WO2015090084A1 - 一种用于合成乙撑亚胺的催化剂、制备方法及应用 - Google Patents

一种用于合成乙撑亚胺的催化剂、制备方法及应用 Download PDF

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WO2015090084A1
WO2015090084A1 PCT/CN2014/086008 CN2014086008W WO2015090084A1 WO 2015090084 A1 WO2015090084 A1 WO 2015090084A1 CN 2014086008 W CN2014086008 W CN 2014086008W WO 2015090084 A1 WO2015090084 A1 WO 2015090084A1
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catalyst
carrier
ions
ethyleneimine
magnesium
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PCT/CN2014/086008
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English (en)
French (fr)
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杨建明
吕剑
梅苏宁
余秦伟
惠丰
李亚妮
赵锋伟
王为强
王伟
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西安近代化学研究所
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Priority to US15/105,499 priority Critical patent/US9920008B2/en
Publication of WO2015090084A1 publication Critical patent/WO2015090084A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
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    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention belongs to the technical field of chemical industry, and particularly relates to a catalyst, a preparation method and an application thereof for synthesizing ethyleneimine.
  • Ethyleneimine also known as aziridine
  • aziridine is an important fine chemical product with a wide range of uses in the fields of medicine, pesticides, high-energy fuels, and bonding agents.
  • the initial industrial preparation method of ethyleneimine is liquid phase method, using monoethanolamine as raw material, using concentrated sulfuric acid as dehydrating agent, and adding concentrated alkali in the reaction, the cost is high and the useless inorganic salt by-product is produced, which causes serious Environmental pollution.
  • No. 4,301,036 discloses catalysts consisting of tungsten oxides and silicon oxides, and their use in the synthesis of ethyleneimine.
  • No. 4,337,17 discloses a process for the production of ethyleneimine using a composite oxide catalyst of Nb or Ta oxide with an alkaline earth metal oxide (BaO).
  • the chloride of Nb or Ta is made into a dipping solution for loading, supported on a surface of a carrier (0.1 m 2 /g to 1.0 m 2 /g), and calcined at 450 to 550 ° C for 2 to 4 hours to prepare a catalyst.
  • the reaction temperature is 400 ° C
  • the conversion of ethanolamine is 13.87 (mol)%
  • the selectivity of ethyleneimine is 82.09 (mol)%
  • a small amount of acetaldehyde, ethylamine, pyrazine and alkylpyrazine are formed.
  • a catalyst for the synthesis of ethyleneimine compounds is disclosed.
  • the catalyst composition is: X a Y b O e (HZSM-5) d , wherein X is selected from an alkali metal, Y is selected from phosphorus or boron, 0 is oxygen, and a, b, c, d are X, Y, 0.
  • the reaction temperature is 420 ° C, and the conversion of ethanolamine is 84 (mol)%.
  • the ethyleneimine selectivity is 84 (mol)%.
  • the specific surface area and acid-base strength of the ethyleneimine catalyst are closely related to the activity and selectivity of the catalyst.
  • the specific surface area is large, the supported catalyst has a higher catalytic activity, and the preparation of the catalyst requires a high temperature ( ⁇ 600 ° C) calcination step, and the local high temperature formed by the strong exothermic reaction causes the catalyst to be sintered.
  • the surface area is greatly reduced, resulting in a decrease in catalyst activity and selectivity.
  • the intramolecular dehydration reaction of the amino alcohol is lower at a lower temperature ( ⁇ 370 ° C), the catalyst activity and selectivity are lower, the reaction temperature is high, and the reaction temperature is generally higher than 400 ° C.
  • the occurrence of deamination and intermolecular condensation reaction is likely to occur, and by-products are increased, resulting in a decrease in selectivity of ethyleneimine, a general weight selectivity of less than 65%, and a short service life.
  • the catalyst provided by the present invention comprises a carrier and a metal ion supported on the carrier, the carrier being a composite oxide containing titanium, silicon and phosphorus elements; the metal ions are magnesium ions, iron ions and cerium ions, and The molar ratio of magnesium ion, iron ion and cerium ion is: 1 ⁇ 10: 1 : 0.1, and the mass of all metal ions is 0.5% ⁇ 10% of the mass of the carrier.
  • Another object of the present invention is to provide a process for producing the above carrier and a process for preparing the catalyst.
  • the preparation method of the provided carrier comprises:
  • silica, titania, and ammonium phosphate in the form of an oxide, Si0 2 : Ti0 2 : ⁇ 2 0 5 by weight: 5 to 20: 80: 15 to 5, and then adding a binder, kneading , extruded strips, dry, Calcination at 600 ⁇ 900 ° C to produce a composite oxide containing titanium, silicon and phosphorus;
  • the ammonium phosphate salt is ammonium phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate;
  • the binder is a silica sol or a pseudoboehmite
  • the binder is used in an amount of 10% to 30% by mass of the titanium dioxide.
  • the preparation method of the provided catalyst includes:
  • the catalyst precursor is calcined at 350 ° C to 650 ° C to prepare a catalyst.
  • the catalyst precursor is a mixture of a carrier, a soluble salt of magnesium, a soluble salt of iron and a soluble salt of cerium.
  • the present invention also provides the use of the above catalyst for the synthesis of ethyleneimine from an amino alcohol.
  • the reaction temperature is 370 ° C to 385 ° C.
  • the synthetic ethyleneimine catalyst of the invention adopts S ⁇ as a pore-forming agent at a temperature of 100 ° C to 200 ° C, and utilizes the S ⁇ chain structure in the carrier and easily reacts with HF to form a volatile
  • the capacity is ⁇ 0.20mL/g
  • the average pore diameter is ⁇ 911111, which improves the diffusion effect of the reaction raw materials and products in the catalyst pores.
  • the synthesis of the ethyleneimine catalyst of the present invention significantly lowers the reaction temperature as compared with the general requirement that the temperature be higher than 400 °C.
  • the prepared catalyst can catalyze the intramolecular dehydration reaction of amino alcohol, and has the best selectivity.
  • the conversion of monoethanolamine can reach 38% at 370 ° C, and the ethylene imine selectivity can be selected.
  • the catalyst of the invention has a long service life and the activity is basically maintained stable, the conversion rate of monoethanolamine can reach 32% in 1000h, and the selectivity of ethyleneimine can reach 96%.
  • the catalyst of the present invention can be used in the intramolecular dehydration reaction of various amino alcohols.
  • Si0 2 is used as a pore-forming agent, and the SiO 2 chain structure in the carrier and the volatile fluorinated silicon compound are easily reacted with HF, and once removed by fluorination, The continuous pore structure is flowed down to increase the specific surface area and pore volume, and has a high specific surface area and a large pore volume.
  • the active component is further impregnated by an impregnation step to prepare a catalyst.
  • the amount of the binder of the present invention is determined by the fact that the mixture in the step (1) can be extruded.
  • the silica sol used is an aqueous solution having a silica content of 20% to 30% by mass.
  • the soluble salt of magnesium used in the present invention is preferably a nitrate or a chloride
  • the soluble salt of iron is preferably a nitrate or a chloride
  • the soluble salt of cerium is preferably a nitrate or a chloride.
  • the synthetic ethyleneimine catalyst prepared by the present invention can be carried out in a conventional fixed bed tubular reactor with a reactor size of 7OOmmx04Ommx6mm.
  • the catalyst was charged into the reactor, heated to the reaction temperature, fed through a metering pump, and sampled and analyzed after the reaction.
  • the analytical instrument was a GC-930 gas chromatograph.
  • ethanolamine conversion rate and ethyleneimine selectivity described in the present invention are defined as follows:
  • Ethanolamine conversion rate C MEA , % 1 - Percentage of chromatographic area of ethanolamine in product solution
  • Product selectivity S, % Percentage of chromatographic area of ethyleneamine in product liquor / Percentage of chromatographic area minus ethanolamine in product liquor
  • the catalyst for synthesizing ethyleneimine of the present invention including intramolecular dehydration for other amino alcohols
  • the amino alcohol is an amino alcohol compound having an ortho structure, and its structure is:
  • R 2 is hydrogen, methyl, ethyl or hydroxymethyl
  • A is hydroxy or amino
  • B is hydroxy or amino
  • a and B are not hydroxy or amino at the same time
  • the amino alcohol is ethanolamine, isopropanolamine, 3-amino-1,2-propanediol, 2-amino-2-methyl-1-propanol, and other aminobutanol or aminopentanol. Preference is given to 3-amino-1,2-propanediol and 2-amino-2-methyl-1-propanol.
  • the weight ratio of Si0 2 : Ti0 2 : P 2 0 5 in terms of oxide is 5:80:15 stoichiometric.
  • 10 g of white carbon black, 160 g of titanium dioxide and 55.7 g of diammonium hydrogen phosphate were uniformly mixed, and then silica sol was added.
  • the amount of silica sol added was 20% of the mass of titanium dioxide, kneaded, extruded, and dried at 120 ° C for 6 h. It was calcined in a muffle furnace at 350 ° C for 6 h, and calcined at 650 ° C for 6 h at 1 ° C / min to prepare a composite oxide composed of titanium, silicon and phosphorus.
  • the carrier was measured by a low temperature nitrogen adsorption method with a specific surface area of 42 m 2 /g, a pore volume of 0.22 mL/g, and an average pore diameter of 5.6 nm.
  • Example 2 The preparation process in Example 2 was basically the same as that in Example 1, except that the weight ratio of Si0 2 : Ti0 2 : P 2 0 5 was 10:80:10 stoichiometric.
  • the catalyst carrier was measured by a low temperature nitrogen adsorption method with a specific surface area of 43.2 m 2 /g, a pore volume of 0.21 mL/g, and an average pore diameter of 5.8 nm.
  • the metal ion as the carrier mass of 5.3% load the molar ratio of magnesium ion, iron ion and strontium ion is 8:1:0.1, the soluble metal salt solution is disposed, and the obtained catalyst carrier is immersed for 8 hours, taken out and dried, at 350°.
  • the catalyst was prepared by calcination under nitrogen in C.
  • the above catalyst was charged into the reactor, the loading amount was 30 mL, and the heating was carried out to a reaction temperature of 380 ° C.
  • Nitrogen was used as a shielding gas.
  • the volume ratio of nitrogen gas to monoethanolamine gas was 16, and the total gas space velocity in the standard state was 3000 h" 1 .
  • the reaction gas was absorbed and sampled and analyzed.
  • the conversion of monoethanolamine was 68%, the selectivity of ethyleneimine was 96%, and after 1000 h, the conversion of monoethanolamine was 56%.
  • the imine selectivity is 94%.
  • Example 2 The preparation process in Example 2 was basically the same as that in Example 1, except that the weight ratio of Si0 2 : Ti0 2 : P 2 0 5 was 15:80:5.
  • the catalyst carrier was measured by a low temperature nitrogen adsorption method with a specific surface area of 46.8 m 2 /g, a pore volume of 0.25 mL/g, and an average pore diameter of 6.1 nm.
  • the molar ratio of magnesium ion, iron ion and strontium ion is 1: 1: 0.1
  • the soluble metal salt solution is disposed, and the obtained catalyst carrier is immersed for 8 hours, and taken out. After drying, the catalyst was prepared by calcination at 650 ° C with air.
  • the above catalyst was charged into the reactor, the loading amount was 30 mL, and the reaction temperature was 380 ° C.
  • the nitrogen gas was used as a shielding gas.
  • the volume ratio of nitrogen gas to monoethanolamine gas was 16.
  • the total gas space velocity in the standard state was 3200 h" 1 .
  • the reaction gas was absorbed and sampled and analyzed.
  • the conversion of monoethanolamine was 86%, and the selectivity of ethyleneimine was 92%.
  • Example 4 The operation of Example 4 is basically the same as that of Example 1, except that the metal ion is used as the carrier mass of 10.0% load, and the molar ratio of magnesium ion, iron ion and cerium ion is 5:1:0.1, and the soluble metal salt solution is disposed.
  • the obtained catalyst carrier was immersed for 8 hours, taken out, dried, and calcined at 650 ° C to obtain a catalyst.
  • Isopropanolamine was used as the reaction raw material, and the catalytic reaction conditions and analytical conditions were the same as in Example 1.
  • the conversion of isopropanolamine was 52%, and the selectivity of 2-methylethyleneimine was 86%.
  • Example 5 The operation of Example 5 is basically the same as that of Example 2, except that the metal ion is used as the carrier mass of 8.5% load, and the molar ratio of magnesium ion, iron ion and cerium ion is 3:1:0.1, and the soluble metal salt solution is disposed.
  • the obtained catalyst carrier was immersed for 8 hours, taken out, dried, and calcined at 650 ° C to obtain a catalyst.
  • 3-amino-1,2-propanediol was used as a reaction material, and the reaction temperature was 385 °C.
  • the catalytic reaction conditions and analytical conditions were the same as in Example 1.
  • the selectivity was 9.1%, the other 13.0%.
  • Example 6 The operation of Example 6 was basically the same as that of Example 3, except that 2-amino-2-methyl-1-propanol was used. The reaction material was reacted at a temperature of 379 °C. The catalytic reaction conditions and analytical conditions were the same as in Example 1. The conversion of 2 -ammonia_2_methyl_ ⁇ propanol was 47 %, and the selectivity of 2,2-dimethylethyleneimine was 87.5%.

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Abstract

本发明涉及用于合成乙撑亚胺的催化剂、制备方法及应用。所涉及的催化剂包括载体和负载在载体上的金属离子，所述载体为含钛、硅和磷元素的复合氧化物；所述金属离子为镁离子、铁离子和铯离子，且镁离子、铁离子、铯离子的摩尔比为：1～10:1:0.1，所有金属离子的质量为载体质量的0.5％～10％。所涉及的制备方法是将催化剂前驱体在350℃～650℃下，焙烧制得催化剂，所述催化剂前驱体为载体、镁的可溶性盐、铁的可溶性盐与铯的可溶性盐的混合物。本发明还提供了上述催化剂用于以氨基醇为原料合成乙撑亚胺中的应用。本发明的催化剂，与一般要求温度高于400℃相比降低显著降低了反应温度。制得的催化剂能够催化氨基醇分子内脱水反应，并具有较优的选择性。

Description

一种用于合成乙撑亚胺的催化剂、 制备方法及应用
技术领域
本发明属于化工技术领域， 具体涉及一种合成乙撑亚胺用的催化剂、 制 备方法及应用。
背景技术
乙撑亚胺， 又称氮丙啶， 是一种重要的精细化工产品， 在医药、 农药、 高能燃料、 键合剂等领域有着广泛的用途。
乙撑亚胺最初的工业制法为液相法， 以单乙醇胺为原料， 采用浓硫酸为 脱水剂， 反应中需要加入浓碱， 成本较高且产生无用的无机盐副产， 造成了 严重的环境污染。
US4301036 公开了钨氧化物及硅氧化物组成的催化剂， 及其在合成乙撑 亚胺中的应用。
US4488591中公开了使用铌 /钽氧化物与碱土金属和（或）铁 /铬氧化物作 为催化剂合成乙撑亚胺的方法。
US433717公开了一种用 Nb或 Ta氧化物与碱土金属氧化物 (BaO)的复合 氧化物催化剂生产乙撑亚胺的方法。 先将 Nb或 Ta的氯化物制成负载所用浸 渍溶液， 负载于载体 (0.1 m2/g 〜1.0m2/g)表面 ， 经 450〜550°C焙烧处理 2〜 4h， 制得催化剂。 反应温度 400°C， 乙醇胺转化率 13.87(mol)%， 乙撑亚胺选 择性 82.09(mol)%， 并有少量乙醛、 乙胺、 吡嗪及烷基吡嗪生成。
CN2007100109625 公开了一种用于合成乙撑亚胺类化合物的催化剂。 该 催化剂组成为： XaYbOe(HZSM-5)d， 其中 X选自碱金属， Y选自磷或硼元素， 0为氧元素， a、b、c、 d是 X、 Y、0、ZSM-5沸石的摩尔比，当 d=l时， a=0.01〜 0.1， b=0.001〜0.1， c值取决于 a、 b。反应温度 420 °C，乙醇胺转化率 84(mol)%， 乙撑亚胺选择性 84(mol)%。
乙撑亚胺催化剂比表面积和酸碱强度与催化剂活性、 选择性密切相关。 一般比表面积较大时， 负载的催化剂才具有较高催化活性， 而该类催化剂的 制备需经过高温 （≥600°C ) 焙烧步骤， 由于强烈放热反应形成的局部高温， 使催化剂烧结后比表面积大幅度降低， 导致催化剂活性和选择性降低。 考虑 工业过程中的经济性因素， 通常追求催化剂的更高选择性和更长寿命比物料 转化率更重要， 以保证物料转化成尽可能多的所需目标产品而减少不必要副 产物的生成。
现有技术中， 氨基醇的分子内脱水反应在较低温度 （〜370°C ) 下， 催化 剂活性和选择性较低， 反应温度高， 一般要求温度高于 400°C反应才能较快地 进行， 但容易发生脱氨基及分子间缩合反应的发生而使副产物增多， 导致乙 撑亚胺选择性降低， 一般重量选择性低于 65%， 且使用寿命短。
发明内容
针对现有技术的缺陷或不足， 本发明的目的之一在于提供一种比表面积 大、 孔容大、 低温活性高、 使用寿命长的用于合成乙撑亚胺的催化剂。
为此，本发明提供的催化剂包括载体和负载在载体上的金属离子，所述载 体为含钛、 硅和磷元素的复合氧化物； 所述金属离子为镁离子、 铁离子和铯 离子， 且镁离子、 铁离子、 铯离子的摩尔比为： 1〜10： 1 : 0.1， 所有金属离子 的质量为载体质量的 0.5%~10%。
本发明的另一目的在于提供上述载体的制备方法及催化剂的制备方法。 为此， 所述提供的载体的制备方法包括：
( 1 )将二氧化硅、二氧化钛、磷酸铵盐混合， 以氧化物形式计 Si02 : Ti02 : Ρ205重量比为 5〜20： 80 : 15〜5， 再加入粘结剂， 捏合， 挤条成形， 干燥， 600~900°C焙烧， 制得含钛、 硅和磷元素的复合氧化物；
所述磷酸铵盐为磷酸铵、 磷酸氢二铵或磷酸二氢铵；
所述粘结剂为硅溶胶或拟薄水铝石；
(2 )在无氧、 100°C〜200°C条件下， 步骤（1 )所得复合氧化物与氟化氢 进行氟化反应制得催化剂载体。
优选的， 所述粘结剂的用量为二氧化钛的质量的 10%~30%。
所提供的催化剂的制备方法包括：
将催化剂前驱体在 350°C〜 650°C下， 焙烧制得催化剂， 所述催化剂前驱 体为载体、 镁的可溶性盐、 铁的可溶性盐与铯的可溶性盐的混合物。
针对现有技术缺陷或不足， 本发明还提供了上述催化剂用于以氨基醇为 原料合成乙撑亚胺中的应用。
优选的， 在上述催化剂存在条件下， 以氨基醇为原料合成乙撑亚胺时， 反应温度为 370°C〜385°C。
与现有技术相比， 本发明的有益效果在于：
( 1 ) 本发明的合成乙撑亚胺催化剂， 采用在 100°C~200°C温度下， 选用 S ^作为造孔剂， 利用载体中的 S ^链型结构及易与 HF反应形成挥发性氟 化硅化合物的特点， 一经被氟化除去后就会流下连续孔道结构， 从而增加比 表面积和孔容， 制备具有高的比表面积和大孔容的催化剂， 比表面积 ≥40m2/g， 孔容≥0.20mL/g， 平均孔径≤911111， 改善了反应原料及产品在催化剂 孔内的扩散效果。
(2 ) 本发明的合成乙撑亚胺催化剂， 与一般要求温度高于 400°C相比降 低显著降低了反应温度。 制得的催化剂能够催化氨基醇分子内脱水反应， 并 具有最佳的选择性，在 370°C时单乙醇胺转化率可达 38%， 乙撑亚胺选择性可 (3 ) 本发明的催化剂使用寿命长， 活性基本维持稳定， 1000h 内单乙醇 胺转化率可达 32%， 乙撑亚胺选择性可达 96%。
( 4 ) 本发明的催化剂能用于多种氨基醇分子内脱水反应中。
具体实施方式
为了实现上述任务， 本发明采取如下的技术解决方案： 采用在
100°C~200°C温度下， 选用 Si02作为造孔剂， 利用载体中的 Si02链型结构及 易与 HF反应形成挥发性氟化硅化合物的特点，一经被氟化除去后就会流下连 续孔道结构， 从而增加比表面积和孔容， 具有高的比表面积和大孔容。 再经 浸渍步骤浸渍活性组分， 制得催化剂。
本发明粘结剂的用量根据步骤 （1 ) 中的混合物能够挤条成形确定。 其中 所用硅溶胶为二氧化硅质量百分含量为 20%~30%的水溶液。
本发明所使用的镁的可溶性盐优选硝酸盐或氯化物，铁的可溶性盐优选硝 酸盐或氯化物， 铯的可溶性盐优选硝酸盐或氯化物。
本发明制备的合成乙撑亚胺催化剂， 其活性评价装置可在普通固定床管 式反应器中进行， 反应器尺寸为 7OOmmx04Ommx6mm。将催化剂装填进反应 器，加热至反应温度，通过计量泵进料，反应后取样分析，分析仪器为 GC-930 气相色谱仪。
本发明所述的乙醇胺转化率、 乙撑亚胺选择性定义如下：
乙醇胺转化率 CMEA， ％= 1—产物液中乙醇胺的色谱面积百分数
产物选择性 S， % =产物液中乙撑胺的色谱面积百分数 /产物液中扣除乙 醇胺的色谱面积百分数
本发明合成乙撑亚胺用的催化剂， 包括用于其它的氨基醇的分子内脱水 反应中， 氨基醇为具有邻位结构的氨基醇类化合物， 其结构为：
Figure imgf000006_0001
为氢、 甲基、 乙基或羟甲基， R2为氢、 甲基、 乙基或羟甲基， A为羟 基或氨基， B为羟基或氨基， 且 A和 B不同时为羟基或氨基； 其中氨基醇为 乙醇胺、 异丙醇胺、 3-氨基 -1,2-丙二醇、 2-氨基 -2-甲基 -1-丙醇， 也可以是其 它氨基丁醇、 氨基戊醇。 优选 3-氨基 -1,2-丙二醇、 2-氨基 -2-甲基 -1-丙醇。 以下是发明人给出的实施例， 这些实施例是较优的例子， 主要用于解释 和进一步理解本发明的技术方案， 本发明不限于这些实施例。 实施例 1:
按照以氧化物计 Si02： Ti02： P205 重量比为 5： 80 : 15化学计量比配置。 将白炭黑 10 g， 二氧化钛 160 g , 磷酸氢二铵 55.7 g混合均匀后， 再加 入硅溶胶， 硅溶胶加入量为二氧化钛的质量的 20%， 捏合， 挤条成形， 120°C 干燥 6h， 在马弗炉中 350°C焙烧 6h， 在 l °C/min程序升温至 650°C焙烧 6 h， 制得钛、 硅、 磷组成的复合氧化物。
将钛、 硅、 磷组成的复合氧化物冷却后装入管式反应器， 升温至 150°C， 然后用体积比为HF : N2 = l: 5的混合物氟化2 h， 得到催化剂载体。 该载体用 低温氮吸附法测定其比表面积 42 m2/g， 孔容 0.22mL/g， 平均孔径 5.6 nm。
按照镁离子、铁离子、 铯离子的摩尔比为 10: 1： 0.1负载， 取硝酸镁 29.6 g、 硝酸铁 4.84 g、 硝酸铯 0.4 g配置成溶液， 将得到的催化剂载体浸渍 8h， 取出后干燥， 在 450°C下用空气焙烧制得催化剂。 将上述催化剂装填进反应器， 装填量 30mL， 加热至反应温度 370°C， 氮 气作为保护气体， 氮气与单乙醇胺气体体积比 16， 以标准状态计气体总空速: 3600 h"1, 反应在常压或真空条件下进行， 反应 8 h后， 反应气体水吸收后取 样分析， 单乙醇胺转化率 38%， 乙撑亚胺选择性 95%， 反应 1000 h后， 单乙 醇胺转化率 32%， 乙撑亚胺选择性 96%。
实施例 2:
实施例 2与实施例 1中制备过程基本相同，不同的是按照 Si02： Ti02： P205 重量比为 10： 80 : 10化学计量比配置。 催化剂载体用低温氮吸附法测定其比 表面积 43.2 m2/g， 孔容 0.21mL/g， 平均孔径 5.8 nm。
按照金属离子为载体质量的 5.3%负载， 镁离子、 铁离子、 铯离子的摩尔 比为 8 : 1 : 0.1， 配置可溶性金属盐溶液， 将得到的催化剂载体浸渍 8h， 取出 后干燥， 在 350°C下氮气中焙烧制得催化剂。
将上述催化剂装填进反应器， 装填量 30mL， 加热至反应温度 380°C， 氮 气作为保护气体， 氮气与单乙醇胺气体体积比 16， 以标准状态计气体总空速: 3000 h"1, 反应在常压或真空条件下进行， 反应 8 h后， 反应气体水吸收后取 样分析， 单乙醇胺转化率 68%， 乙撑亚胺选择性 96%， 反应 1000 h后， 单乙 醇胺转化率 56%， 乙撑亚胺选择性 94%。
实施例 3:
实施例 2与实施例 1中制备过程基本相同，不同的是按照 Si02： Ti02： P205 重量比为 15： 80： 5化学计量比配置。 催化剂载体用低温氮吸附法测定其比表 面积 46.8 m2/g， 孔容 0.25 mL/g， 平均孔径 6.1 nm。
按照金属离子为载体质量的 0.5 %负载， 镁离子、 铁离子、 铯离子的摩尔 比为 1 : 1 : 0.1， 配置可溶性金属盐溶液， 将得到的催化剂载体浸渍 8h， 取出 后干燥， 在 650°C下用空气焙烧制得催化剂。
将上述催化剂装填进反应器， 装填量 30mL， 加热至反应温度 380°C， 氮 气作为保护气体， 氮气与单乙醇胺气体体积比 16， 以标准状态计气体总空速: 3200 h"1, 反应在常压或真空条件下进行， 反应 8 h后， 反应气体水吸收后取 样分析， 单乙醇胺转化率 86%， 乙撑亚胺选择性 92%。
实施例 4:
实施例 4操作与实施例 1基本相同，所不同的是按照金属离子为载体质量 的 10.0 %负载， 镁离子、 铁离子、 铯离子的摩尔比为 5: 1 : 0.1， 配置可溶性金 属盐溶液， 将得到的催化剂载体浸渍 8h， 取出后干燥， 在 650°C下用空气焙 烧制得催化剂。
采用异丙醇胺为反应原料， 催化反应条件及分析条件同实施例 1。异丙醇 胺转化率 52%， 2-甲基乙撑亚胺选择性 86%。
实施例 5:
实施例 5操作与实施例 2基本相同，所不同的是按照金属离子为载体质量 的 8.5 %负载， 镁离子、 铁离子、 铯离子的摩尔比为 3: 1 : 0.1， 配置可溶性金 属盐溶液， 将得到的催化剂载体浸渍 8h， 取出后干燥， 在 650°C下用空气焙 烧制得催化剂。
采用 3-氨基 -1,2-丙二醇为反应原料， 反应温度为 385 °C。催化反应条件及 分析条件同实施例 1。 3-氨基 -1,2-丙二醇转化率 62%， 3-羟基 -1-氮杂环丁烷选 择性 53.2%， 2-羟甲基乙撑亚胺选择性 24.7%， 3-氨基环氧丙烷选择性 9.1%， 其它 13.0%。
实施例 6:
实施例 6操作与实施例 3基本相同， 所不同的是采用 2-氨基 -2-甲基 -1-丙醇为 反应原料， 反应温度为 379°C。 催化反应条件及分析条件同实施例 1。 2-氨 _2_甲基 _μ丙醇转化率 47%， 2,2-二甲基乙撑亚胺选择性 87.5%。

Claims

权利要求书
1、 一种用于合成乙撑亚胺的催化剂， 其特征在于， 该催化剂包括载体和 负载在载体上的金属离子， 所述载体为含钛、 硅和磷元素的复合氧化物； 所 述金属离子为镁离子、 铁离子和铯离子， 且镁离子、 铁离子、 铯离子的摩尔 比为： 1〜： 10 : 1 : 0.1， 所有金属离子的质量为载体质量的 0.5%~10%。
2、 如权利要求 1所述的用于合成乙撑亚胺的催化剂， 其特征在于， 所述 载体的制备包括：
( 1 )将二氧化硅、二氧化钛、磷酸铵盐混合， 以氧化物形式计 Si02： Ti02： P205重量比为 5〜20： 80 : 15〜5， 再加入粘结剂， 捏合， 挤条成形， 干燥， 600~900°C焙烧， 制得含钛、 硅和磷元素的复合氧化物；
所述磷酸铵盐为磷酸铵、 磷酸氢二铵或磷酸二氢铵；
所述粘结剂为硅溶胶或拟薄水铝石；
(2)在无氧、 100°C〜200°C条件下， 步骤（1 )所得复合氧化物与氟化氢 进行氟化反应制得催化剂载体。
3、 如权利要求 2所述的用于合成乙撑亚胺的催化剂， 其特征在于， 所述 粘结剂的用量为二氧化钛的质量的 10%~30%。
4、 如权利要求 2所述的用于合成乙撑亚胺的催化剂， 其特征在于， 该催 化剂的制备方法包括：
将催化剂前驱体在 350°C〜 650°C下， 焙烧制得催化剂， 所述催化剂前驱 体为载体、 镁的可溶性盐、 铁的可溶性盐与铯的可溶性盐的混合物。
5、 权利要求 1-4任一权利要求所述的催化剂用于以氨基醇为原料合成乙 撑亚胺中的应用。 、 如权利要求 5所述的应用， 其特征在于， 反应温度为 370°C〜385°C
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