体系往往存在反应界面小、 传质阻力大等弊端， 使得 催化性能较均相体系有大幅度降低， 或由于其它一些原因无法广泛应用。  In the field of catalytic research, homogeneous catalysis has gradually transitioned to heterogeneous catalysis. The use of solid bases instead of liquid bases for catalysis has the following advantages: (1) high activity, high selectivity, and high product purity; (2) the catalyst is easy to separate (3) less corrosive to equipment, less waste liquid generated, and reduce environmental pollution. However, heterogeneous catalysis systems often have disadvantages such as small reaction interface and large mass transfer resistance, which make the catalytic performance significantly lower than that of homogeneous systems, or cannot be widely used for other reasons.
水滑石 （LDH )类化合物在多相催化研究领域中展现出良好的应用前 景， 通过控制前体晶粒尺寸及其分布并调变孔结构可有效的发挥择形作 用； 经前体煅烧而成的纳米级复合金属氧化物颗粒尺寸极其细小， 比表面 积 4艮大， 能与基质充分接触， 实现高效的催化活性， 而且具有很好的热稳 定性。 缺点是在液固催化体系分散性差， 难以分离和回收； 在气固催化体 系催化剂颗粒细小， 导致床层阻力大， 为其工业应用带来了困难。  Hydrotalcite (LDH) compounds have shown good application prospects in the field of heterogeneous catalysis. By controlling the precursor grain size and distribution and adjusting the pore structure, it can effectively play a shape-selective role. The nano-sized composite metal oxide particles are extremely small in size, have a large specific surface area, can be in full contact with the substrate, achieve efficient catalytic activity, and have good thermal stability. The disadvantage is that the dispersion in the liquid-solid catalyst system is poor, and it is difficult to separate and recover. In the gas-solid catalyst system, the catalyst particles are small, resulting in large bed resistance, which brings difficulties to its industrial application.
EP0421677A1 , EP0421678A1 描述了碱性水滑石及经过焙烧的水滑石 作为合成醇醚的固体碱催化剂，水滑石的通式为 [M2+ aN3+ b ( OH )(2a+3b)] [X] b, 其中 M为二价金属离子， N为三价金属离子， X为等价阴离子， 经过焙烧 则变成 Mg-Al-0复合物。 但都没有谈到如何解决催化剂的分散、 分离回收 等问题。 发明内容 EP0421677A1, EP0421678A1 describe alkaline hydrotalcite and calcined hydrotalcite as solid base catalysts for the synthesis of alcohol ethers. The general formula of hydrotalcite is [M 2+ a N 3+ b (OH) ( 2a + 3b) ] [X ] b , where M is a divalent metal ion, N is a trivalent metal ion, and X is an equivalent anion, which becomes a Mg-Al-0 complex after firing. However, there is no talk about how to solve the problems of catalyst dispersion, separation and recovery. Summary of the invention
本发明提供一种带有磁性的纳米级固体碱催化剂， 即一种在磁性核外 包覆了固体碱活性组分的催化剂， 其在使用过程中可通过控制外加磁场的 磁场强度和方向实现反症体系中催化剂颗粒的高度分散及反应后催化剂的 富集回收。 该催化剂的制备方法是， 先采用液-液反应的全反混液膜反应器 进行快速成核反应的方法（见专利申请： 00132145.5 ) 制备纳米级磁性核， 将该磁性核与相应的盐溶液混合， 再利用全反混液膜反应器进行快速成核 反应， 得到含有磁性核的水滑石， 经高温焙烧水滑石转变为相应的固体碱 复合氧化物 , 磁性核被包覆在复合氧化物内。 The invention provides a nano-scale solid alkali catalyst with magnetic properties, that is, a catalyst coated with a solid alkali active component on the outside of a magnetic core. During use, the reaction can be achieved by controlling the intensity and direction of a magnetic field applied by an external magnetic field. Dispersion of catalyst particles Enrichment and recycling. The preparation method of the catalyst is to firstly perform a rapid nucleation reaction using a liquid-liquid reaction all-reverse liquid film reactor (see patent application: 00132145.5) to prepare a nano-level magnetic core, and mix the magnetic core with a corresponding salt solution. An all-reverse liquid film reactor is used to perform a rapid nucleation reaction to obtain a hydrotalcite containing a magnetic core. The hydrotalcite is converted to a corresponding solid alkali composite oxide by high-temperature roasting, and the magnetic core is coated in the composite oxide.
本发明所制备的磁性纳米固体碱催化剂的化学式为：  The chemical formula of the magnetic nano solid base catalyst prepared by the present invention is:
M善 (0)/ M，Fe204 Mshan (0) / M ， Fe 2 0 4
其含量为：  Its content is:
M，Fe204: 15%~38%； M, Fe 2 0 4 : 15% ~ 38%;
M-N-(O): 85%~62  M-N- (O): 85% ~ 62
其中 M为二价金属离子 Mg2+ 、 Ni 2+ 、 Zn2+ 、 Ca2+或 Co2+其中的任 何一种， N为三价金属离子 Fe3+、 V3+、 Al3+或 Gr^其中的任何一种； M，为 Mg" Cu2+、 Ba2\ Ni2+三价金属离子其中的任何一种， M与 M，可以相同 也可以不同； Where M is any one of the divalent metal ions Mg 2+ , Ni 2+ , Zn 2+ , Ca 2+ or Co 2+ , and N is the trivalent metal ion Fe 3+ , V 3+ , Al 3+ or Gr ^ any one of them; M is any one of Mg "Cu 2+ , Ba 2 \ Ni 2+ trivalent metal ion, M and M may be the same or different;
M，Fe204为磁性物种， M-N-(O)为包覆在 M，Fe204外的由相应的水滑石 经焙烧形成的复合氧化物。 M, Fe 2 0 4 is a magnetic species, and MN- (O) is a composite oxide formed by baking the corresponding hydrotalcite, which is coated on M, Fe 2 0 4 .
该催化剂的制备方法是：  The preparation method of the catalyst is:
( 1 ). 纳米磁性核 M'Fe204粉体制备 (1). Preparation of nanometer magnetic core M'Fe 2 0 4 powder
将 M，的可溶性无机盐和三价铁的可溶性无机盐配制成混合溶液， 其中 M7Fe3+摩尔比为 0.5 2.0， M，的摩尔浓度为 0.1~2.5M, Fe3+的摩尔浓度为 0.2-5.0M ； 用 NaOH和 Na2C03配制混合碱溶液,其中 NaOH摩尔浓度为 0.1-5.0M, Na2C03摩尔浓度为 0.1〜4.8M; The soluble inorganic salt of M, and the soluble inorganic salt of ferric iron are formulated into a mixed solution, wherein the molar ratio of M7Fe 3+ is 0.5 2.0, the molar concentration of M is 0.1-2.5M, and the molar concentration of Fe 3+ is 0.2- 5.0M; a mixed alkali solution was prepared with NaOH and Na 2 C0 3 , wherein the molar concentration of NaOH is 0.1-5.0M, and the molar concentration of Na 2 C0 3 is 0.1 ~ 4.8M;
将上述盐溶液和碱溶液同时倒入全反混液膜反应器 （见专利申请 00132145 ), 控制转子的转速为 1000~8000rpm， 物料在反应器内停留时间 为 l-8min, 经液体分部器分散后， 在转子与定子之间的缝隙处充分混合， 经出料口排到晶化釜， 在 80~120°C恒温晶化 2〜10h， 反复抽滤、 洗涤， 干 燥， 经 800〜1000°C高温焙烧得到粒径范围在 20~80nm的 M，Fe204粉体。 碱溶液的加入量应使混合后的液体的 PH值在 8.5~11.0。 The above salt solution and alkaline solution are simultaneously poured into an all-reverse liquid film reactor (see patent application 00132145), the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the materials in the reactor is 1 to 8 minutes, which are dispersed by the liquid separator. After that, mix thoroughly in the gap between the rotor and the stator, discharge to the crystallization kettle through the discharge port, and crystallize at 80 ~ 120 ° C for 2 ~ 10h at a constant temperature. Repeat suction filtration, washing, and drying. It is dried and calcined at a high temperature of 800 ~ 1000 ° C to obtain M, Fe 2 0 4 powder with a particle size range of 20 ~ 80nm. The amount of alkali solution should be added so that the PH value of the mixed liquid is 8.5 ~ 11.0.
( 2 )、 磁性前体 M-N- LDH I M'Fe204的制备 (2) Preparation of magnetic precursor MN-LDH I M'Fe 2 0 4
将可溶性二价无机金属盐 M2 Cn')2/n和可溶性三价无机金属盐 Ν3χΧη-)3/η 配制成混合盐溶液， Μ2+ Ν3+的摩尔比为 2〜4, 二价金属离子的摩尔浓度为 0.2-2.5Μ, 三价金属离子的摩尔浓度为 1.6〜4.5Μ; 按 M，Fe204与上述混合 盐溶液中二价无机金属盐的质量比为 1 : 17.1〜5.0 的比例， 称取相应的 M，Fe204粉体加入混合盐溶液中， 搅拌混和均匀； Soluble divalent inorganic metal M 2 C n ') 2 / n and soluble trivalent inorganic metal salt Ν 3 χΧ η -) 3 / η formulated as a mixed salt solution, Μ 2+ Ν 3+ molar ratio of 2 ~ 4, the molar concentration of divalent metal ions is 0.2-2.5M, the molar concentration of trivalent metal ions is 1.6 ~ 4.5M; according to M, the mass ratio of Fe 2 0 4 to the divalent inorganic metal salt in the mixed salt solution is 1: 17.1 ~ 5.0 ratio, weigh the corresponding M, Fe 2 0 4 powder into the mixed salt solution, stir and mix well;
用 NaOH和 Na2CO^e<制混合碱溶液。 NaOH摩尔浓度为 0.1-5.0M, Na2C03摩尔浓度为 0.1~4.8M; A mixed alkali solution was prepared with NaOH and Na 2 CO ^ e. The molar concentration of NaOH is 0.1-5.0M, and the molar concentration of Na 2 C0 3 is 0.1-4.8M;
将盐溶液和碱溶液同时倒入全反混液膜反应器， 控制转子的转速为 1000~8000rpm, 物料在反应器内停留时间为 l-8min, 经液体 ^器^ 在转子与定子之间的缝隙处充分混合， 经出料口排到晶化釜， 在 80〜120°C恒 温晶化 4〜： LOh, 反复抽滤、 洗涤， 干燥得到带磁性核 M，Fe204的水滑石 M-N- LDH I M，Fe204。 碱溶液的加入量应使混合后的液体的 PH值在 8.5-11.0 。 The salt solution and the alkaline solution are simultaneously poured into an all-reverse liquid film reactor, and the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the material in the reactor is 1 to 8 minutes, and the liquid is passed through the gap between the rotor and the stator Mix thoroughly at the place, drain to the crystallization kettle through the discharge port, and crystallize at 80 ~ 120 ° C for 4 ~: LOh, repeatedly suction filtration, washing, and drying to obtain hydrotalcite MN- with magnetic core M, Fe 2 0 4 LDH IM, Fe 2 0 4 . The amount of alkali solution should be added so that the PH value of the mixed liquid is 8.5-11.0.
( 3 )、 催化剂 M-N-(O)/ M'Fe204的制备 (3) Preparation of catalyst MN- (O) / M'Fe 2 0 4
将上述 M-N- LDH / M，Fe204于 400〜600°C中焙烧 2~5小时， 升温速 率 10°C/分， 得到粒径范围在 30〜100nm的磁性固体碱催化剂 M-N-(O)/ M'Fe204o The above-mentioned MN-LDH / M and Fe204 are calcined at 400 ~ 600 ° C for 2 ~ 5 hours, and the heating rate is 10 ° C / min, to obtain a magnetic solid base catalyst MN- (O) / M with a particle size range of 30 ~ 100nm. 'Fe204 o
步驟（1 ) 中铁的三价盐可以是： Fe2(S04)3、 Fe Cl3 ^ Fe (N03)3 何一种； M，盐可以是： M，S04、 M，C12、 M，(N03)2中的任何一种， M，优选 Zn2+、 Mg2+或 Ni2+。 The trivalent salt of iron in step (1) may be: Fe 2 (S0 4 ) 3 , Fe Cl 3 ^ Fe (N0 3 ) 3 ; M, the salt may be: M, S0 4 , M, C1 2 , Any of M, (N0 3 ) 2 , M, preferably Zn 2+ , Mg 2+ or Ni 2+ .
步骤（2 ) 中 X为 Cl-、 S04 2-、 N03-、 C03 2_中的任何一种， n为阴离子 X的价态, n=l或 2。 In step (2), X is any one of Cl-, S0 4 2- , N0 3- , and C0 3 2 _, n is a valence state of anion X, and n = 1 or 2.
由于制备磁性核和固体碱催化剂均采用全反混液膜反应器进行快速成 核反应， 可使反应物瞬时充分接触、 碰撞， 成核反应瞬时完成， 晶核同步 增长， 所以得到的磁性核和固体碱催化剂均为纳米尺寸的粒子。 在合成Because the preparation of magnetic cores and solid base catalysts uses a fully reversed liquid film reactor for rapid nucleation reaction, the reactants can be fully contacted and collided instantaneously, the nucleation reaction is completed instantaneously, and the crystal nuclei are synchronized. Growth, so the resulting magnetic core and solid base catalyst are both nano-sized particles. In synthesis
M-N-LDH/ M'Fe204过程中， 由于大量晶核在磁核 M'Fe204表面于相同晶 化条件下同步生长， 保证了包覆结构的均匀性。 该催化剂粒径在 30~100 nm,其磁性能指标：矫顽力 He为 120 ~108A/m,比饱和磁化强度 为 2~18 A/m。 由于该催化剂具有磁性， 在使用过程中可通过控制外加磁场的磁场 强度和方向实现反应体系中催化剂颗粒的高度分散及反应后催化剂的富集 回收， 从而解决了以前该类催化剂的难于分散、 回收的难题。 具体实施方案 During the MN-LDH / M'Fe 2 0 4 process, since a large number of crystal nuclei grow simultaneously on the surface of the magnetic core M'Fe 2 0 4 under the same crystallization conditions, the uniformity of the coating structure is guaranteed. The particle size of the catalyst is 30 ~ 100 nm, and its magnetic properties are as follows: the coercive force He is 120 ~ 108A / m, and the specific saturation magnetization is 2 ~ 18 A / m. Due to the magnetic properties of the catalyst, it is possible to achieve high dispersion of catalyst particles in the reaction system and enrichment and recovery of the catalyst after the reaction by controlling the magnetic field strength and direction of the applied magnetic field during use, thereby solving the difficulty of dispersing and recovering such catalysts in the past. Puzzle. Specific implementation plan
实施例 1  Example 1
( 1 )磁性核 MgFe204纳米粉体的制备 (1) Preparation of magnetic core MgFe 2 0 4 nano powder
以镁 尔比为 1: 2的比例， 称取 8.46gMg(N03)2'6H20和 27.07gFe (Ν03)3·9Η20溶于去 130ml离子水中配成混合盐溶液， 称取 6.40gNaOH和 14.20gNa2CO3溶于 130ml去离子水中配成混合减溶液； 将盐溶液和碱溶液 同时倒入已开启的全反混液膜反应器中， 转子的转速控制在 3000rpm, 反 应混合液在反应器内停留 5min， 再将得到的浆液倒入晶化釜， 于 100°C下 恒温晶化 6h， 然后反复抽滤、 洗涤至 pH值等于 7， 将滤饼置于 70°C烘箱 千燥 24h后研细， 再于 900°C、 空气氛中焙烧 2h, 升温速率 10°C/分， 制 得磁核 MgFe204; With a molar ratio of 1: 2, 8.46gMg (N0 3 ) 2 '6H 2 0 and 27.07gFe (N0 3 ) 3 · 9Η 2 0 were dissolved in 130 ml of ionized water to prepare a mixed salt solution. Weighed 6.40g of NaOH and 14.20g of Na 2 CO 3 were dissolved in 130ml of deionized water to prepare a mixed minus solution; the salt solution and the alkaline solution were simultaneously poured into the opened all-reverse liquid film reactor, and the speed of the rotor was controlled at 3000 rpm, and the reaction mixture was Stay in the reactor for 5min, then pour the obtained slurry into the crystallization kettle, and crystallize at 100 ° C for 6h, then repeatedly filter and wash until the pH is equal to 7, and place the filter cake in a 70 ° C oven. Grinded after drying for 24h, and then calcined at 900 ° C in an air atmosphere for 2h at a heating rate of 10 ° C / min to obtain magnetic core MgFe 2 0 4 ;
( 2 )磁性前体 MgAl-LDH/MgFe204的制备 (2) Preparation of magnetic precursor MgAl-LDH / MgFe 2 0 4
以镁铝摩尔比为 3:1 的比例， 称取 38.46gMg(N03)2.6H20 和 18.78gAl(N03)3-9H20 溶于 130ml 去离子水中配成混合盐溶液， 并以 Mg(N03)2'6H20/MgFe204摩尔比为 17.10的比例， 将制得的 MgFe204粉体 加入混合盐溶液中， 搅拌混和均匀； 称取 12.8gNaOH和 10.6gNa2CO3溶于 130ml去离子水中配成混合碱溶液； 将上述两种溶液同时倒入已开启的全 反混液膜反应器中， 转子的转速控制在 3000rpm, 反应混合液在反应器内 停留 5.0min， 再将得到的胶状物倒入晶化釜， 于 100°C下恒温晶化 6h, 然 后反复抽滤、 洗涤至 pH值等于 7, 将滤饼置于供箱干燥 24h即得磁性前 体 MgAl-LDH/ MgFe204„ With a molar ratio of magnesium to aluminum of 3: 1, weigh 38.46gMg (N0 3 ) 2 .6H 2 0 and 18.78gAl (N0 3 ) 3 -9H 2 0 in 130ml deionized water to prepare a mixed salt solution, and At a ratio of Mg (N0 3 ) 2 '6H 2 0 / MgFe 2 0 4 to 17.10, the prepared MgFe 2 0 4 powder was added to the mixed salt solution, stirred and mixed uniformly; 12.8 g of NaOH and 10.6 g of Na were weighed. 2 CO 3 was dissolved in 130 ml of deionized water to prepare a mixed alkali solution; the two solutions were simultaneously poured into the opened all-reverse liquid film reactor, the speed of the rotor was controlled at 3000 rpm, and the reaction mixture was in the reactor. Leave it for 5.0min, then pour the obtained gum into a crystallization kettle, crystallize at 100 ° C for 6h, and then repeat suction filtration and washing until the pH value is equal to 7, and put the filter cake in the supply box to dry for 24h. Magnetic precursor MgAl-LDH / MgFe 2 0 4 „
( 3 )催化剂 MgAl(0)/MgFe204的制备 (3) Preparation of catalyst MgAl (0) / MgFe 2 04
将磁性前体 MgAl-LDH/ MgFe204于 600°C空气氛中焙烧 2小时， 升温 速率 10°C/分， 得到磁性固体碱催化剂 MgAl(0)/ MgFe204。 The magnetic precursor MgAl-LDH / MgFe 2 0 4 was calcined in an air atmosphere at 600 ° C. for 2 hours, and the temperature rising rate was 10 ° C./minute to obtain a magnetic solid base catalyst MgAl (0) / MgFe 2 0 4 .
测得该催化剂晶粒尺寸在 30~85nm范围内， 最可几晶粒尺寸为 62nm。 矫顽力 He值为 120.0A/m, 比饱和磁化强度 6 *为 2.1A/m。 实施例 2  The measured grain size of the catalyst is in the range of 30-85 nm, and the maximum grain size is 62 nm. The coercive force He value is 120.0A / m, and the specific saturation magnetization 6 * is 2.1A / m. Example 2
( 1 )磁性核 NiFe204纳米粉体的制备 (1) Preparation of magnetic core NiFe 2 0 4 nanometer powder
以镍 /铁摩尔比为 1 : 2的比例， 称取 9.60g Ni(N03)2'6H20和 27.07g Fe (Ν03)3·9Η20溶于去 130ml离子水中配成混合盐溶液， 称取 8.00gNaOH和 14.20gNa2CO3溶于 130ml去离子水中配成混合碱溶液； 将盐溶液和碱溶液 同时倒入已开启的全反混液膜反应器中， 转子的转速控制在 5000rpm, 反 应混合液在反应器内停留 3min, 再将得到的浆液倒入晶化釜， 于 10(TC下 恒温晶化 6h, 然后反复抽滤、 洗涤至 pH值等于 7， 将滤饼置于 70°C烘箱 干燥 24h后研细， 再于 900°C、 空气氛中焙烧 2h, 升温速率 10°C/分， 制 得磁核 NiFe204o Weigh 9.60g Ni (N0 3 ) 2 '6H 2 0 and 27.07g Fe (N0 3 ) 3 · 9Η 2 0 in a molar ratio of nickel / iron of 1: 2 to dissolve in 130ml of ionized water to make a mixed salt. Solution, weigh 8.00 g of NaOH and 14.20 g of Na 2 CO 3 and dissolve in 130 ml of deionized water to prepare a mixed alkali solution; pour the salt solution and alkali solution into the opened all-reverse liquid-film reactor at the same time, and control the speed of the rotor at 5000 rpm The reaction mixture stays in the reactor for 3 minutes, and then the obtained slurry is poured into a crystallization kettle, and crystallized at a constant temperature of 10 ° C for 6 hours, and then repeatedly filtered and washed until the pH is equal to 7, and the filter cake is placed at 70 After drying in an oven at 24 ° C for 24 hours, it was pulverized, and then calcined in an air atmosphere at 900 ° C for 2 hours. The heating rate was 10 ° C / min, and the magnetic core NiFe 2 0 4o was obtained.
( 2 )磁性前体 ZnAl-LDH/NiFe2O 制备 (2) Preparation of ZnAl-LDH / NiFe 2 O magnetic precursor
以锌 /铝摩尔比为 2:1 的比例， 称取 39.56gZn(N03)2.6H20 和 25.13gWith a zinc / aluminum molar ratio of 2: 1, weigh 39.56g Zn (N0 3 ) 2 .6H 2 0 and 25.13g
Α1(Ν03)3·9Η20溶于 130ml去离子水中配成混合盐溶液，并以 Ζη(Ν03)2·6Η20 /NiFe204摩尔比为 11.40的比例，将制得的 NiFe204 体加入混合盐溶液中， 搅拌混和均匀； 称取 14.4gNaOH和 10.6gNa2CO3溶于 130ml去离子水中配 成混合减溶液； 将上述两种溶液同时倒入已开启的全反混液膜反应器中， 转子的转速控制在 5000rpm, 反应混合液在反应器内停留 3min， 再将得到 的胶状物倒入晶化釜， 于 100°C下恒温晶化 6h, 然后反复抽滤、 洗涤至 pH 值等于 7， 将滤饼置于烘箱干燥 24h即得磁性前体 ZnAl-LDH/NiFe204。 Α1 (Ν0 3) 3 · 9Η 2 0 was dissolved in 130ml of deionized water mixed salt solution is formulated, and is Ζη 2 · 6Η 2 0 2 0 4 molar ratio of (Ν0 3) / NiFe a ratio of 11.40, the resulting NiFe 2 0 4 body was added to the mixed salt solution, stirred and mixed uniformly; 14.4 g of NaOH and 10.6 g of Na 2 CO 3 were weighed and dissolved in 130 ml of deionized water to prepare a mixed subtraction solution; the two solutions were simultaneously poured into the opened all-reflection In a mixed-film reactor, the rotation speed of the rotor is controlled at 5000 rpm, and the reaction mixture is left in the reactor for 3 minutes. The gelatinous substance was poured into a crystallization kettle, and was crystallized at a constant temperature of 100 ° C for 6 hours, and then repeatedly filtered with suction and washed to a pH value of 7. The filter cake was dried in an oven for 24 hours to obtain the magnetic precursor ZnAl-LDH / NiFe. 2 0 4 .
( 3 )催化剂 ZnAl(0)/NiFe204的制备 . (3) Preparation of ZnAl (0) / NiFe 2 0 4 catalyst.
将磁性前体 ZnAl-LDH/NiFe204于 600°C空气氛中焙烧 5小时， 升温速 率 10。C/分， 得到磁性固体碱催化剂 ZnAl(0)/NiFe204。 The magnetic precursor ZnAl-LDH / NiFe 2 0 4 was fired in an air atmosphere at 600 ° C. for 5 hours, and the temperature rising rate was 10. C / min to obtain a magnetic solid base catalyst ZnAl (0) / NiFe 2 0 4 .
测得晶粒尺寸在 30~80nm范围内， 最可几晶粒尺寸为 58nm。 矫顽力 He值为 110.5A/m, 比饱和磁化强度 6 x为 3.5A/m 实施例 3 The measured grain size is in the range of 30 ~ 80nm, and the maximum grain size is 58nm. The coercive force He value is 110.5A / m, and the specific saturation magnetization 6 x is 3.5A / m. Example 3
( 1 )磁性核 NiFe204纳米粉体的制备 (1) Preparation of magnetic core NiFe 2 0 4 nanometer powder
以镍 /铁摩尔比为 1: 2的比例， 称取 9.60gZn(NO3)2'6H2O和 27.07gFe (Ν03)3·9Η20溶于去 130ml离子水中配成混合盐溶液， 称取 8.80gNaOH和 10.65gNa2CO3溶于 130ml去离子水中配成混合碱溶液； 将盐溶液和碱溶液 同时倒入已开启的全反混液膜反应器中， 转子的转速控制在 7000rpm, 反 应混合液在反应器内停留 2min， 再将得到的浆液倒入晶化釜， 于 100°C下 恒温晶化 6h, 然后反复抽滤、 洗涤至 pH值等于 7， 将滤饼置于 70°C烘箱 干燥 24h后研细， 再于 900°C、 空气氛中焙烧 2h, 升温速率 10°C/分， 制 得磁核 NiFe204„ With a nickel / iron molar ratio of 1: 2, 9.60 g of Zn (NO 3 ) 2 '6H 2 O and 27.07 g of Fe (N0 3 ) 3 · 9Η 2 0 were dissolved in 130 ml of ionized water to prepare a mixed salt solution. Weigh 8.80 g of NaOH and 10.65 g of Na 2 CO 3 and dissolve them in 130 ml of deionized water to prepare a mixed alkali solution; pour the salt solution and alkali solution into the opened all-reverse liquid film reactor at the same time. The speed of the rotor is controlled at 7000 rpm. The mixed solution stayed in the reactor for 2 minutes, and then the obtained slurry was poured into a crystallization kettle, and was crystallized at 100 ° C for 6 hours, and then repeatedly filtered and washed to a pH value of 7, and the filter cake was placed at 70 ° C. After drying in an oven for 24 hours, it was pulverized, and then calcined in an air atmosphere at 900 ° C for 2 hours. The heating rate was 10 ° C / min, and the magnetic core NiFe 2 0 4 was obtained .
( 2 )磁性前体 MgAl-LDH/NiFe204的制备 (2) Preparation of magnetic precursor MgAl-LDH / NiFe 2 0 4
以镁铝摩尔比为 4:1 的比例， 称取 41,03g Mg(N03)2-6H20和 15.01g Α1(Ν03)3·9Η20 溶于 130ml 去离子水中配成混合盐溶液， 并以 Mg(N03)2.6H20/NiFe204摩尔比为 5.00的比例， 将制得的 NiFe204粉体加入 混合盐溶液中，搅拌混和均匀；称取 12.8g NaOH和 8.48g Na2C03溶于 BOml 去离子水中配成混合碱溶液； 将上述两种溶液同时倒入已开启的全反混液 膜反应器中， 转子的转速控制在 7000rpm, 反应混合液在反应器内停留 2min, 再将得到的胶状物倒入晶化釜， 于 100°C下恒温晶化 6h， 然后反复 抽滤、 洗涤至 pH值等于 7 , 将滤饼置于烘箱干燥 24h 即得磁性前体 MgAl-LD丽 iFe204。 With a magnesium-aluminum molar ratio of 4: 1, weigh 41,03g Mg (N0 3 ) 2 -6H 2 0 and 15.01g Α1 (Ν0 3 ) 3 · 9Η 2 0 in 130ml deionized water to form a mixed salt Solution, and at a molar ratio of Mg (N0 3 ) 2 .6H 2 0 / NiFe 2 0 4 to 5.00, add the prepared NiFe 2 0 4 powder to the mixed salt solution, stir and mix uniformly; weigh 12.8 g NaOH and 8.48g Na 2 C0 3 were dissolved in BOml deionized water to prepare a mixed alkali solution; the two solutions were simultaneously poured into the opened all-reverse liquid film reactor. The rotor speed was controlled at 7000 rpm, and the reaction mixture was Remain in the reactor for 2min, then pour the obtained gum into the crystallization kettle, crystallize at 100 ° C for 6h, and then repeat Suction filtration, washing until the pH is equal to 7, and drying the filter cake in an oven for 24 hours to obtain the magnetic precursor MgAl-LD Li iFe 2 0 4 .
( 3 )催化剂 MgAl(0)/ NiFe204的制备 (3) Preparation of catalyst MgAl (0) / NiFe 2 0 4
将磁性前体 MgAl-LDH/NiFe204于 550°C空气氛中焙烧 2小时， 升温 速率 10°C/分， 得到磁性固体碱催化剂 MgAl(0)/ NiFe204。 The magnetic precursor MgAl-LDH / NiFe 2 0 4 was calcined in an air atmosphere at 550 ° C. for 2 hours, and the temperature rising rate was 10 ° C./minute to obtain a magnetic solid base catalyst MgAl (0) / NiFe 2 0 4 .
测得晶粒尺寸在 35~90nm范围内。 最可几晶粒尺寸为 65nm。 矫頑力 He值为 130.2A/m, 比饱和磁化强度 6 x为 2.6A/m。 The measured grain size is in the range of 35 ~ 90nm. The maximum grain size is 65nm. The coercive force He value was 130.2 A / m, and the specific saturation magnetization 6 x was 2.6 A / m.

Claims

权 利 要 求 Rights request
1.一种磁性纳米固体碱催化剂， 其化学式为： 1. A magnetic nano solid base catalyst, the chemical formula of which is:
M-N-(O)/ M，Fe204 MN- (O) / M, Fe 2 0 4
其含量为：  Its content is:
M'Fe204: 15%~38%； M'Fe 2 0 4 : 15% ~ 38%;
M-N-(O): 85%~62%。  M-N- (O): 85% ~ 62%.
其中 M为二价金属离子 Mg2+ 、 Ni 2+ 、 Zn2+ 、 Ca2+或 Co2+其中的任 何一种， N为三价金属离子 Fe3+、 V3+、 Al3+或 Gr3+其中的任何一种， M，为 Mg2+、 Cu2\ Ba2+、 Ni2+三价金属离子其中的任何一种， M与 M，可以相同 也可以不同； Where M is any one of the divalent metal ions Mg 2+ , Ni 2+ , Zn 2+ , Ca 2+ or Co 2+ , and N is the trivalent metal ion Fe 3+ , V 3+ , Al 3+ or Any of Gr 3+ , M is any one of Mg 2+ , Cu 2 \ Ba 2+ , Ni 2+ trivalent metal ion, M and M may be the same or different;
M，Fe204为磁性物种， M-N-(O)为包覆在 M，Fe204外的由相应的水滑 石经焙烧形成的复合氧化物。 M, Fe 2 0 4 is a magnetic species, and MN- (O) is a composite oxide formed by baking the corresponding hydrotalcite, which is coated on M, Fe 2 0 4 .
2. —种如权利要求 1所述的磁性纳米固体碱催化剂的制备方法，步骤如下： ( 1 ). 纳米磁性核 M，Fe204粉体制备 2. A method for preparing a magnetic nano solid alkali catalyst according to claim 1, the steps are as follows: (1). Preparation of nano magnetic core M, Fe 2 0 4 powder
将 M，的可溶性无机盐和三价铁的可溶性无机盐配制成混合溶液， 其 中 M7Fe3+摩尔比为 0.5〜2.0， M，的摩尔浓度为 0.1~2·5Μ， Fe3+的摩尔浓度 为 0.2〜5.0M ； 用 NaOH和 Na2C03配制混合碱溶液,其中 NaOH摩尔浓度 为 0.1~5.0M， Na2C03摩尔浓度为 0.1~4.8M; The soluble inorganic salt of M, and the soluble inorganic salt of ferric iron are formulated into a mixed solution, wherein the molar ratio of M7Fe 3+ is 0.5 to 2.0, the molar concentration of M is 0.1 to 2.5 M, and the molar concentration of Fe 3+ is 0.2 ~ 5.0M; Prepare a mixed alkali solution with NaOH and Na 2 C0 3 , where the molar concentration of NaOH is 0.1 ~ 5.0M, and the molar concentration of Na 2 C0 3 is 0.1 ~ 4.8M;
将上述盐溶液和碱溶液同时倒入全反混液膜反应器， 控制转子的转速 为 1000~8000rpm， 物料在反应器内停留时间为 l〜8min， 经液体分部器分 散后， 在转子与定子之间的缝隙处充分混合， 经出料口排到晶化釜， 在 80~120°C恒温晶化 2~10h, 反复抽滤、 洗涤， 干燥， 经 800~100(TC高温焙 烧得到粒径范围在 0〜80nm的 M'Fe204粉体； 碱溶液的量应使混合后的液 体的 PH值在 8.5〜11.0； The above salt solution and alkaline solution are simultaneously poured into a fully reversed liquid film reactor, the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the materials in the reactor is 1 to 8 minutes. After being dispersed by the liquid divider, the rotor and the stator are dispersed. The gap between them is fully mixed, discharged to the crystallization kettle through the discharge port, and crystallized at 80 ~ 120 ° C for 2 ~ 10h at constant temperature. Repeated suction filtration, washing, drying, and particle size obtained by calcination at 800 ~ 100 (TC high temperature) M'Fe 2 0 4 powder in the range of 0 ~ 80nm; the amount of the alkali solution should be such that the PH value of the mixed liquid is 8.5 ~ 11.0;
( 2 )、 磁性前体 M-N- LDH I M'Fe204的制备 将可溶性二价无机金属盐 M2XXn-)2/n和可溶性三价无机金属盐 N3p )3/n 配制成混合盐溶液， M2+ N3+的摩尔比为 2〜4, 二价金属离子的摩尔浓度为 0.2-2.5M, 三价金属离子的摩尔浓度为 1.6〜4.5M; 按 M，Fe204与上述混合 盐溶液中二价无机金属盐的质量比为 1 : 17-5的比例，称取相应的 M，Fe204 粉体加入混合盐溶液中， 搅拌混和均匀； 用 NaOH和 Na2C03配制混合碱 溶液， NaOH摩尔浓度为 0.1~5.0M， Na2C03摩尔浓度为 0.1〜4·8Μ; (2) Preparation of magnetic precursor MN-LDH I M'Fe 2 0 4 The soluble divalent inorganic metal salt M 2 XX n- ) 2 / n and the soluble trivalent inorganic metal salt N 3 p) 3 / n are formulated into a mixed salt solution, and the molar ratio of M 2+ N 3+ is 2 ~ 4, The molar concentration of the divalent metal ion is 0.2-2.5M, and the molar concentration of the trivalent metal ion is 1.6 ~ 4.5M; according to M, the mass ratio of Fe 2 0 4 to the divalent inorganic metal salt in the mixed salt solution is 1: 17-5 ratio, weigh the corresponding M, Fe 2 0 4 powder into the mixed salt solution, stir and mix well; prepare a mixed alkali solution with NaOH and Na 2 C 0 3 , the molar concentration of NaOH is 0.1 ~ 5.0M, Na 2 C0 3 molar concentration is 0.1 ~ 4.8M ;
将盐溶液和碱溶液同时倒入全反混液膜反应器， 控制转子的转速为 1000~8000rpm, 物料在反应器内停留时间为 l-8min, 经液体分部器^：后， 在转子与定子之间的缝隙处充分混合， 经出料口排到晶化釜， 在 80~120°C 恒温晶化 4〜10h, 反复抽滤、 洗涤， 干燥得到带磁性核 M，Fe204的水滑石 M-N-LDH I M'Fe204; 碱溶液的量应使混合后的液体的 PH值在 8.5〜11.0; The salt solution and the alkaline solution are simultaneously poured into an all-reverse liquid-film reactor, and the rotation speed of the rotor is controlled to be 1000 to 8000 rpm, and the residence time of the materials in the reactor is 1 to 8 minutes. After the liquid distributor, the rotor and stator The gaps between them are fully mixed, discharged to the crystallization kettle through the discharge port, and crystallized at a constant temperature of 80 ~ 120 ° C for 4 ~ 10h. Repeated suction filtration, washing, and drying to obtain water with magnetic core M, Fe 2 0 4 Talc MN-LDH I M'Fe 2 0 4 ; The amount of the alkali solution should be such that the PH value of the mixed liquid is 8.5 ~ 11.0;
( 3 )、 催化剂 M-N-(O)/ M'Fe204的制备 (3) Preparation of catalyst MN- (O) / M'Fe 2 0 4
将上述 M-N- LDH I M'Fe204于 400~600 °C中焙烧 2~5小时， 升温速率 10 °C /分， 得到粒径范围在 20〜100nm 的磁性固体碱催化剂 M-N-(O)/ M，Fe204。 The above-mentioned MN-LDH I M'Fe 2 0 4 is calcined at 400 to 600 ° C for 2 to 5 hours, and the heating rate is 10 ° C / min, to obtain a magnetic solid base catalyst MN- (O ) / M, Fe 2 0 4 .
3.根据权利要求 1所述的磁性纳米固 咸催化剂的制备方法，其特征是: 步驟（1 ) 中铁的三价盐可以是： Fe2(S04)3、 FeCl3或 Fe (N03)3中的任 何一种； M，盐可以是： M，S04、 M，C12、 M，(N03)2中的任何一种， M，优选The method for preparing a magnetic nanometer salty catalyst according to claim 1, wherein the trivalent salt of iron in step (1) is: Fe 2 (S0 4 ) 3 , FeCl 3 or Fe (N0 3 ) Any one of 3 ; M, the salt may be: any one of M, S0 4 , M, C1 2 , M, (N0 3 ) 2 , M, preferably
Mg2+或 Ni2+; Mg 2+ or Ni 2+ ;
步骤（2 ) 中 X为 Cl_、 S04 2-、 N03-、 C03 2-中的任何一种， n为阴离子 X的价态， n=l或 2。 In step (2), X is any one of Cl_, S0 4 2- , N0 3- , and C0 3 2- , n is a valence state of anion X, and n = 1 or 2.
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