WO2023134779A1 - Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol - Google Patents

Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol Download PDF

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WO2023134779A1
WO2023134779A1 PCT/CN2023/072644 CN2023072644W WO2023134779A1 WO 2023134779 A1 WO2023134779 A1 WO 2023134779A1 CN 2023072644 W CN2023072644 W CN 2023072644W WO 2023134779 A1 WO2023134779 A1 WO 2023134779A1
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hydrogenation
catalyst
hydrogenation catalyst
alkaline earth
earth metal
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PCT/CN2023/072644
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French (fr)
Chinese (zh)
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向明林
周冬京
汪永军
丰明
邱长玖
罗文星
佘喜春
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湖南长炼新材料科技股份公司
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases

Definitions

  • the present invention relates to the technical field of preparation of isohexanediol and methyl isobutyl carbinol, in particular to a hydrogenation catalyst for preparing isohexanediol and methyl isobutyl carbinol, a preparation method thereof, and preparation of isohexanediol and methyl isobutyl carbinol Methods.
  • Isohexanediol (MPD for short) is a colorless, non-toxic liquid with a slightly fresh sweet smell, soluble in water, alcohol, ether and lower aliphatic hydrocarbons. Isohexanediol has the characteristics of environmental protection, low toxicity, and oil-water miscibility, and can be widely used in various fields such as water-based coatings, PU synthesis, fragrance intermediate synthesis, and pesticide stabilizers.
  • the synthesis method of isohexanediol in China is divided into two types according to the different raw material routes: one is prepared from the methanolysis of 2,4,4,6-tetramethyl-1,3-dioxane; the other is One is to use acetone condensate - diacetone alcohol as raw material for hydrogenation reduction synthesis.
  • the latter method is currently the main synthetic production process.
  • MIBC Methyl isobutyl carbinol
  • MIBC is a medium-boiling solvent with excellent performance, mainly used in the fields of mineral flotation, coating, pesticide, medicine, synthetic resin, cellulose and binder.
  • mineral flotation MIBC is used as a foaming and flotation solvent, which can improve the processing capacity of ore and reduce the amount of foaming agent.
  • foaming agents dispersants, detergents, plasticizers, surfactants, lubricants, cosmetics, and pharmaceuticals for the photographic industry.
  • the existing production routes of methyl isobutyl carbinol mainly include: one is to obtain by-products when synthesizing anti-aging agent 6PPD; the other is to synthesize methyl isobutyl ketone (MIBK) through catalytic hydrogenation of acetone/mesopropylidene Jointly obtained.
  • MIBK methyl isobutyl ketone
  • the product obtained by the former method has low purity and a large amount of impurities, which is difficult to separate and purify, and is not suitable for industrial production.
  • the process route of MIBC is obtained by co-producing MIBK through the catalytic hydrogenation of acetone/mesopropylidene acetone. What you get is a mixture of both.
  • the purpose of the present invention is to provide a method for preparing isohexanediol and methyl isobutyl carbinol in order to overcome the problems of poor catalyst selectivity and limited process raw materials in the existing hydrogenation process route for preparing isohexanediol and methyl isobutyl ketone Hydrogenation catalyst and its preparation method and preparation method of isohexanediol and methyl isobutyl carbinol.
  • acetone in the preparation process of acetone derivatives, acetone can obtain a series of important compounds through condensation reaction and separation and refining process, such as products such as diacetone alcohol and mesityl oxide, and through The acetone condensation reaction liquid containing diacetone alcohol, mesityl oxide and other products is directly subjected to hydrogenation reaction without separation and purification to obtain multiple hydrogenation products at the same time, which has a good technical effect.
  • the present invention was thus obtained.
  • the first aspect of the present invention provides a hydrogenation catalyst for the preparation of isohexanediol and methyl isobutyl carbinol, wherein the hydrogenation catalyst includes a modified carrier, and is loaded on the modified carrier Active components and additive components; wherein, the modified carrier includes alkaline earth metal oxides and carrier oxides, the carrier oxide is aluminum oxide and/or silicon oxide, and the active component is selected from ruthenium, At least one of palladium and platinum, the additive component is copper.
  • a second aspect of the present invention provides a method for preparing a hydrogenation catalyst for isohexanediol and methyl isobutyl carbinol, wherein the method comprises:
  • the modified carrier is contacted with a solution containing an active component element compound and an auxiliary component element compound for impregnation, and the obtained product is subjected to second drying or non-drying and second calcination to obtain a pre-catalyst;
  • the active component is selected from at least ruthenium, palladium and platinum
  • the additive component is copper;
  • the pre-catalyst is contacted with a reducing agent to carry out a reduction reaction to obtain the hydrogenation catalyst.
  • the third aspect of the present invention provides a method for preparing isohexanediol and methyl isobutyl carbinol, wherein the method comprises: hydrogenating the acetone condensation reaction liquid with hydrogen in the presence of a hydrogenation catalyst and hydrogenation conditions, Obtain isohexanediol and methyl isobutyl carbinol;
  • the acetone condensation reaction solution contains diacetone alcohol and mesityl oxide;
  • the hydrogenation catalyst is the hydrogenation catalyst provided by the present invention and/or the hydrogenation catalyst prepared by the method provided by the present invention.
  • the present invention can obtain the following beneficial technical effects:
  • the active component and the co-catalyst copper form an alloy structure, and the synergistic effect between the two can greatly increase the catalytic activity, improve the conversion rate of raw materials and the selectivity of target products, and can reduce the reaction temperature;
  • the pore size of the catalyst is moderate and relatively concentrated, and the reactants and product molecules can quickly enter and exit the catalyst pores, which can avoid the strong adsorption or partial polymerization of the high-boiling fraction generated by the acetone condensation reaction on the surface of the catalyst to cause catalyst deactivation; while the existing nickel Catalysts, high boiling point components have a greater impact on the activity of nickel catalysts;
  • the surface properties of the catalyst can be significantly improved, and the active carbon-carbon double bond and carbon-oxygen double bond can be prevented from forming colloids or other by-products on the surface of the catalyst to block the pores or cover the hydrogenation active sites of the catalyst; At the same time, it also weakens the side reactions of dehydration and bond breaking of the hydroxyl group on the surface of the catalyst, thus greatly improving the selectivity of the catalyst.
  • the first aspect of the present invention provides a hydrogenation catalyst for the preparation of isohexanediol and methyl isobutyl carbinol, wherein the hydrogenation catalyst includes a modified carrier, and an active component and a co-catalyst loaded on the modified carrier agent component; wherein, the modified carrier includes alkaline earth metal oxide and carrier oxide, the carrier oxide is alumina and/or silicon oxide, and the active component is selected from at least one of ruthenium, palladium and platinum One, the additive component is copper.
  • the content of the alkaline earth metal oxide in terms of metal is 0.5-3wt%, preferably 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% and 3wt%, and any value in the range formed by any two of the above numerical values.
  • the modified carrier is obtained by introducing alkaline earth metals. The content of the introduced alkaline earth metals is moderate within the above range. If the amount is too small, the catalytic effect will be slightly poor. If the amount is too high, the pore volume of the catalyst will be affected, which cannot meet the requirements for macropores. demand.
  • the alkaline earth metal oxide is at least one selected from magnesium oxide, calcium oxide and barium oxide.
  • the content of the active component is 0.1-3 wt%, and the content of the auxiliary component is 0.1-0.5 wt%, so The content of the modified carrier is 96.5-99.8wt%.
  • the content of the active component is 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt% %, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4 wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt% and 3wt%, and any value in the range formed by any two of the above values; the content of the auxiliary component is 0.1 wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, and any value in the range formed by any two of the above values;
  • the specific surface area of the hydrogenation catalyst is 160-220m 2 /g
  • the pore volume is 0.4-0.7cm 3 /g
  • the volume of pores with a pore diameter of 7-12nm accounts for 55-80% of the total pore volume of the hydrogenation catalyst.
  • the present invention provides a catalyst with the above-mentioned technical characteristics, which can provide better activity of the hydrogenation reaction for preparing isohexanediol and methyl isobutyl carbinol, such as high conversion rate of raw materials and high selectivity of target products, and longer catalyst operation Time, good stability.
  • a second aspect of the present invention provides a method for preparing a hydrogenation catalyst for isohexanediol and methyl isobutyl carbinol, wherein the method comprises:
  • the modified carrier is contacted with a solution containing an active component element compound and an auxiliary component element compound for impregnation, and the obtained product is subjected to second drying or non-drying and second calcination to obtain a pre-catalyst;
  • the active component is selected from at least ruthenium, palladium and platinum
  • the additive component is copper;
  • the pre-catalyst is contacted with a reducing agent to carry out a reduction reaction to obtain the hydrogenation catalyst.
  • the temperature of the first drying is 80-120°C
  • the time of the first drying is 4-20h
  • the first calcined The temperature is 600-950° C.
  • the time for the first calcination is 2-10 hours.
  • the alkaline earth metal compound is selected from at least one of alkaline earth metal inorganic salts, alkaline earth metal organic salts and alkaline earth metal hydroxides, preferably alkaline earth metal nitrates, alkaline earth metal At least one of acetate and alkaline earth metal hydroxide, more preferably at least one of nitrate, acetate and hydroxide of at least one of Mg, Ca and Ba.
  • the amount of the alkaline earth metal compound is such that the content of the alkaline earth metal in the modified support is 0.5-3 wt%. It may be preferably 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% and 3wt%, and any value in the range formed by any two of the above numerical values.
  • the carrier may be selected from alumina and/or silicon oxide, and the carrier precursor may be selected from at least one of pseudo-boehmite, alumina powder or silica gel.
  • Both the carrier and the carrier precursor are selected from materials with few small pores and large pores, which may refer to materials with a pore volume greater than 1.0 cm 3 /g, such as large-pore pseudo-boehmite in the field.
  • the small pores refer to substances with a pore volume of less than 0.9 cm 3 /g.
  • the forming may be extruded, pelletized or tableted, so that the strength of the carrier meets the requirements for industrial use.
  • the temperature of the second drying is 80-120°C
  • the time of the second drying is 4-20h
  • the second calcined The temperature is 350-500° C.
  • the time for the second calcination is 4-10 hours.
  • the amount of the active component element compound and the auxiliary component element compound is such that, in the hydrogenation catalyst, based on the total amount of the hydrogenation catalyst, the The content of the active component is 0.1-3wt%, and the content of the auxiliary component is 0.1-0.5wt%.
  • the active component element compound is selected from at least one of nitrate, chloride and acetate of the active component, preferably selected from ruthenium chloride , platinum chloride, palladium acetate at least one.
  • the element compound of the auxiliary component is selected from at least one of sulfate, chloride, nitrate and acetate of the auxiliary component, preferably At least one selected from copper nitrate, copper sulfate and copper chloride or a hydrate thereof.
  • the reducing agent is at least one selected from hydrazine hydrate, sodium borohydride and formaldehyde. It is sufficient to reduce the active component element compound and the auxiliary component element compound into corresponding metal elements.
  • the elemental compound of the active component and the elemental compound of the auxiliary component are calculated as the active component and the auxiliary component respectively, and the reducing agent and the active component and the The molar ratio of the sum of the auxiliary components is 3-6:1.
  • the reduction conditions include: the reduction temperature is 30-80°C, preferably 40-60°C, the reduction time is 2-10h, preferably 4-6h; and non-oxidizing sex atmosphere.
  • the reduction reaction in the step (3) of the present invention also includes drying the obtained product, and the drying can be carried out at a temperature of 60-150°C, preferably at a temperature of 80-120°C.
  • the duration of the drying can be selected according to the drying temperature, whichever can remove or substantially remove the solvent therein. Generally, the duration of the drying may be 8-24 hours, preferably 12-20 hours.
  • the drying is carried out in a non-oxidizing atmosphere, such as a nitrogen atmosphere and/or a zero-group element atmosphere (such as argon).
  • the third aspect of the present invention provides a method for preparing isohexanediol and methyl isobutyl carbinol, wherein the method comprises: hydrogenating the acetone condensation reaction liquid with hydrogen in the presence of a hydrogenation catalyst and hydrogenation conditions, Obtain isohexanediol and methyl isobutyl carbinol;
  • the acetone condensation reaction solution contains diacetone alcohol and mesityl oxide;
  • the hydrogenation catalyst is the hydrogenation catalyst provided by the present invention and/or the hydrogenation catalyst prepared by the method provided by the present invention.
  • the acetone condensation reaction liquid contains acetone, isophorone and impurities.
  • the impurities may be some low molecular weight polymers of acetone.
  • the content of diacetone alcohol is 10-90wt%
  • the content of mesityl oxide is 5-90wt%
  • acetone, isopropylidene is within 5wt%.
  • the ketone condensation reaction solution is a product formed by the condensation reaction of acetone under the condition of a basic catalyst, wherein the temperature of the condensation reaction is 0-80°C, which can be obtained The acetone condensation reaction liquid of above-mentioned composition.
  • the hydrogenation conditions include: The hydrogenation temperature is 50-120°C, the hydrogenation pressure is 1-7MPa, the volume ratio of hydrogen to the acetone condensation reaction liquid is 30-100:1, and the liquid hourly space velocity of the acetone condensation reaction liquid is 0.2-4h - 1 ;
  • the hydrogenation temperature is 60-110°C
  • the hydrogenation pressure is 3-5MPa
  • the volume ratio of hydrogen to the acetone condensation reaction liquid is 40-70:1
  • the liquid hourly space velocity of the acetone condensation reaction liquid is 0.3- 1.8h -1 .
  • the hydrogenation reaction can be carried out in a tubular fixed-bed reactor.
  • the acetone condensation reaction solution is contacted with hydrogen in the reactor, and the acetone condensation reaction solution is contacted with hydrogen.
  • the method can be that the acetone condensation reaction liquid and hydrogen pass through the reactor from top to bottom, and can also pass through the reactor from bottom to top.
  • each metal content parameter in the catalyst is measured by an atomic emission spectrometer; the acetone raw material is a commercial product.
  • the conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the content of diacetone alcohol is 90wt%, the content of mesityl oxide is 5wt%, the content of acetone is 3wt%, the content of isophorone is 1.3wt%, and the balance is impurities;
  • the temperature was 85°C
  • the hydrogenation pressure was 5MPa
  • the volume ratio of hydrogen to acetone condensation reaction solution was 30:1
  • the liquid hourly space velocity of the acetone condensation reaction solution was 2h -1 .
  • the reaction results are shown in Table 1.
  • the conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the content of diacetone alcohol is 50wt%, the content of mesityl oxide is 46wt%, the content of acetone is 2wt%, the content of isophorone is 1wt%, and the balance is impurities; the hydrogenation temperature is 50 °C, the hydrogenation pressure is 7MPa, the volume ratio of hydrogen to the acetone condensation reaction solution is 100:1, and the liquid hourly space velocity of the acetone condensation reaction solution is 0.5h -1 .
  • the reaction results are shown in Table 1.
  • the conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the diacetone alcohol content is 85wt%, the mesityl oxide content is 12wt%, the acetone content is 2wt%, the isophorone content is 0.5wt%, and the balance is impurities; the hydrogenation temperature is 120°C, hydrogenation pressure 1MPa, volume ratio of hydrogen to acetone condensation reaction liquid 50:1, liquid hourly space velocity of acetone condensation reaction liquid 4h -1 , reaction results are shown in Table 1.
  • the conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the diacetone alcohol content is 10wt%, the mesityl oxide content is 87wt%, the acetone content is 2wt%, the isophorone content is 0.2wt%, and the balance is impurities; the hydrogenation temperature is 90°C, hydrogenation pressure 3MPa, volume ratio of hydrogen to acetone condensation reaction liquid 45:1, liquid hourly space velocity of acetone condensation reaction liquid 1.5h -1 , reaction results are shown in Table 1.
  • the conditions of the hydrogenation reaction include: the content of diacetone alcohol in the acetone condensation reaction liquid is 90wt%, the content of mesityl oxide is 5wt%, the content of acetone is 3wt%, the content of isophorone is 0.7wt%, and the balance is impurities;
  • the hydrogenation temperature was 115°C
  • the hydrogenation pressure was 5MPa
  • the volume ratio of hydrogen to acetone condensation reaction solution was 70:1
  • the liquid hourly space velocity of the acetone condensation reaction solution was 1.0h -1 .
  • the reaction results are shown in Table 1.
  • the preparation process of the hydrogenation catalyst is the same as that of Example 1, except that the support is not modified by alkaline earth metal Mg.
  • the hydrogenation reaction conditions are the same.
  • the preparation process of the hydrogenation catalyst was the same as in Example 1, except that no Cu additive was added to the catalyst.
  • the hydrogenation reaction conditions are the same.
  • the preparation process of the hydrogenation catalyst is the same as in Example 1, except that the large-pore pseudo-boehmite is replaced by small-pore alumina powder (pore volume less than 0.9 cm 3 /g).
  • the hydrogenation reaction conditions are the same.
  • the catalyst is Ni/Al 2 O 3 , wherein the Ni content is 30wt%.
  • the hydrogenation reaction conditions are the same.
  • the preparation process of the hydrogenation catalyst is the same as that of Comparative Example 2, except that the hydrogenation temperature in the hydrogenation reaction conditions is different, and the hydrogenation temperature is 105°C.
  • Catalyst D of Example 4 was used to investigate the activity and stability of the catalyst.
  • the hydrogenation raw materials were: in the acetone condensation reaction liquid, the content of diacetone alcohol was 86%, the content of mesityl oxide was 10%, the content of acetone was 2%, and the content of isophorone was 0.9% %, the balance is impurities; the conditions of the hydrogenation reaction are: the hydrogenation temperature is 80-90 ° C hydrogenation, the pressure of the acetone condensation reaction liquid is 5MPa, hydrogen and The volume ratio of the acetone condensation reaction solution is 40-60:1, and the liquid hourly space velocity of the acetone condensation reaction solution is 0.8h -1 .
  • the reaction results are shown in Table 2. It can be seen from the running results that the catalyst has good activity, selectivity and high stability.
  • Example 1 and Comparative Example 2 show that the addition of co-catalyst can obviously improve the catalyst activity, acetone conversion rate 100%, isohexanediol and methyl iso The selectivity of butyl alcohol is all higher;
  • the contrast of embodiment 1 and comparative example 1 shows, the addition of alkaline earth metal, the selectivity of isohexanediol rises to 99.9% by 93.3%, the selectivity of methyl isobutyl alcohol by 94.6% % rises to 100%, can obviously improve the selectivity of catalysis;
  • Embodiment 1 and comparative example 3 contrast show, when the catalyzer control pore structure provided by the present invention is in the limited scope, reactant and product molecule can enter and exit catalyst pore rapidly, Thereby the catalytic activity is improved;
  • the comparison of Example 1 and Comparative Example 4 shows that the activity of the nickel catalyst is significantly lower than that of the catalyst of Example 1; the
  • Embodiment 1 comparative example 2 are compared with comparative example 5, as can be seen as adding without co-catalyst, comparative example 5 needs to increase reaction temperature and just can obtain the raw material conversion rate close to embodiment 1, it can be seen that catalyst of the present invention can reduce Hydrogenation reaction temperature to obtain good catalytic activity.

Abstract

Provided are a hydrogenation catalyst for preparing isohexanediol and methyl isobutyl carbinol, and a preparation method therefor. In addition, also provided is a method for preparing isohexanediol and methyl isobutyl carbinol. The hydrogenation catalyst comprises a modified support, and an active component and an auxiliary component loaded on the modified support, wherein the modified support comprises an alkaline earth metal oxide and a support oxide, the support oxide is aluminum oxide and/or silicon oxide, the active component is at least one selected from ruthenium, palladium, and platinum, and the auxiliary component is copper. The hydrogenation catalyst is high in activity, high in raw material conversion rate, good in selectivity, and good in stability.

Description

加氢催化剂及其制备方法和制备异己二醇和甲基异丁基甲醇的方法Hydrogenation catalyst and its preparation method and method for preparing isohexanediol and methyl isobutyl carbinol
相关申请的交叉引用Cross References to Related Applications
本申请要求2022年01月17日提交的中国专利申请202210047953.8的权益，该申请的内容通过引用被合并于本文。This application claims the rights and interests of Chinese patent application 202210047953.8 filed on January 17, 2022, the contents of which are incorporated herein by reference.
技术领域technical field
本发明涉及异己二醇和甲基异丁基甲醇的制备技术领域，具体涉及一种制备异己二醇和甲基异丁基甲醇的加氢催化剂及其制备方法和制备异己二醇和甲基异丁基甲醇的方法。The present invention relates to the technical field of preparation of isohexanediol and methyl isobutyl carbinol, in particular to a hydrogenation catalyst for preparing isohexanediol and methyl isobutyl carbinol, a preparation method thereof, and preparation of isohexanediol and methyl isobutyl carbinol Methods.
背景技术Background technique
异己二醇(简称MPD)，为无色、无毒的液体，略有清新的甜香气味，溶于水、醇、醚和低级脂肪烃。异己二醇具有环保、低毒、油水混溶等特性，可以广泛应用于水性涂料、PU合成、香料中间体合成、农药稳定剂等各个领域。Isohexanediol (MPD for short) is a colorless, non-toxic liquid with a slightly fresh sweet smell, soluble in water, alcohol, ether and lower aliphatic hydrocarbons. Isohexanediol has the characteristics of environmental protection, low toxicity, and oil-water miscibility, and can be widely used in various fields such as water-based coatings, PU synthesis, fragrance intermediate synthesis, and pesticide stabilizers.
目前国内异己二醇的合成方法依原料路线的不同分为两种：一种是从2,4,4,6-四甲基-1,3-二氧环己烷的甲醇分解来制备；另一种是用丙酮缩合物--二丙酮醇为原料加氢还原合成。后一种方法是目前主要的合成生产工艺。At present, the synthesis method of isohexanediol in China is divided into two types according to the different raw material routes: one is prepared from the methanolysis of 2,4,4,6-tetramethyl-1,3-dioxane; the other is One is to use acetone condensate - diacetone alcohol as raw material for hydrogenation reduction synthesis. The latter method is currently the main synthetic production process.
目前已公开的二丙酮醇加氢制备异己二醇的专利，如CN1066608A、CN102329193、CN1228354A、CN1565730A等，大多 采用釜式间歇方法生产，采用Ni系催化剂或在Ni系催化剂中加入碱性化合物，其存在制备方法复杂，催化剂用量大、生产效率低并且异己二醇选择性低等缺点，且在制备异己二醇过程中使用有机溶剂，存在后续分离复杂，生产成本高等问题。Currently disclosed patents for preparing isohexanediol by hydrogenation of diacetone alcohol, such as CN1066608A, CN102329193, CN1228354A, CN1565730A, etc., mostly It is produced by a kettle-type batch method, using a Ni-based catalyst or adding a basic compound to the Ni-based catalyst, which has the disadvantages of complicated preparation methods, large catalyst consumption, low production efficiency, and low selectivity of isohexanediol. The use of organic solvents in the alcohol process has problems such as subsequent separation complexity and high production costs.
甲基异丁基甲醇(简称MIBC)，是一种性能优良的中沸点溶剂，主要用于矿物浮选、涂料、农药、医药、合成树脂、纤维素以及粘结剂等领域。在矿物浮选中，MIBC作为起泡及浮选溶剂，可以提高矿石的处理能力，降低起泡剂的用量。此外，还用作发泡剂、分散剂、洗涤剂、增塑剂、表面活性剂、润滑剂及化妆品、照相工业用药品等的制造。现有甲基异丁基甲醇的生产路线主要包括：一种是合成防老剂6PPD时副产获得；另一种是通过丙酮/异丙叉丙酮催化加氢合成甲基异丁基甲酮(MIBK)时联产获得。但前一种方法得到的产品纯度低、夹杂有大量杂质，难以分离提纯，不适合工业生产，而通过丙酮/异丙叉丙酮催化加氢合成MIBK时联产得到MIBC的工艺路线，一般情况下得到的是两者混合物。如果以镍或铜为催化剂，气相加氢条件比较温和时，则得到较多的部分加氢产物MIBK，当温度控制为170-210℃，氢与异丙叉丙酮的摩尔配比较大时，则较多获得完全加氢产物MIBC。由此可见，催化剂选择性有待进一步提高。Methyl isobutyl carbinol (abbreviated as MIBC) is a medium-boiling solvent with excellent performance, mainly used in the fields of mineral flotation, coating, pesticide, medicine, synthetic resin, cellulose and binder. In mineral flotation, MIBC is used as a foaming and flotation solvent, which can improve the processing capacity of ore and reduce the amount of foaming agent. In addition, it is also used in the manufacture of foaming agents, dispersants, detergents, plasticizers, surfactants, lubricants, cosmetics, and pharmaceuticals for the photographic industry. The existing production routes of methyl isobutyl carbinol mainly include: one is to obtain by-products when synthesizing anti-aging agent 6PPD; the other is to synthesize methyl isobutyl ketone (MIBK) through catalytic hydrogenation of acetone/mesopropylidene Jointly obtained. However, the product obtained by the former method has low purity and a large amount of impurities, which is difficult to separate and purify, and is not suitable for industrial production. However, the process route of MIBC is obtained by co-producing MIBK through the catalytic hydrogenation of acetone/mesopropylidene acetone. What you get is a mixture of both. If nickel or copper is used as a catalyst and the gas phase hydrogenation conditions are relatively mild, more partial hydrogenation product MIBK will be obtained. When the temperature is controlled at 170-210°C and the molar ratio of hydrogen to mesityl oxide is large, then More complete hydrogenation product MIBC is obtained. It can be seen that the catalyst selectivity needs to be further improved.
对于现有技术制备异己二醇和甲基异丁基甲酮的加氢工艺路线都存在的问题，需要提供一种新的改进技术。For the problems existing in the hydrogenation process routes for preparing isohexanediol and methyl isobutyl ketone in the prior art, a new improved technology needs to be provided.
发明内容 Contents of the invention
本发明的目的是为了克服现有制备异己二醇和甲基异丁基甲酮的加氢工艺路线中催化剂选择性差，工艺原料受限制的问题，提供了一种制备异己二醇和甲基异丁基甲醇的加氢催化剂及其制备方法和制备异己二醇和甲基异丁基甲醇的方法。The purpose of the present invention is to provide a method for preparing isohexanediol and methyl isobutyl carbinol in order to overcome the problems of poor catalyst selectivity and limited process raw materials in the existing hydrogenation process route for preparing isohexanediol and methyl isobutyl ketone Hydrogenation catalyst and its preparation method and preparation method of isohexanediol and methyl isobutyl carbinol.
在本发明的研究过程中，发明人发现，在丙酮衍生物的制备过程中，丙酮通过缩合反应及分离精制过程可以获得一系列重要化合物，如二丙酮醇、异丙叉丙酮等产品，而通过将含二丙酮醇、异丙叉丙酮等产品的丙酮缩合反应液不经分离精制而直接进行加氢反应来同时获得多个加氢产品，具有很好的技术效果。由此得到本发明。In the research process of the present invention, the inventor found that in the preparation process of acetone derivatives, acetone can obtain a series of important compounds through condensation reaction and separation and refining process, such as products such as diacetone alcohol and mesityl oxide, and through The acetone condensation reaction liquid containing diacetone alcohol, mesityl oxide and other products is directly subjected to hydrogenation reaction without separation and purification to obtain multiple hydrogenation products at the same time, which has a good technical effect. The present invention was thus obtained.
为了实现上述发明目的，本发明第一方面提供一种制备异己二醇和甲基异丁基甲醇的加氢催化剂，其中，所述加氢催化剂包括改性载体，和负载在所述改性载体上的活性组分和助剂组分；其中，所述改性载体包括碱土金属氧化物和载体氧化物，所述载体氧化物为氧化铝和/或氧化硅，所述活性组分选自钌、钯和铂中的至少一种，所述助剂组分为铜。In order to achieve the purpose of the above invention, the first aspect of the present invention provides a hydrogenation catalyst for the preparation of isohexanediol and methyl isobutyl carbinol, wherein the hydrogenation catalyst includes a modified carrier, and is loaded on the modified carrier Active components and additive components; wherein, the modified carrier includes alkaline earth metal oxides and carrier oxides, the carrier oxide is aluminum oxide and/or silicon oxide, and the active component is selected from ruthenium, At least one of palladium and platinum, the additive component is copper.
本发明第二方面提供一种制备异己二醇和甲基异丁基甲醇的加氢催化剂的方法，其中，所述方法包括：A second aspect of the present invention provides a method for preparing a hydrogenation catalyst for isohexanediol and methyl isobutyl carbinol, wherein the method comprises:
(1)将碱土金属化合物与载体和/或载体前驱体进行成型，然后经过第一干燥或不干燥后进行第一焙烧，得到改性载体；(1) molding the alkaline earth metal compound and the carrier and/or the carrier precursor, and then performing the first calcination after the first drying or not drying to obtain the modified carrier;
(2)将所述改性载体与含有活性组分元素化合物和助剂组分元素化合物的溶液接触进行浸渍，得到的产物经第二干燥或不干燥后进行第二焙烧，得到预催化剂；其中，活性组分选自钌、钯和铂中的至少 一种，助剂组分为铜；(2) The modified carrier is contacted with a solution containing an active component element compound and an auxiliary component element compound for impregnation, and the obtained product is subjected to second drying or non-drying and second calcination to obtain a pre-catalyst; wherein , the active component is selected from at least ruthenium, palladium and platinum One, the additive component is copper;
(3)在还原条件下，将所述预催化剂与还原剂接触进行还原反应，得到所述加氢催化剂。(3) Under reducing conditions, the pre-catalyst is contacted with a reducing agent to carry out a reduction reaction to obtain the hydrogenation catalyst.
本发明第三方面提供一种制备异己二醇和甲基异丁基甲醇的方法，其中，该方法包括：在加氢催化剂存在及加氢条件下，将丙酮缩合反应液与氢气进行加氢反应，得到异己二醇和甲基异丁基甲醇；The third aspect of the present invention provides a method for preparing isohexanediol and methyl isobutyl carbinol, wherein the method comprises: hydrogenating the acetone condensation reaction liquid with hydrogen in the presence of a hydrogenation catalyst and hydrogenation conditions, Obtain isohexanediol and methyl isobutyl carbinol;
其中，所述丙酮缩合反应液含有二丙酮醇和异丙叉丙酮；所述加氢催化剂为本发明提供的的加氢催化剂和/或本发明提供的方法制得的加氢催化剂。Wherein, the acetone condensation reaction solution contains diacetone alcohol and mesityl oxide; the hydrogenation catalyst is the hydrogenation catalyst provided by the present invention and/or the hydrogenation catalyst prepared by the method provided by the present invention.
通过上述技术方案，本发明能够获得以下有益的技术效果：Through the above technical scheme, the present invention can obtain the following beneficial technical effects:
(1)活性组分与助催化剂铜形成合金结构，两者之间的协同作用可大幅提高催化活性，提高原料的转化率和目标产品的选择性，且可以降低反应温度；(1) The active component and the co-catalyst copper form an alloy structure, and the synergistic effect between the two can greatly increase the catalytic activity, improve the conversion rate of raw materials and the selectivity of target products, and can reduce the reaction temperature;
(2)催化剂孔径适中且较集中，反应物和产物分子可快速出入催化剂孔道，可避免丙酮缩合反应生成的高沸点馏分在催化剂表面的强吸附或部分聚合而造成催化剂失活；而现有镍催化剂，高沸点组分对镍催化剂活性影响较重；(2) The pore size of the catalyst is moderate and relatively concentrated, and the reactants and product molecules can quickly enter and exit the catalyst pores, which can avoid the strong adsorption or partial polymerization of the high-boiling fraction generated by the acetone condensation reaction on the surface of the catalyst to cause catalyst deactivation; while the existing nickel Catalysts, high boiling point components have a greater impact on the activity of nickel catalysts;
(3)通过碱土金属的引入，可显著改善催化剂的表面性质，避免活泼的碳碳双键和碳氧双键在催化剂表面形成胶质或其他副产物而堵塞孔道或覆盖催化剂加氢活性位；同时，也减弱了羟基在催化剂表面发生脱水、断键的副反应，因而可大幅提高催化剂的选择性。 (3) Through the introduction of alkaline earth metals, the surface properties of the catalyst can be significantly improved, and the active carbon-carbon double bond and carbon-oxygen double bond can be prevented from forming colloids or other by-products on the surface of the catalyst to block the pores or cover the hydrogenation active sites of the catalyst; At the same time, it also weakens the side reactions of dehydration and bond breaking of the hydroxyl group on the surface of the catalyst, thus greatly improving the selectivity of the catalyst.
具体实施方式Detailed ways
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
本发明第一方面提供一种制备异己二醇和甲基异丁基甲醇的加氢催化剂，其中，所述加氢催化剂包括改性载体，和负载在所述改性载体上的活性组分和助剂组分；其中，所述改性载体包括碱土金属氧化物和载体氧化物，所述载体氧化物为氧化铝和/或氧化硅，所述活性组分选自钌、钯和铂中的至少一种，所述助剂组分为铜。The first aspect of the present invention provides a hydrogenation catalyst for the preparation of isohexanediol and methyl isobutyl carbinol, wherein the hydrogenation catalyst includes a modified carrier, and an active component and a co-catalyst loaded on the modified carrier agent component; wherein, the modified carrier includes alkaline earth metal oxide and carrier oxide, the carrier oxide is alumina and/or silicon oxide, and the active component is selected from at least one of ruthenium, palladium and platinum One, the additive component is copper.
在本发明的一些优选实施方式中，优选地，基于所述改性载体的总量，所述碱土金属氧化物以金属计的含量为0.5-3wt％，可以优选为0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％和3wt％，以及上述任意两个数值形成的范围中的任意值。本发明中，引入碱土金属得到改性载体，引入碱土金属的含量在上述范围内适中，如量太小，催化效果稍差，如量太高，催化剂的孔容有影响，不能满足对大孔的需求。In some preferred embodiments of the present invention, preferably, based on the total amount of the modified carrier, the content of the alkaline earth metal oxide in terms of metal is 0.5-3wt%, preferably 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% and 3wt%, and any value in the range formed by any two of the above numerical values. In the present invention, the modified carrier is obtained by introducing alkaline earth metals. The content of the introduced alkaline earth metals is moderate within the above range. If the amount is too small, the catalytic effect will be slightly poor. If the amount is too high, the pore volume of the catalyst will be affected, which cannot meet the requirements for macropores. demand.
在本发明的一些优选实施方式中，优选地，所述碱土金属氧化物选自氧化镁、氧化钙和氧化钡中的至少一种。In some preferred embodiments of the present invention, preferably, the alkaline earth metal oxide is at least one selected from magnesium oxide, calcium oxide and barium oxide.
在本发明的一些优选实施方式中，优选地，基于所述催化剂的总量，所述活性组分的含量为0.1-3wt％，所述助剂组分的含量为0.1-0.5wt％，所述改性载体的含量为96.5-99.8wt％。其中可以进一步 优选所述活性组分的含量为0.1wt％、0.2wt％、0.3wt％、0.4wt％、0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2wt％、2.1wt％、2.2wt％、2.3wt％、2.4wt％、2.5wt％、2.6wt％、2.7wt％、2.8wt％、2.9wt％和3wt％，以及上述任意两个数值形成的范围中的任意值；所述助剂组分的含量为0.1wt％、0.2wt％、0.3wt％、0.4wt％和0.5wt％，以及上述任意两个数值形成的范围中的任意值；所述改性载体的含量为96.5wt％、97wt％、97.5wt％、98wt％、98.5wt％、99wt％、99.5wt％和99.8wt％，以及上述任意两个数值形成的范围中的任意值。In some preferred embodiments of the present invention, preferably, based on the total amount of the catalyst, the content of the active component is 0.1-3 wt%, and the content of the auxiliary component is 0.1-0.5 wt%, so The content of the modified carrier is 96.5-99.8wt%. which can be further Preferably the content of the active component is 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt% %, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4 wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt% and 3wt%, and any value in the range formed by any two of the above values; the content of the auxiliary component is 0.1 wt%, 0.2wt%, 0.3wt%, 0.4wt% and 0.5wt%, and any value in the range formed by any two of the above values; the content of the modified carrier is 96.5wt%, 97wt%, 97.5wt% %, 98wt%, 98.5wt%, 99wt%, 99.5wt% and 99.8wt%, and any value in the range formed by any two of the above numerical values.
在本发明的一些优选实施方式中，优选地，所述加氢催化剂的比表面积为160-220m2/g，孔体积为0.4-0.7cm3/g，孔径在7-12nm的孔的体积占所述加氢催化剂的总孔体积的55-80％。In some preferred embodiments of the present invention, preferably, the specific surface area of the hydrogenation catalyst is 160-220m 2 /g, the pore volume is 0.4-0.7cm 3 /g, and the volume of pores with a pore diameter of 7-12nm accounts for 55-80% of the total pore volume of the hydrogenation catalyst.
本发明提供具有上述技术特征的催化剂，能够提供制备异己二醇和甲基异丁基甲醇的加氢反应的活性更好，如原料的转化率和目标产品的选择性高，以及催化剂运行更长的时间，稳定性好。The present invention provides a catalyst with the above-mentioned technical characteristics, which can provide better activity of the hydrogenation reaction for preparing isohexanediol and methyl isobutyl carbinol, such as high conversion rate of raw materials and high selectivity of target products, and longer catalyst operation Time, good stability.
本发明第二方面提供一种制备异己二醇和甲基异丁基甲醇的加氢催化剂的方法，其中，所述方法包括：A second aspect of the present invention provides a method for preparing a hydrogenation catalyst for isohexanediol and methyl isobutyl carbinol, wherein the method comprises:
(1)将碱土金属化合物与载体和/或载体前驱体进行成型，然后经过第一干燥或不干燥后进行第一焙烧，得到改性载体；(1) molding the alkaline earth metal compound and the carrier and/or the carrier precursor, and then performing the first calcination after the first drying or not drying to obtain the modified carrier;
(2)将所述改性载体与含有活性组分元素化合物和助剂组分元素化合物的溶液接触进行浸渍，得到的产物经第二干燥或不干燥后进行第二焙烧，得到预催化剂；其中，活性组分选自钌、钯和铂中的至少 一种，助剂组分为铜；(2) The modified carrier is contacted with a solution containing an active component element compound and an auxiliary component element compound for impregnation, and the obtained product is subjected to second drying or non-drying and second calcination to obtain a pre-catalyst; wherein , the active component is selected from at least ruthenium, palladium and platinum One, the additive component is copper;
(3)在还原条件下，将所述预催化剂与还原剂接触进行还原反应，得到所述加氢催化剂。(3) Under reducing conditions, the pre-catalyst is contacted with a reducing agent to carry out a reduction reaction to obtain the hydrogenation catalyst.
在本发明的一些优选实施方式中，优选地，步骤(1)中，所述第一干燥的温度为80-120℃、所述第一干燥的时间为4-20h，所述第一焙烧的温度为600-950℃、所述第一焙烧的时间为2-10h。In some preferred embodiments of the present invention, preferably, in step (1), the temperature of the first drying is 80-120°C, the time of the first drying is 4-20h, and the first calcined The temperature is 600-950° C., and the time for the first calcination is 2-10 hours.
在本发明的一些优选实施方式中，优选地，所述碱土金属化合物选自碱土金属无机盐、碱土金属有机盐和碱土金属氢氧化物中的至少一种，优选为碱土金属硝酸盐、碱土金属乙酸盐和碱土金属氢氧化物中的至少一种，更优选为Mg、Ca和Ba中的至少一种的硝酸盐、乙酸盐和氢氧化物中的至少一种。In some preferred embodiments of the present invention, preferably, the alkaline earth metal compound is selected from at least one of alkaline earth metal inorganic salts, alkaline earth metal organic salts and alkaline earth metal hydroxides, preferably alkaline earth metal nitrates, alkaline earth metal At least one of acetate and alkaline earth metal hydroxide, more preferably at least one of nitrate, acetate and hydroxide of at least one of Mg, Ca and Ba.
在本发明的一些优选实施方式中，优选地，所述碱土金属化合物的用量使得所述改性载体中，碱土金属的含量为0.5-3wt％。可以优选为0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％和3wt％，以及上述任意两个数值形成的范围中的任意值。In some preferred embodiments of the present invention, preferably, the amount of the alkaline earth metal compound is such that the content of the alkaline earth metal in the modified support is 0.5-3 wt%. It may be preferably 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% and 3wt%, and any value in the range formed by any two of the above numerical values.
本发明中，所述载体可以选自氧化铝和/或氧化硅，所述载体前驱体可以选自拟薄水铝石、氧化铝粉或硅胶中的至少一种。所述载体和载体前驱体均选用小孔较少，而具有大孔的物质，可以是指满足孔体积大于1.0cm3/g的物质，例如本领域的大孔拟薄水铝石。所述小孔是指孔体积小于0.9cm3/g的物质。In the present invention, the carrier may be selected from alumina and/or silicon oxide, and the carrier precursor may be selected from at least one of pseudo-boehmite, alumina powder or silica gel. Both the carrier and the carrier precursor are selected from materials with few small pores and large pores, which may refer to materials with a pore volume greater than 1.0 cm 3 /g, such as large-pore pseudo-boehmite in the field. The small pores refer to substances with a pore volume of less than 0.9 cm 3 /g.
本发明中，所述成型可以是挤条、成球或压片，使得载体强度满足工业使用要求。 In the present invention, the forming may be extruded, pelletized or tableted, so that the strength of the carrier meets the requirements for industrial use.
在本发明的一些优选实施方式中，优选地，步骤(2)中，所述第二干燥的温度为80-120℃、所述第二干燥的时间为4-20h，所述第二焙烧的温度为350-500℃、所述第二焙烧的时间为4-10h。In some preferred embodiments of the present invention, preferably, in step (2), the temperature of the second drying is 80-120°C, the time of the second drying is 4-20h, and the second calcined The temperature is 350-500° C., and the time for the second calcination is 4-10 hours.
在本发明的一些优选实施方式中，优选地，所述活性组分元素化合物和助剂组分元素化合物的用量使得，所述加氢催化剂中，基于所述加氢催化剂的总量，所述活性组分的含量为0.1-3wt％，所述助剂组分的含量为0.1-0.5wt％。In some preferred embodiments of the present invention, preferably, the amount of the active component element compound and the auxiliary component element compound is such that, in the hydrogenation catalyst, based on the total amount of the hydrogenation catalyst, the The content of the active component is 0.1-3wt%, and the content of the auxiliary component is 0.1-0.5wt%.
在本发明的一些优选实施方式中，优选地，所述活性组分元素化合物选自所述活性组分的硝酸盐、氯化盐和醋酸盐中的至少一种，优选选自氯化钌、氯化铂、醋酸钯中的至少一种。In some preferred embodiments of the present invention, preferably, the active component element compound is selected from at least one of nitrate, chloride and acetate of the active component, preferably selected from ruthenium chloride , platinum chloride, palladium acetate at least one.
在本发明的一些优选实施方式中，优选地，所述助剂组分元素化合物选自所述助剂组分的硫酸盐、氯化盐、硝酸盐和醋酸盐中的至少一种，优选选自硝酸铜、硫酸铜和氯化铜中的至少一种或其水合物。In some preferred embodiments of the present invention, preferably, the element compound of the auxiliary component is selected from at least one of sulfate, chloride, nitrate and acetate of the auxiliary component, preferably At least one selected from copper nitrate, copper sulfate and copper chloride or a hydrate thereof.
在本发明的一些优选实施方式中，优选地，步骤(3)中，所述还原剂选自水合肼、硼氢化钠和甲醛中的至少一种。足以使所述活性组分元素化合物和助剂组分元素化合物还原成为相应的金属元素。In some preferred embodiments of the present invention, preferably, in step (3), the reducing agent is at least one selected from hydrazine hydrate, sodium borohydride and formaldehyde. It is sufficient to reduce the active component element compound and the auxiliary component element compound into corresponding metal elements.
在本发明的一些优选实施方式中，优选地，所述活性组分元素化合物和助剂组分元素化合物分别以活性组分和助剂组分计，所述还原剂与所述活性组分和助剂组分的总和的摩尔比为3-6:1。In some preferred embodiments of the present invention, preferably, the elemental compound of the active component and the elemental compound of the auxiliary component are calculated as the active component and the auxiliary component respectively, and the reducing agent and the active component and the The molar ratio of the sum of the auxiliary components is 3-6:1.
在本发明的一些优选实施方式中，优选地，所述还原条件包括：还原温度为30-80℃、优选为40-60℃，还原时间为2-10h、优选为4-6h；以及非氧化性气氛。 In some preferred embodiments of the present invention, preferably, the reduction conditions include: the reduction temperature is 30-80°C, preferably 40-60°C, the reduction time is 2-10h, preferably 4-6h; and non-oxidizing sex atmosphere.
本发明的步骤(3)中所述还原反应还包括将得到的产物进行干燥，所述干燥可以在60-150℃的温度下进行，优选在80-120℃的温度下进行。所述干燥的持续时间可以根据进行干燥的温度进行选择，以能将其中的溶剂脱除或基本脱除为准。一般地，所述干燥的持续时间可以为8-24小时，优选为12-20小时。所述干燥在非氧化性气氛中进行，所述非氧化性气氛例如氮气气氛和/或零族元素气氛(如氩气)。The reduction reaction in the step (3) of the present invention also includes drying the obtained product, and the drying can be carried out at a temperature of 60-150°C, preferably at a temperature of 80-120°C. The duration of the drying can be selected according to the drying temperature, whichever can remove or substantially remove the solvent therein. Generally, the duration of the drying may be 8-24 hours, preferably 12-20 hours. The drying is carried out in a non-oxidizing atmosphere, such as a nitrogen atmosphere and/or a zero-group element atmosphere (such as argon).
本发明第三方面提供一种制备异己二醇和甲基异丁基甲醇的方法，其中，该方法包括：在加氢催化剂存在及加氢条件下，将丙酮缩合反应液与氢气进行加氢反应，得到异己二醇和甲基异丁基甲醇；The third aspect of the present invention provides a method for preparing isohexanediol and methyl isobutyl carbinol, wherein the method comprises: hydrogenating the acetone condensation reaction liquid with hydrogen in the presence of a hydrogenation catalyst and hydrogenation conditions, Obtain isohexanediol and methyl isobutyl carbinol;
其中，所述丙酮缩合反应液含有二丙酮醇和异丙叉丙酮；所述加氢催化剂为本发明提供的的加氢催化剂和/或本发明提供的方法制得的加氢催化剂。Wherein, the acetone condensation reaction solution contains diacetone alcohol and mesityl oxide; the hydrogenation catalyst is the hydrogenation catalyst provided by the present invention and/or the hydrogenation catalyst prepared by the method provided by the present invention.
在本发明的一些优选实施方式中，优选地，所述丙酮缩合反应液含有丙酮、异佛尔酮和杂质。所述杂质可以是丙酮的一些低分子聚合物。In some preferred embodiments of the present invention, preferably, the acetone condensation reaction liquid contains acetone, isophorone and impurities. The impurities may be some low molecular weight polymers of acetone.
在本发明的一些优选实施方式中，优选地，基于所述丙酮缩合反应液的总量，二丙酮醇的含量为10-90wt％，异丙叉丙酮的含量为5-90wt％，丙酮、异佛尔酮和杂质的总含量为5wt％以内。In some preferred embodiments of the present invention, preferably, based on the total amount of the acetone condensation reaction liquid, the content of diacetone alcohol is 10-90wt%, the content of mesityl oxide is 5-90wt%, acetone, isopropylidene The total content of phorone and impurities is within 5wt%.
在本发明的一些优选实施方式中，优选地，所述酮缩合反应液为丙酮在碱性催化剂条件下发生缩合反应形成的产物，其中，所述缩合反应的温度为0-80℃，可以获得上述组成的丙酮缩合反应液。In some preferred embodiments of the present invention, preferably, the ketone condensation reaction solution is a product formed by the condensation reaction of acetone under the condition of a basic catalyst, wherein the temperature of the condensation reaction is 0-80°C, which can be obtained The acetone condensation reaction liquid of above-mentioned composition.
在本发明的一些优选实施方式中，优选地，所述加氢条件包括： 加氢温度为50-120℃，加氢压力为1-7MPa，氢气与所述丙酮缩合反应液的体积比为30-100:1，所述丙酮缩合反应液的液时空速为0.2-4h-1；In some preferred embodiments of the present invention, preferably, the hydrogenation conditions include: The hydrogenation temperature is 50-120°C, the hydrogenation pressure is 1-7MPa, the volume ratio of hydrogen to the acetone condensation reaction liquid is 30-100:1, and the liquid hourly space velocity of the acetone condensation reaction liquid is 0.2-4h - 1 ;
优选，加氢温度为60-110℃，加氢压力为3-5MPa，氢气与所述丙酮缩合反应液的体积比为40-70:1，所述丙酮缩合反应液的液时空速为0.3-1.8h-1。Preferably, the hydrogenation temperature is 60-110°C, the hydrogenation pressure is 3-5MPa, the volume ratio of hydrogen to the acetone condensation reaction liquid is 40-70:1, and the liquid hourly space velocity of the acetone condensation reaction liquid is 0.3- 1.8h -1 .
本发明中，所述加氢反应可以在列管式固定床反应器中进行，在催化剂存在及加氢条件下，将丙酮缩合反应液与氢气在反应器中接触，丙酮缩合反应液与氢气接触的方式可以为丙酮缩合反应液与氢气由上而下经过反应器，也可以由下而上经过反应器。In the present invention, the hydrogenation reaction can be carried out in a tubular fixed-bed reactor. In the presence of a catalyst and hydrogenation conditions, the acetone condensation reaction solution is contacted with hydrogen in the reactor, and the acetone condensation reaction solution is contacted with hydrogen. The method can be that the acetone condensation reaction liquid and hydrogen pass through the reactor from top to bottom, and can also pass through the reactor from bottom to top.
以下将通过实施例对本发明进行详细描述。以下实施例中，催化剂中各金属含量参数通过原子发射光谱仪测得；丙酮原料为市售品。The present invention will be described in detail below by way of examples. In the following examples, each metal content parameter in the catalyst is measured by an atomic emission spectrometer; the acetone raw material is a commercial product.
实施例1Example 1
制备加氢催化剂A：Preparation of hydrogenation catalyst A:
(1)将9.25g的Mg(NO3)2和大孔拟薄水铝石(以Al2O3计为98.5g，孔体积大于1.0cm3/g，下同)充分混合后，进行挤条成型，然后将所得产物在100℃下干燥20h，然后于750℃下焙烧5h，得到镁改性载体；(1) After fully mixing 9.25g of Mg(NO 3 ) 2 and macroporous pseudo-boehmite (98.5g as Al 2 O 3 , the pore volume is greater than 1.0cm 3 /g, the same below), extrude Strip molding, then drying the obtained product at 100°C for 20h, and then calcining at 750°C for 5h to obtain a magnesium-modified carrier;
(2)将含1.02g的RuCl3和0.46g的Cu(NO3)2·6H2O的水溶液与镁改性载体接触进行浸渍，以将RuCl3和Cu(NO3)2负载到镁改性载体上，然后于80℃下干燥20h，然后在450℃下焙烧4h，得到预催化剂；(2) The aqueous solution containing 1.02g of RuCl 3 and 0.46g of Cu(NO 3 ) 2 ·6H 2 O was impregnated in contact with the magnesium-modified support to load RuCl 3 and Cu(NO 3 ) 2 onto the magnesium-modified support. on the carrier, then dried at 80°C for 20h, and then calcined at 450°C for 4h to obtain a pre-catalyst;
(3)将预催化剂置于水合肼水溶液(水合肼与Cu和Ru总量的摩尔 比为4:1)中，在60℃的温度下进行还原反应4h后，用去离子水洗涤3次，并在80℃的温度下于N2气氛中干燥8h，得到加氢催化剂A，催化剂重量百分数组成及物化参数见表1。(3) pre-catalyst is placed in hydrazine hydrate aqueous solution (the mole of hydrazine hydrate and Cu and Ru total amount In the ratio of 4:1), the reduction reaction was carried out at a temperature of 60 ° C for 4 h, washed three times with deionized water, and dried at a temperature of 80 ° C in an N atmosphere for 8 h to obtain a hydrogenation catalyst A, the catalyst See Table 1 for weight percent composition and physical and chemical parameters.
丙酮缩合反应液加氢制备异己二醇和甲基异丁基甲醇：Hydrogenation of acetone condensation reaction liquid to prepare isohexanediol and methyl isobutyl carbinol:
取5.0g的催化剂A装入内径为10mm、长度为90cm的固定床不锈钢反应器中，反应器上下两端装填石英砂，中间装填催化剂，以保证催化剂在反应器的恒温区(如无特别说明，以下实施例均使用该反应器，装填方式也一致)，然后进行丙酮缩合反应液的加氢反应；Get 5.0g of catalyst A and put it into a fixed-bed stainless steel reactor with an internal diameter of 10mm and a length of 90cm. The upper and lower ends of the reactor are filled with quartz sand, and the middle is filled with catalyst to ensure that the catalyst is in the constant temperature zone of the reactor (if no special instructions , the following examples all use this reactor, and the filling method is also consistent), and then carry out the hydrogenation reaction of the acetone condensation reaction liquid;
其中，加氢反应的条件包括：丙酮缩合反应液中二丙酮醇含量90wt％，异丙叉丙酮含量5wt％，丙酮含量3wt％，异佛尔酮含量1.3wt％，余量为杂质；加氢温度为85℃，加氢压力为5MPa，氢气与丙酮缩合反应液的体积比为30:1，丙酮缩合反应液的液时空速为2h-1，反应结果见表1。Wherein, the conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the content of diacetone alcohol is 90wt%, the content of mesityl oxide is 5wt%, the content of acetone is 3wt%, the content of isophorone is 1.3wt%, and the balance is impurities; The temperature was 85°C, the hydrogenation pressure was 5MPa, the volume ratio of hydrogen to acetone condensation reaction solution was 30:1, and the liquid hourly space velocity of the acetone condensation reaction solution was 2h -1 . The reaction results are shown in Table 1.
实施例2Example 2
制备加氢催化剂B：Preparation of hydrogenation catalyst B:
(1)将3.08g的Mg(NO3)2、SiO2溶胶及大孔拟薄水铝石(以SiO2-Al2O3计为99.5g，其中SiO2含量为30wt％)充分混合后，进行挤条成型，然后将所得产物在120℃下干燥10h，然后于600℃下焙烧5h，得到镁改性载体；(1) After fully mixing 3.08g of Mg(NO 3 ) 2 , SiO 2 sol and macroporous pseudo-boehmite (99.5g as SiO 2 -Al 2 O 3 , wherein the SiO 2 content is 30wt%) , extruded, then dried at 120°C for 10 hours, and then calcined at 600°C for 5 hours to obtain a magnesium-modified carrier;
(2)将含6.08g的RuCl3和1.88g的Cu(NO3)2·3H2O的水溶液与镁改性载体接触以进行浸渍，以将RuCl3和Cu(NO3)2负载到镁改性载 体上，然后于120℃下干燥10h，然后在500℃下焙烧10h，得到预催化剂；(2) An aqueous solution containing 6.08 g of RuCl 3 and 1.88 g of Cu(NO 3 ) 2 3H 2 O was contacted with a magnesium-modified support for impregnation to load RuCl 3 and Cu(NO 3 ) 2 onto magnesium modified loading body, then dried at 120°C for 10h, and then calcined at 500°C for 10h to obtain a pre-catalyst;
(3)将预催化剂置于硼氢化钠水溶液(硼氢化钠与Ru和Cu总量的摩尔比为5:1)中，在50℃的温度下进行还原反应5h后，用去离子水洗涤3次，并在80℃的温度下于Ar气氛中干燥8h，得到加氢催化剂B，催化剂重量百分数组成及物化参数见表1。(3) Place the pre-catalyst in an aqueous solution of sodium borohydride (the molar ratio of sodium borohydride to the total amount of Ru and Cu is 5:1), perform a reduction reaction at a temperature of 50°C for 5 hours, and wash with deionized water for 3 times, and dried in an Ar atmosphere at a temperature of 80° C. for 8 hours to obtain a hydrogenation catalyst B. The composition and physical and chemical parameters of the catalyst are shown in Table 1.
丙酮缩合反应液加氢制备异己二醇和甲基异丁基甲醇：Hydrogenation of acetone condensation reaction liquid to prepare isohexanediol and methyl isobutyl carbinol:
加氢反应的条件包括：丙酮缩合反应液中二丙酮醇含量50wt％，异丙叉丙酮含量46wt％，丙酮含量2wt％，异佛尔酮含量1wt％，余量为杂质；加氢温度为50℃，加氢压力为7MPa，氢气与丙酮缩合反应液的体积比为100:1，丙酮缩合反应液的液时空速为0.5h-1，反应结果见表1。The conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the content of diacetone alcohol is 50wt%, the content of mesityl oxide is 46wt%, the content of acetone is 2wt%, the content of isophorone is 1wt%, and the balance is impurities; the hydrogenation temperature is 50 ℃, the hydrogenation pressure is 7MPa, the volume ratio of hydrogen to the acetone condensation reaction solution is 100:1, and the liquid hourly space velocity of the acetone condensation reaction solution is 0.5h -1 . The reaction results are shown in Table 1.
实施例3Example 3
制备加氢催化剂C：Preparation of hydrogenation catalyst C:
(1)将12.3g的Ca(NO3)2和SiO2溶胶(以SiO2计为97.0g)充分混合后，进行挤条成型，然后将所得产物在120℃下干燥6h，然后于950℃下焙烧2h，得到钙改性载体；(1) After fully mixing 12.3g of Ca(NO 3 ) 2 and SiO 2 sol (97.0g as SiO 2 ), extrusion molding was carried out, and then the resulting product was dried at 120°C for 6h, and then dried at 950°C Lower roasting for 2 hours to obtain the calcium-modified carrier;
(2)将含0.17g的PtCl4和1.07g的CuCl2·2H2O的水溶液与钙改性载体接触以进行浸渍，将PtCl4和CuCl2负载到钙改性载体上，然后于120℃下干燥10h，然后在350℃下焙烧4h，得到预催化剂；(2) Contact an aqueous solution containing 0.17g of PtCl 4 and 1.07g of CuCl 2 ·2H 2 O with the calcium-modified carrier for impregnation, load PtCl 4 and CuCl 2 on the calcium-modified carrier, and then drying at 350°C for 10 hours, and then calcined at 350°C for 4 hours to obtain a pre-catalyst;
(3)将预催化剂置于硼氢化钠水溶液(硼氢化钠与Pt和Cu总量的 摩尔比为6:1)中，在80℃的温度下进行还原反应2h后，用去离子水洗涤3次，并在100℃的温度下于Ar气氛中干燥7h，得到加氢催化剂C，催化剂重量百分数组成及物化参数见表1。(3) pre-catalyst is placed in sodium borohydride aqueous solution (sodium borohydride and Pt and Cu total amount The molar ratio is 6:1), after the reduction reaction was carried out at a temperature of 80 ° C for 2 h, washed with deionized water for 3 times, and dried in an Ar atmosphere at a temperature of 100 ° C for 7 h to obtain a hydrogenation catalyst C, the catalyst See Table 1 for weight percent composition and physical and chemical parameters.
丙酮缩合反应液加氢制备异己二醇和甲基异丁基甲醇：Hydrogenation of acetone condensation reaction liquid to prepare isohexanediol and methyl isobutyl carbinol:
加氢反应的条件包括：丙酮缩合反应液中二丙酮醇含量85wt％，异丙叉丙酮含量12wt％，丙酮含量2wt％，异佛尔酮含量0.5wt％，余量为杂质；加氢温度为120℃，加氢压力为1MPa，氢气与丙酮缩合反应液的体积比为50:1，丙酮缩合反应液的液时空速为4h-1，反应结果见表1。The conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the diacetone alcohol content is 85wt%, the mesityl oxide content is 12wt%, the acetone content is 2wt%, the isophorone content is 0.5wt%, and the balance is impurities; the hydrogenation temperature is 120°C, hydrogenation pressure 1MPa, volume ratio of hydrogen to acetone condensation reaction liquid 50:1, liquid hourly space velocity of acetone condensation reaction liquid 4h -1 , reaction results are shown in Table 1.
实施例4Example 4
制备加氢催化剂D：Preparation of hydrogenation catalyst D:
(1)将7.9g的Ca(CH3COO)2和氢氧化铝粉(以Al2O3计为98.0g)充分混合后，进行挤条成型，然后将所得产物在120℃下干燥6h，然后于750℃下焙烧2h，得到钙改性载体；(1) After fully mixing 7.9 g of Ca(CH 3 COO) 2 and aluminum hydroxide powder (98.0 g as Al 2 O 3 ), perform extrusion molding, and then dry the resulting product at 120° C. for 6 h, Then calcined at 750°C for 2 hours to obtain a calcium-modified carrier;
(2)将含0.63g的Pd(CH3COO)2和0.78g的CuSO4·5H2O的水溶液与钙改性载体接触进行浸渍，以将Pd(CH3COO)2和CuSO4负载到钙改性载体上，然后于110℃下干燥9h，然后在450℃下焙烧6h，得到预催化剂；(2) An aqueous solution containing 0.63 g of Pd(CH 3 COO) 2 and 0.78 g of CuSO 4 ·5H 2 O was impregnated in contact with the calcium-modified support to load Pd(CH 3 COO) 2 and CuSO 4 on Calcium-modified carrier, then dried at 110°C for 9h, and then calcined at 450°C for 6h to obtain a pre-catalyst;
(3)将预催化剂置于水合肼、甲醛水溶液(水合肼、甲醛与Pd和Cu总量的摩尔比为6:1)中，在70℃的温度下反应5h后，用去离子水洗涤3次，并在120℃的温度下于N2气氛中干燥6h，得到加氢催化 剂D，催化剂重量百分数组成及物化参数见表1。(3) Place the precatalyst in hydrazine hydrate and formaldehyde aqueous solution (the molar ratio of hydrazine hydrate, formaldehyde to the total amount of Pd and Cu is 6:1), react at a temperature of 70°C for 5h, and wash with deionized water for 3 times, and dried at 120 °C in N2 atmosphere for 6 h to obtain the hydrogenation catalyst Agent D, catalyst weight percent composition and physical and chemical parameters are shown in Table 1.
丙酮缩合反应液加氢制备异己二醇和甲基异丁基甲醇：Hydrogenation of acetone condensation reaction liquid to prepare isohexanediol and methyl isobutyl carbinol:
加氢反应的条件包括：丙酮缩合反应液中二丙酮醇含量10wt％，异丙叉丙酮含量87wt％，丙酮含量2wt％，异佛尔酮含量0.2wt％，余量为杂质；加氢温度为90℃，加氢压力为3MPa，氢气与丙酮缩合反应液的体积比为45:1，丙酮缩合反应液的液时空速为1.5h-1，反应结果见表1。The conditions of the hydrogenation reaction include: in the acetone condensation reaction liquid, the diacetone alcohol content is 10wt%, the mesityl oxide content is 87wt%, the acetone content is 2wt%, the isophorone content is 0.2wt%, and the balance is impurities; the hydrogenation temperature is 90°C, hydrogenation pressure 3MPa, volume ratio of hydrogen to acetone condensation reaction liquid 45:1, liquid hourly space velocity of acetone condensation reaction liquid 1.5h -1 , reaction results are shown in Table 1.
实施例5Example 5
制备加氢催化剂E：Preparation of hydrogenation catalyst E:
(1)将1.87g的Ba(OH)2和氢氧化铝粉(以Al2O3计为98.5g)充分混合后，进行挤条成型，然后将所得产物在100℃下干燥6h，然后于800℃下焙烧4h，得到钡改性载体；(1) After fully mixing 1.87g of Ba(OH) 2 and aluminum hydroxide powder (98.5g as Al 2 O 3 ), carry out extrusion molding, and then dry the obtained product at 100°C for 6h, and then Calcined at 800°C for 4 hours to obtain a barium-modified carrier;
(2)将含1.26g的Pd(CH3COO)2和0.81g的Cu(NO3)2·3H2O的水溶液与钡改性载体接触进行浸渍，以将Pd(CH3COO)2和Cu(NO3)2负载到钡改性载体上，然后于110℃下干燥10h，然后在400℃下焙烧8h，得到预催化剂；(2) Contact an aqueous solution containing 1.26g of Pd(CH 3 COO) 2 and 0.81g of Cu(NO 3 ) 2 ·3H 2 O with the barium-modified support for impregnation, so that Pd(CH 3 COO) 2 and Cu(NO 3 ) 2 was loaded onto the barium-modified carrier, then dried at 110°C for 10 hours, and then calcined at 400°C for 8 hours to obtain a pre-catalyst;
(3)将预催化剂置于甲醛水溶液(甲醛与Pd和Cu总量的摩尔比为3:1)中，在65℃的温度下反应5h后，用去离子水洗涤3次，并在100℃的温度下于N2气氛中干燥5h，得到加氢催化剂E，催化剂重量百分数组成及物化参数见表1。(3) Place the pre-catalyst in an aqueous formaldehyde solution (the molar ratio of formaldehyde to the total amount of Pd and Cu is 3:1), react at a temperature of 65°C for 5h, wash with deionized water three times, and The hydrogenation catalyst E was obtained by drying in an N atmosphere for 5 hours at a temperature of 100°C. The composition and physical and chemical parameters of the catalyst weight percent are shown in Table 1.
丙酮缩合反应液加氢制备异己二醇和甲基异丁基甲醇： Hydrogenation of acetone condensation reaction liquid to prepare isohexanediol and methyl isobutyl carbinol:
加氢反应的条件包括：丙酮缩合反应液中二丙酮醇含量90wt％，异丙叉丙酮含量5wt％，丙酮含量3wt％，异佛尔酮含量0.7wt％，余量为杂质；The conditions of the hydrogenation reaction include: the content of diacetone alcohol in the acetone condensation reaction liquid is 90wt%, the content of mesityl oxide is 5wt%, the content of acetone is 3wt%, the content of isophorone is 0.7wt%, and the balance is impurities;
加氢温度为115℃，加氢压力为5MPa，氢气与丙酮缩合反应液的体积比为70:1，丙酮缩合反应液的液时空速为1.0h-1，反应结果见表1。The hydrogenation temperature was 115°C, the hydrogenation pressure was 5MPa, the volume ratio of hydrogen to acetone condensation reaction solution was 70:1, and the liquid hourly space velocity of the acetone condensation reaction solution was 1.0h -1 . The reaction results are shown in Table 1.
对比例1Comparative example 1
加氢催化剂制备过程与实施例1相同，不同的是载体未经碱土金属Mg改性处理。加氢反应条件相同。The preparation process of the hydrogenation catalyst is the same as that of Example 1, except that the support is not modified by alkaline earth metal Mg. The hydrogenation reaction conditions are the same.
对比例2Comparative example 2
加氢催化剂制备过程与实施例1相同，不同的是，催化剂中未添加Cu助剂。加氢反应条件相同。The preparation process of the hydrogenation catalyst was the same as in Example 1, except that no Cu additive was added to the catalyst. The hydrogenation reaction conditions are the same.
对比例3Comparative example 3
加氢催化剂制备过程与实施例1相同，不同的是，用小孔氧化铝粉(孔体积小于0.9cm3/g)替代大孔拟薄水铝石。加氢反应条件相同。The preparation process of the hydrogenation catalyst is the same as in Example 1, except that the large-pore pseudo-boehmite is replaced by small-pore alumina powder (pore volume less than 0.9 cm 3 /g). The hydrogenation reaction conditions are the same.
对比例4Comparative example 4
催化剂采用Ni/Al2O3，其中Ni含量为30wt％。加氢反应条件相同。 The catalyst is Ni/Al 2 O 3 , wherein the Ni content is 30wt%. The hydrogenation reaction conditions are the same.
对比例5Comparative example 5
加氢催化剂制备过程与对比例2相同，不同的是，加氢反应条件中加氢温度不同，加氢温度为105℃。The preparation process of the hydrogenation catalyst is the same as that of Comparative Example 2, except that the hydrogenation temperature in the hydrogenation reaction conditions is different, and the hydrogenation temperature is 105°C.
表1实施例、对比例催化剂及反应结果
Table 1 embodiment, comparative example catalyst and reaction result
实施例6Example 6
采用实施例4催化剂D，进行催化剂活性稳定性考察，加氢原料为：丙酮缩合反应液中二丙酮醇含量86％，异丙叉丙酮含量10％，丙酮含量2％，异佛尔酮含量0.9％，余量为杂质；加氢反应的条件为：加氢温度为80-90℃加氢，丙酮缩合反应液的压力为5MPa，氢气与 丙酮缩合反应液的体积比为40-60:1，丙酮缩合反应液的液时空速为0.8h-1，其反应结果见表2。由运行结果可知，催化剂活性、选择性好，稳定性高。Catalyst D of Example 4 was used to investigate the activity and stability of the catalyst. The hydrogenation raw materials were: in the acetone condensation reaction liquid, the content of diacetone alcohol was 86%, the content of mesityl oxide was 10%, the content of acetone was 2%, and the content of isophorone was 0.9% %, the balance is impurities; the conditions of the hydrogenation reaction are: the hydrogenation temperature is 80-90 ° C hydrogenation, the pressure of the acetone condensation reaction liquid is 5MPa, hydrogen and The volume ratio of the acetone condensation reaction solution is 40-60:1, and the liquid hourly space velocity of the acetone condensation reaction solution is 0.8h -1 . The reaction results are shown in Table 2. It can be seen from the running results that the catalyst has good activity, selectivity and high stability.
表2 实施例6催化剂稳定性考察结果
Table 2 Example 6 Catalyst Stability Investigation Results
由实施例、对比例和表1、2的数据可以看出：实施例1与对比例2对比表明，助催化剂的加入，可明显提高催化剂活性，丙酮转化率100％，异己二醇和甲基异丁基醇的选择性都更高；实施例1与对比例1对比表明，碱土金属的加入，异己二醇的选择性由93.3％升至99.9％，甲基异丁基醇的选择性由94.6％升至100％，可明显提高催化的选择性；实施例1与对比例3对比表明，本发明提供的催化剂控制孔结构在限定的范围内时，反应物和产物分子可快速出入催化剂孔道，从而提高催化活性；实施例1与对比例4对比表明，镍催化剂活性明显低于实施例1催化剂；实施例6催化剂稳定性考察结果表明，本发明的催化剂活性、稳定性较好。 As can be seen from the data of Examples, Comparative Examples and Tables 1 and 2: the comparison between Example 1 and Comparative Example 2 shows that the addition of co-catalyst can obviously improve the catalyst activity, acetone conversion rate 100%, isohexanediol and methyl iso The selectivity of butyl alcohol is all higher; The contrast of embodiment 1 and comparative example 1 shows, the addition of alkaline earth metal, the selectivity of isohexanediol rises to 99.9% by 93.3%, the selectivity of methyl isobutyl alcohol by 94.6% % rises to 100%, can obviously improve the selectivity of catalysis; Embodiment 1 and comparative example 3 contrast show, when the catalyzer control pore structure provided by the present invention is in the limited scope, reactant and product molecule can enter and exit catalyst pore rapidly, Thereby the catalytic activity is improved; the comparison of Example 1 and Comparative Example 4 shows that the activity of the nickel catalyst is significantly lower than that of the catalyst of Example 1; the results of the investigation of the stability of the catalyst in Example 6 show that the catalyst of the present invention has better activity and stability.
实施例1、对比例2和对比例5相比，可以看出如无助催化剂的加入，对比例5需要提高反应温度才能获得与实施例1接近的原料转化率，可见本发明的催化剂可以降低加氢反应温度而获得好的催化活性。Embodiment 1, comparative example 2 are compared with comparative example 5, as can be seen as adding without co-catalyst, comparative example 5 needs to increase reaction temperature and just can obtain the raw material conversion rate close to embodiment 1, it can be seen that catalyst of the present invention can reduce Hydrogenation reaction temperature to obtain good catalytic activity.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。 The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (11)

  1. 一种制备异己二醇和甲基异丁基甲醇的加氢催化剂，其特征在于，所述加氢催化剂包括改性载体，和负载在所述改性载体上的活性组分和助剂组分；其中，所述改性载体包括碱土金属氧化物和载体氧化物，所述载体氧化物为氧化铝和/或氧化硅，所述活性组分选自钌、钯和铂中的至少一种，所述助剂组分为铜。A hydrogenation catalyst for preparing isohexanediol and methyl isobutyl carbinol, characterized in that the hydrogenation catalyst includes a modified carrier, and an active component and an auxiliary component loaded on the modified carrier; Wherein, the modified carrier includes alkaline earth metal oxides and carrier oxides, the carrier oxide is alumina and/or silicon oxide, and the active component is selected from at least one of ruthenium, palladium and platinum, so The additive component mentioned above is copper.
  2. 根据权利要求1所述的加氢催化剂，其特征在于，基于所述改性载体的总量，所述碱土金属氧化物以金属计的含量为0.5-3wt％；The hydrogenation catalyst according to claim 1, characterized in that, based on the total amount of the modified carrier, the content of the alkaline earth metal oxide in terms of metal is 0.5-3wt%;
    优选地，所述碱土金属氧化物选自氧化镁、氧化钙和氧化钡中的至少一种。Preferably, the alkaline earth metal oxide is at least one selected from magnesium oxide, calcium oxide and barium oxide.
  3. 根据权利要求1或2所述的加氢催化剂，其特征在于，基于所述催化剂的总量，所述活性组分的含量为0.1-3wt％，所述助剂组分的含量为0.1-0.5wt％，所述改性载体的含量为96.5-99.8wt％。The hydrogenation catalyst according to claim 1 or 2, characterized in that, based on the total amount of the catalyst, the content of the active component is 0.1-3 wt%, and the content of the auxiliary component is 0.1-0.5 % by weight, the content of the modified carrier is 96.5-99.8% by weight.
  4. 根据权利要求1-3中任意一项所述的加氢催化剂，其特征在于，所述加氢催化剂的比表面积为160-220m2/g，孔体积为0.4-0.7cm3/g，孔径在7-12nm的孔的体积占所述加氢催化剂的总孔体积的55-80％。The hydrogenation catalyst according to any one of claims 1-3, characterized in that, the specific surface area of the hydrogenation catalyst is 160-220m 2 /g, the pore volume is 0.4-0.7cm 3 /g, and the pore diameter is between The volume of pores of 7-12 nm accounts for 55-80% of the total pore volume of the hydrogenation catalyst.
  5. 一种制备异己二醇和甲基异丁基甲醇的加氢催化剂的方法，其特征在于，所述方法包括： A method for preparing a hydrogenation catalyst of isohexanediol and methyl isobutyl carbinol, characterized in that the method comprises:
    (1)将碱土金属化合物与载体和/或载体前驱体进行成型，然后经过第一干燥或不干燥后进行第一焙烧，得到改性载体；(1) molding the alkaline earth metal compound and the carrier and/or the carrier precursor, and then performing the first calcination after the first drying or not drying to obtain the modified carrier;
    (2)将所述改性载体与含有活性组分元素化合物和助剂组分元素化合物的溶液接触进行浸渍，得到的产物经第二干燥或不干燥后进行第二焙烧，得到预催化剂；其中，活性组分选自钌、钯和铂中的至少一种，助剂组分为铜；(2) The modified carrier is contacted with a solution containing an active component element compound and an auxiliary component element compound for impregnation, and the obtained product is subjected to second drying or non-drying and second calcination to obtain a pre-catalyst; wherein , the active component is selected from at least one of ruthenium, palladium and platinum, and the auxiliary component is copper;
    (3)在还原条件下，将所述预催化剂与还原剂接触进行还原反应，得到所述加氢催化剂。(3) Under reducing conditions, the pre-catalyst is contacted with a reducing agent to carry out a reduction reaction to obtain the hydrogenation catalyst.
  6. 根据权利要求5所述的方法，其特征在于，步骤(1)中，所述第一干燥的温度为80-120℃、所述第一干燥的时间为4-20h，所述第一焙烧的温度为600-950℃、所述第一焙烧的时间为2-10h；The method according to claim 5, characterized in that, in step (1), the temperature of the first drying is 80-120°C, the time of the first drying is 4-20h, and the first roasting The temperature is 600-950°C, and the time for the first calcination is 2-10h;
    优选地，所述碱土金属化合物选自碱土金属无机盐、碱土金属有机盐和碱土金属氢氧化物中的至少一种，优选为碱土金属硝酸盐、碱土金属醋酸盐和碱土金属氢氧化物中的至少一种，更优选为Mg、Ca和Ba中的至少一种的硝酸盐、醋酸盐和氢氧化物中的至少一种；Preferably, the alkaline earth metal compound is selected from at least one of alkaline earth metal inorganic salts, alkaline earth metal organic salts and alkaline earth metal hydroxides, preferably alkaline earth metal nitrates, alkaline earth metal acetates and alkaline earth metal hydroxides At least one of, more preferably at least one of nitrate, acetate and hydroxide of at least one of Mg, Ca and Ba;
    优选地，所述碱土金属化合物的用量使得所述改性载体中，碱土金属的含量为0.5-3wt％。Preferably, the amount of the alkaline earth metal compound is such that the content of the alkaline earth metal in the modified carrier is 0.5-3 wt%.
  7. 根据权利要求5或6所述的方法，其特征在于，步骤(2)中，所述第二干燥的温度为80-120℃、所述第二干燥的时间为4-20h，所述第二焙烧的温度为350-500℃、所述第二焙烧的时间为4-10h； The method according to claim 5 or 6, characterized in that, in step (2), the temperature of the second drying is 80-120°C, the time of the second drying is 4-20h, and the second drying The calcination temperature is 350-500°C, and the second calcination time is 4-10h;
    优选地，所述活性组分元素化合物和助剂组分元素化合物的用量使得，所述加氢催化剂中，所述活性组分的含量为0.1-3wt％，所述助剂组分的含量为0.1-0.5wt％；Preferably, the amount of the element compound of the active component and the element compound of the auxiliary component is such that, in the hydrogenation catalyst, the content of the active component is 0.1-3wt%, and the content of the auxiliary component is 0.1-0.5wt%;
    优先地，所述活性组分元素化合物选自所述活性组分的硝酸盐、氯化盐和醋酸盐中的至少一种，所述助剂组分元素化合物选自所述助剂组分的硫酸盐、氯化盐、硝酸盐和醋酸盐中的至少一种。Preferably, the active component element compound is selected from at least one of nitrate, chloride and acetate of the active component, and the auxiliary component element compound is selected from the auxiliary component At least one of sulfate, chloride, nitrate and acetate.
  8. 根据权利要求5-7中任意一项所述的方法，其特征在于，步骤(3)中，所述还原剂选自水合肼、硼氢化钠和甲醛中的至少一种；The method according to any one of claims 5-7, characterized in that, in step (3), the reducing agent is selected from at least one of hydrazine hydrate, sodium borohydride and formaldehyde;
    优选地，所述活性组分元素化合物和助剂组分元素化合物分别以活性组分和助剂组分计，所述还原剂与所述活性组分和助剂组分的总和的摩尔比为3-6:1；Preferably, the active component elemental compound and the auxiliary component elemental compound are calculated based on the active component and the auxiliary component respectively, and the molar ratio of the reducing agent to the sum of the active component and the auxiliary component is 3-6:1;
    优选地，所述还原条件包括：还原温度为30-80℃、还原时间为2-10h，以及非氧化性气氛。Preferably, the reduction conditions include: a reduction temperature of 30-80° C., a reduction time of 2-10 h, and a non-oxidizing atmosphere.
  9. 一种制备异己二醇和甲基异丁基甲醇的方法，其特征在于，该方法包括：在加氢催化剂存在及加氢条件下，将丙酮缩合反应液与氢气进行加氢反应，得到异己二醇和甲基异丁基甲醇；A method for preparing isohexanediol and methyl isobutyl carbinol, characterized in that the method comprises: in the presence of a hydrogenation catalyst and under hydrogenation conditions, hydrogenating the acetone condensation reaction liquid with hydrogen to obtain isohexanediol and Methyl isobutyl carbinol;
    其中，所述丙酮缩合反应液含有二丙酮醇和异丙叉丙酮；所述加氢催化剂为权利要求1-4中任意一项所述的加氢催化剂和/或权利要求5-8中任意一项所述的方法制得的加氢催化剂。 Wherein, the acetone condensation reaction liquid contains diacetone alcohol and mesityl oxide; the hydrogenation catalyst is the hydrogenation catalyst described in any one of claims 1-4 and/or any one of claims 5-8 The hydrogenation catalyst prepared by the method.
  10. 根据权利要求9所述的方法，其特征在于，所述丙酮缩合反应液含有丙酮、异佛尔酮和杂质；The method according to claim 9, wherein the acetone condensation reaction liquid contains acetone, isophorone and impurities;
    优选地，基于所述丙酮缩合反应液的总量，二丙酮醇的含量为10-90wt％，异丙叉丙酮的含量为5-90wt％，丙酮、异佛尔酮和杂质的总含量为5wt％以内。Preferably, based on the total amount of the acetone condensation reaction liquid, the content of diacetone alcohol is 10-90wt%, the content of mesityl oxide is 5-90wt%, and the total content of acetone, isophorone and impurities is 5wt% % within.
  11. 根据权利要求9或10所述的方法，其特征在于，所述加氢条件包括：加氢温度为50-120℃，加氢压力为1-7MPa，氢气与所述丙酮缩合反应液的体积比为30-100:1，所述丙酮缩合反应液的液时空速为0.2-4h-1；The method according to claim 9 or 10, wherein the hydrogenation conditions include: the hydrogenation temperature is 50-120°C, the hydrogenation pressure is 1-7MPa, the volume ratio of hydrogen to the acetone condensation reaction liquid For 30-100:1, the liquid hourly space velocity of described acetone condensation reaction liquid is 0.2-4h −1 ;
    优选，加氢温度为60-110℃，加氢压力为3-5MPa，氢气与所述丙酮缩合反应液的体积比为40-70:1，所述丙酮缩合反应液的液时空速为0.3-1.8h-1。 Preferably, the hydrogenation temperature is 60-110°C, the hydrogenation pressure is 3-5MPa, the volume ratio of hydrogen to the acetone condensation reaction liquid is 40-70:1, and the liquid hourly space velocity of the acetone condensation reaction liquid is 0.3- 1.8h -1 .
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