CN111001432A - Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof - Google Patents

Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof Download PDF

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CN111001432A
CN111001432A CN201811166040.8A CN201811166040A CN111001432A CN 111001432 A CN111001432 A CN 111001432A CN 201811166040 A CN201811166040 A CN 201811166040A CN 111001432 A CN111001432 A CN 111001432A
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catalyst
oxide
molecular sieve
acetone
diisobutyl ketone
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宋超
唐国旗
向良玉
李宝芹
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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

Abstract

The invention relates to a catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, a preparation method and application thereof, belonging to the technical field of ketone hydrogenation condensation. The catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation comprises the following components in percentage by weight: (1) 2% -25% of copper or its oxide; (2) 7-35% of zinc or its oxide; (3) 2% -40% of cobalt or its oxide; (4) 1-10% of barium or its oxide; (5)10 to 80 percent of alumina; (6)1 to 70 percent of molecular sieve. The catalyst takes copper, zinc, cobalt and the like as load components, properly adjusts the balance of the acidity and the alkalinity and the hydrogenation property of the catalyst, prepares a proper catalyst pore channel structure, is used at a lower reaction temperature, has very high acetone conversion rate, few byproducts, high product selectivity and low energy consumption for subsequent separation. After long-period examination, the catalyst shows ideal stability.

Description

Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof
Technical Field
The invention relates to the technical field of ketone hydrogenation condensation, and in particular relates to a catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and a preparation method and application thereof.
Background
Methyl isobutyl ketone (abbreviated as MIBK) is a colorless transparent liquid and has an odor similar to camphor. MIBK is primarily used in medium boiling solvents and organic synthesis feedstocks. In the aspect of solvent use, compared with common solvents (such as acetone, ethyl acetate, cyclohexanone, methyl ethyl ketone and the like), the MIBK has the characteristics of low volatility, good compatibility, no toxicity and the like, and is a high-grade solvent used in the industries of coatings, printing inks, paints, adhesives, epoxy resins and the like. As a paint solvent, the MIBK has excellent performance (good leveling property, hard paint film, moderate volatility, capability of preparing low-viscosity solution and preventing gelation), so that the MIBK has a wide application prospect in high-grade paint. The method has wide application in petroleum dewaxing, metal beneficiation, medicine, atomic absorption spectrum and other aspects. In the aspect of organic synthetic raw materials, the rubber antioxidant 4020 is mainly used for producing synthetic rubber antioxidant 4020, and the antioxidant 4020 is an excellent protective agent for resisting thermal oxidation and fatigue oxidation of rubber, and is developed rapidly in China in recent years. MIBK is also used in small quantities as a specialty surfactant for synthetic inks and agricultural applications.
The existing industrial production method of MIBK mainly comprises an acetone route and an isopropanol route according to raw materials, and in terms of the acetone route, the method also comprises a three-step method and a one-step method, and compared with the three-step method, the one-step method has obvious advantages. At present, the acetone one-step technique of MIBK abroad is mainly the Taxaco process of Taxaco corporation of germany, the Veba-Chimie process of Veba corporation, the korean DARI corporation technique, the american Eastman technique, the Sasol technique, and the japanese Tokuyama Soda technique, which are relatively mature and have industrial devices built in the united states, western europe, and japan, respectively.
The industrialized one-step acetone-process MIBK synthesis reaction is generally carried out under high pressure, a Pd/resin catalyst is mostly adopted, although high MIBK selectivity can be obtained, the service life is short, the resin is not high-temperature resistant and is difficult to regenerate, the development of the catalyst is not interrupted in the long-term research process of methyl isobutyl ketone, the research aspect of the catalyst in the field of MIBK synthesis is greatly developed, and the future research focuses on further researching and developing a high-performance industrial catalyst to further synthesize MIBK with high selectivity and conversion rate under non-harsh process conditions, so that the process flow is shortened, and the product selectivity is improved.
Disclosure of Invention
In order to solve the problems of the prior art that the cost of the catalyst is high and the product is mainly MIBK, the invention provides a catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation. In particular to a catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, a preparation method and application thereof. The catalyst provided by the invention has high activity and excellent selectivity, and simultaneously supports non-noble metal, so that the cost of the catalyst is reduced, MIBK is produced, and diisobutyl ketone (DIBK) with high additional value can be co-produced.
One of the purposes of the invention is to provide a catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, which comprises the following components in percentage by weight based on the total weight of the catalyst:
(1) 2% -25% of copper or its oxide;
(2) 7-35% of zinc or its oxide;
(3) 2% -40% of cobalt or its oxide;
(4) 1-10% of barium or its oxide;
(5)10 to 80 percent of alumina;
(6)1 to 70 percent of molecular sieve.
Preferred ranges are:
(1) 5% -15% of copper or its oxide;
(2) 10% -25% of zinc or its oxide; preferably from 10% to 15% zinc or an oxide thereof;
(3) 6-36% cobalt or its oxide; preferably 6% to 15% cobalt or an oxide thereof;
(4) 4% -8% of barium or its oxide;
(5)20 to 58 percent of alumina; preferably 20% to 50% alumina;
(6)15 to 51 percent of molecular sieve.
In order to obtain more excellent activity and selectivity, the weight ratio of the sum of copper and oxides thereof to the sum of zinc and oxides thereof in the catalyst can be 1 (0.5-2.5), and preferably 1 (1.0-1.9); the weight ratio of the sum of cobalt and oxides thereof to the sum of barium and oxides thereof in the catalyst can be 1 (0.1-1.2), and preferably 1 (0.3-1.0).
The molecular sieve can be selected from HZSM-5, HY or Beta molecular sieve; the silicon-aluminum ratio of the molecular sieve is 30-250. In order to improve the reaction performance of the catalyst, the preferred silicon-aluminum ratio of the HZSM-5 molecular sieve is 100-220, the preferred silicon-aluminum ratio of the HY molecular sieve is 30-80, and the preferred silicon-aluminum ratio of the Beta molecular sieve is 30-80.
The components of the catalyst have synergistic effect, and the acetone hydrogenation condensation reaction requires the catalyst to provide a hydrogenation active center, an acid site and a basic site simultaneously. Copper and cobalt provide the hydrogenation active center, zinc and barium provide the basic site, and alumina and molecular sieve are the carrier of the catalyst and provide the acid site.
The invention also aims to provide a preparation method of the catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation. According to the formulation of the catalyst for the preparation of methyl isobutyl ketone and diisobutyl ketone by acetone condensation of the present invention, those skilled in the art can select various preparation methods, and in order to achieve the intended purpose of the present invention, the following preparation method is preferred, which may comprise the following steps:
(1) mixing the required amount of alumina precursor, molecular sieve and sesbania powder, stirring (stirring can be performed by a stirring device commonly used in the field, such as a stirrer). The precursor of the alumina is pseudo-boehmite or boehmite; the molecular sieve is a hydrogen type molecular sieve after roasting.
(2) Dropwise adding a proper amount of dilute nitric acid, and continuously stirring; wherein the nitric acid acts as a chemical binder and the nitric acid produces peptization by reacting with the alumina, thereby increasing the strength of the catalyst.
(3) And (3) extruding the solid obtained in the step (2), drying, roasting and molding to obtain the carrier of the catalyst.
(4) Soluble salts of copper, zinc, cobalt and barium in the required amounts are dissolved in water to form a salt mixture solution.
(5) And (4) pouring the salt mixed solution obtained in the step (4) into a catalyst carrier, quickly shaking, uniformly mixing, standing for 1-8 hours, drying and roasting to obtain the oxidation state of the catalyst.
The amount of the salt mixed solution and the catalyst carrier used was determined depending on the water absorption rate measured before the impregnation. The method comprises the following specific steps: the water absorption of the catalyst support is first determined and then the soluble salt is dissolved in water, the solution is suitably heated to ensure complete dissolution is necessary, for example using microwave heating or a hot water bath, and then the catalyst is poured and shaken rapidly, the solution being just completely dissolved in the catalyst support since the water absorption has been previously determined.
(6) And (3) reducing the oxidation state catalyst obtained in the step (5) by using hydrogen or a mixed gas of hydrogen and nitrogen to obtain the catalyst.
In the step (1), the dosage of the sesbania powder is 0.5-5% of the sum of the mass of the alumina precursor and the mass of the molecular sieve, and preferably 1-3%. The sesbania powder is a lubricant, and a very small amount of lubricant is needed to be added in order to ensure that the pressure borne by a powder layer can be well transferred during compression molding, the molding pressure is uniform, the product is easy to demould, and the friction coefficient between walls is reduced.
In the step (2), the dilute nitric acid is a nitric acid solution with the volume fraction concentration of 2-15%, and the dosage of the dilute nitric acid is 1-10% of the sum of the mass of the alumina precursor and the mass of the molecular sieve;
in the step (3), the drying temperature is 80-120 ℃, and the roasting temperature is 400-950 ℃;
in the step (5), the drying temperature range is 80-120 ℃, and the roasting temperature is 400-950 ℃.
The carrier used in the invention can use a plurality of carrier precursors, the molecular sieve can be selected from HZSM-5, HY or Beta molecular sieve according to industrial easy obtaining and expected effect, the precursor of the alumina can be pseudo boehmite or boehmite; the soluble salts of copper, zinc, cobalt and barium can be copper nitrate, zinc nitrate, cobalt nitrate and barium nitrate respectively.
The catalyst of the invention is applied to the reaction of preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and the specific hydrogenation process scheme can be as follows: acetone and hydrogen are used as raw materials, the molar ratio of the hydrogen to the acetone is 15-60: 1, the reaction temperature is 170-260 ℃, the reaction pressure is 1.0-4.5 MPa, and the liquid volume space velocity of the acetone is 0.1-1.0 h-1。
The shape of the catalyst can be various, such as spherical, strip, columnar, annular and the like, the size is 0.3-15 mm, more preferably 0.5-3 mm, and the requirement of the size is mainly based on the design of the fixed bed reactor, so that the fixed bed reactor is convenient to install, and the requirement of reducing the pressure of a bed layer is met. These knowledge are well known to those skilled in the art.
The catalyst of the present invention is reduced before use, the reducing gas may be hydrogen gas, a mixture of hydrogen gas and nitrogen gas, the hydrogen content in the mixture of hydrogen and nitrogen gas may be any content, for example, 2 vol% to 80 vol%, or a higher content gas may be used. From the viewpoint of temperature control of catalyst reduction, a mixed gas having a low hydrogen content is preferred. The larger the space velocity of the gas, the better. The air speed is large, the heat generated by the reaction can be quickly removed in time, the temperature of the catalyst bed is kept stable, and the catalyst is not damaged by temperature runaway. For example, the space velocity of the mixed gas is 300-5000 m3/m3·h-1. The temperature of the reduction may depend on the particular catalyst groupThe catalyst of the invention can gradually increase the temperature of a catalyst bed layer at a rate of 5-20 ℃/h, preferably 5-10 ℃/h, stay at 200 ℃ for 2-8 h, then gradually increase the temperature of the catalyst bed layer at a rate of 5-20 ℃/h, preferably 5-10 ℃/h, until the temperature reaches 300-500 ℃, and keep the temperature for 2-48 h. And then slowly cooling to room temperature, for example, the cooling rate is 5-20 ℃/h. After the temperature is reduced to the room temperature, the nitrogen is switched to the nitrogen, the hydrogen is gradually mixed into the nitrogen, and the hydrogen consumption is gradually increased to increase the hydrogen content in the mixed gas. The amount of hydrogen is adjusted at any time according to the change of the temperature of the catalyst, so that the temperature of a catalyst bed is prevented from being too high, for example, not exceeding 50 ℃. If the catalyst is reduced in the reactor, the temperature of the reduced catalyst is reduced to the reaction temperature, and then the catalyst can be fed for use.
The invention also aims to provide the application of the catalyst for preparing the methyl isobutyl ketone and the diisobutyl ketone by acetone condensation in the reaction for preparing the methyl isobutyl ketone and the diisobutyl ketone by acetone condensation.
The catalyst disclosed by the invention takes copper, zinc, cobalt and the like as load components, properly adjusts the balance of the acidity and alkalinity and the hydrogenation property of the catalyst, prepares a proper catalyst pore channel structure, is used at a lower reaction temperature, has very high acetone conversion rate, few byproducts, high product selectivity and low energy consumption for subsequent separation. After long-period examination, the catalyst shows ideal stability.
Compared with the similar catalysts reported in literature and used in industry, the catalyst of the invention has higher activity and excellent selectivity, the excellent selectivity is derived from the characteristics of the catalyst, and the catalytic performance of the catalyst is derived from the acidity, alkalinity and hydrogenation performance of the catalyst in a microscopic way, which is shown in the difference of adsorption and desorption capacities of reactants, reaction transition substances and reaction products.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
The raw materials of the present application are all commercially available.
The component types and contents of the finished catalyst are tested by XRF and X-ray fluorescence spectrum analysis (Zetium X-ray fluorescence instrument of Pasacaceae, the Netherlands).
Example 1
150g of pseudo-boehmite was poured into a kneader, and 6g of sesbania powder was added thereto, kneaded and mixed. Then 150g of HZSM-5 with the silica-alumina ratio of 30 and 10g of dilute nitric acid with the volume fraction of 20 percent are added to be kneaded into blocks, the blocks are extruded, then the strips are dried at 120 ℃ and roasted at 400 ℃ for 4 hours to obtain a carrier, and the carrier is crushed to 0.5-3 mm for later use. The HZSM-5 molecular sieve is produced by Tianjin south chemical catalyst Co, Ltd, and the model is NKF-5. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.9 mL/g.
31.5 g of copper nitrate, 25.5 g of cobalt nitrate, 50.5 g of zinc nitrate and 10g of barium nitrate were dissolved in 45 g of water in a beaker to form a salt mixed solution. The mixed solution was poured into a beaker containing 60 g of the catalyst support, shaken and left to stand for 3 hours, followed by drying at 120 ℃ and calcination at 450 ℃ for 3 hours to obtain the oxidation state of the catalyst. Before use, the catalyst is reduced by using a mixed gas of 5 vol% of hydrogen and 95 vol% of nitrogen according to a temperature programming mode, the maximum temperature of reduction is 450 ℃, the obtained catalyst is marked as MSZ-1 after temperature reduction, and the component content of the catalyst is tested by XRF (x-ray diffraction) and the result is shown in Table 1.
Example 2
120g of pseudo-boehmite was poured into a kneader, and 6g of sesbania powder was added thereto, kneaded and mixed. And then adding 180g of HZSM-5 with the silica-alumina ratio of 80 and 10g of dilute nitric acid with the volume fraction of 20%, kneading into blocks, extruding the blocks, drying at 120 ℃, roasting at 450 ℃ for 4 hours to obtain a carrier, and crushing to 0.5-3 mm for later use. The HZSM-5 molecular sieve is produced by Tianjin south chemical catalyst Co, Ltd, and the model is NKF-5. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.9 mL/g.
In a beaker 25.5 grams of copper nitrate, 28.5 grams of cobalt nitrate, 40.0 grams of zinc nitrate and 8 grams of barium nitrate were dissolved in 40 grams of water to form a salt mixed solution. The mixed solution was poured into a beaker containing 60 g of the catalyst support, shaken and allowed to stand for 2 hours, followed by drying at 120 ℃ and calcination at 450 ℃ for 3 hours to obtain the oxidation state of the catalyst. Before use, the catalyst is reduced by a mixed gas of 5 vol% of hydrogen and 95 vol% of nitrogen according to a temperature programming mode, the maximum temperature of reduction is 450 ℃, the obtained catalyst is marked as MSZ-2 after temperature reduction, and the component content of the catalyst is tested by XRF (X-ray diffraction) and the result is shown in Table 1.
Example 3
120g of pseudo-boehmite was poured into a kneader, and 6g of sesbania powder was added thereto, kneaded and mixed. Then adding 180g of HZSM-5 with the silica-alumina ratio of 200 and 10g of dilute nitric acid with the volume fraction of 20%, kneading into blocks, extruding the blocks, drying at 120 ℃, roasting at 380 ℃ for 4 hours to obtain a carrier, and crushing to 0.5-3 mm for later use. The HZSM-5 molecular sieve is produced by Tianjin south chemical catalyst Co, Ltd, and the model is NKF-5. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.9 mL/g.
In a beaker, 20.5 g of copper nitrate, 40.5 g of cobalt nitrate, 25.5 g of zinc nitrate and 3 g of barium nitrate were dissolved in 45 g of water to form a salt mixed solution. The mixed solution was poured into a beaker containing 60 g of the catalyst support, shaken and left to stand for 3 hours, then dried at 120 ℃ and calcined at 350 ℃ for 3 hours to obtain the oxidation state of the catalyst. Before use, the catalyst is reduced by using a mixed gas of 5 vol% of hydrogen and 95 vol% of nitrogen according to a temperature programming mode, the maximum temperature of reduction is 350 ℃, the obtained catalyst is marked as MSZ-3 after temperature reduction, and the component content of the catalyst is tested by XRF (x-ray fluorescence) and the result is shown in Table 1.
Example 4
220g of pseudo-boehmite was poured into a kneader, and 6g of sesbania powder was added thereto, kneaded and mixed. And then adding 80g of HY molecular sieve with the silicon-aluminum ratio of 60 and 10g of dilute nitric acid with the volume fraction of 20%, kneading into blocks, extruding the blocks, drying at 120 ℃, roasting at 460 ℃ for 3 hours to obtain a carrier, and crushing to 0.5-3 mm for later use. The HY molecular sieve is produced by Tianjin Minghua catalyst Co., Ltd, and has the model of NKF-8. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.9 mL/g.
In a beaker, 28.5 g of copper nitrate, 45.5 g of cobalt nitrate, 28.5 g of zinc nitrate and 4 g of barium nitrate were dissolved in 50g of water to form a salt mixed solution. The mixed solution was poured into a beaker containing 60 g of the catalyst support, shaken and left to stand for 4 hours, then dried at 120 ℃ and calcined at 450 ℃ for 2 hours to obtain the oxidation state of the catalyst. Before use, the catalyst is reduced by using a mixed gas of 5 vol% of hydrogen and 95 vol% of nitrogen according to a temperature programming mode, the maximum temperature of reduction is 450 ℃, the obtained catalyst is marked as MSZ-4 after temperature reduction, and the component content of the catalyst is tested by XRF (x-ray diffraction) and the result is shown in Table 1.
Example 5
150g of pseudo-boehmite was poured into a kneader, and 6g of sesbania powder was added thereto, kneaded and mixed. And then 150g of Beta molecular sieve with the silicon-aluminum ratio of 60 and 10g of dilute nitric acid with the volume fraction of 20 percent are added, the mixture is kneaded into blocks, the blocks are extruded, then the strips are dried at 120 ℃, and are roasted for 3 hours at 460 ℃ to obtain a carrier, and the carrier is crushed to 0.5-3 mm for later use. The Beta molecular sieve is produced by Tianjin Minghua catalyst Co., Ltd, and has the model of NKF-6. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.9 mL/g.
In a beaker, 28.5 g of copper nitrate, 45.5 g of cobalt nitrate, 28.5 g of zinc nitrate and 4 g of barium nitrate were dissolved in 50g of water to form a salt mixed solution. The mixed solution was poured into a beaker containing 60 g of the catalyst support, shaken and left to stand for 4 hours, then dried at 120 ℃ and calcined at 450 ℃ for 2 hours to obtain the oxidation state of the catalyst. Before use, the catalyst is reduced by using a mixed gas of 5 vol% of hydrogen and 95 vol% of nitrogen according to a temperature programming mode, the maximum temperature of reduction is 450 ℃, the obtained catalyst is marked as MSZ-5 after temperature reduction, and the component content of the catalyst is tested by XRF (x-ray diffraction) and the result is shown in Table 1.
TABLE 1
Figure BDA0001821127060000081
Example 6
This example is an example of catalyst evaluation.
The catalyst is filled in an oil bath controlled isothermal fixed bed reactor, acetone is metered by a metering pump and mixed with hydrogen metered by a gas mass flow meter, the mixture enters the reactor, flows through a catalyst bed layer and reacts under the catalytic action of the catalyst, and the reaction conditions are as follows: inverse directionThe reaction temperature is 180 ℃, the reaction pressure is 1.0MPa, and the space velocity is 0.5h-1The mass ratio of hydrogen to acetone was 30: 1.
The test results are shown in table 2 below.
TABLE 2 test results
Figure BDA0001821127060000091
As can be seen from the test results in Table 2, the catalyst of the present invention has higher conversion rate, and diisobutyl ketone and methyl isobutyl carbinol with higher added value are produced at the same time of producing methyl isobutyl ketone. The catalyst MSZ-3 is subjected to a stability assessment test for 1000 hours, and shows ideal stability. The characterization analysis shows that the catalyst after the evaluation test has no obvious change in the crystal grain and texture parameters, only stores a small amount of low molecular organic matter, and has no graphitized carbon deposit.

Claims (10)

1. A catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, which comprises the following components in percentage by weight:
(1) 2% -25% of copper or its oxide;
(2) 7-35% of zinc or its oxide;
(3) 2% -40% of cobalt or its oxide;
(4) 1-10% of barium or its oxide;
(5)10 to 80 percent of alumina;
(6)1 to 70 percent of molecular sieve.
2. The catalyst for the preparation of methylisobutylketone and diisobutyl ketone by acetone condensation according to claim 1, which comprises the following components in percentage by weight:
(1) 5% -15% of copper or its oxide;
(2) 10% -25% of zinc or its oxide;
(3) 6-36% cobalt or its oxide;
(4) 4% -8% of barium or its oxide;
(5)20 to 58 percent of alumina;
(6)15 to 51 percent of molecular sieve.
3. The catalyst for the preparation of methyl isobutyl ketone and diisobutyl ketone by acetone condensation according to claim 1 or 2, characterized in that:
the molecular sieve is selected from HZSM-5, HY or Beta molecular sieve; the silicon-aluminum ratio of the molecular sieve is 30-250.
4. The catalyst for the preparation of methylisobutylketone and diisobutyl ketone by acetone condensation according to claim 3, wherein:
the silicon-aluminum ratio of the HZSM-5 molecular sieve is 100-220, the silicon-aluminum ratio of the HY molecular sieve is 30-80, and the silicon-aluminum ratio of the Beta molecular sieve is 30-80.
5. The catalyst for the preparation of methyl isobutyl ketone and diisobutyl ketone by acetone condensation according to claim 1 or 2, characterized in that:
the weight ratio of the copper and the oxide thereof to the zinc and the oxide thereof in the catalyst is 1 (0.5-2.5), preferably 1 (1.0-1.9);
the weight ratio of cobalt and oxide thereof to barium and oxide thereof in the catalyst is 1 (0.1-1.2), preferably 1 (0.3-1.0).
6. The process for preparing a catalyst for the condensation of acetone to prepare methyl isobutyl ketone and diisobutyl ketone according to any one of claims 1 to 5, comprising the steps of:
(1) uniformly stirring and mixing the required amount of the alumina precursor, the molecular sieve and the sesbania powder;
(2) dropwise adding dilute nitric acid, and continuously stirring;
(3) extruding and drying the solid obtained in the step (2); then roasting and forming to obtain the carrier of the catalyst;
(4) dissolving soluble salts of copper, zinc, cobalt and barium with required dosage in water to form a salt mixed solution;
(5) pouring the salt mixed solution obtained in the step (4) into a catalyst carrier, quickly shaking, uniformly mixing, standing, drying and roasting to obtain the oxidation state of the catalyst;
(6) and (4) reducing the oxidation state catalyst obtained in the step (5) to obtain the catalyst.
7. The method of claim 6, wherein the catalyst is prepared by condensing acetone to obtain methylisobutylketone and diisobutyl ketone, and the method comprises the following steps:
in the step (1), the molecular sieve is a calcined hydrogen type molecular sieve;
the precursor of the alumina is pseudo-boehmite or boehmite;
the soluble salts of copper, zinc, cobalt and barium are respectively copper nitrate, zinc nitrate, cobalt nitrate and barium nitrate.
8. The method of claim 6, wherein the catalyst is prepared by condensing acetone to obtain methylisobutylketone and diisobutyl ketone, and the method comprises the following steps:
in the step (1), the dosage of the sesbania powder is 0.5-5% of the sum of the mass of the alumina precursor and the mass of the molecular sieve, and preferably 1-3%;
in the step (2), the dilute nitric acid is a nitric acid solution with the volume fraction concentration of 2-15%, and the dosage of the dilute nitric acid is 1-10% of the sum of the mass of the alumina precursor and the mass of the molecular sieve.
9. The method of claim 6, wherein the catalyst is prepared by condensing acetone to obtain methylisobutylketone and diisobutyl ketone, and the method comprises the following steps:
in the step (3), the drying temperature is 80-120 ℃, and the roasting temperature is 400-950 ℃;
in the step (5), the drying temperature range is 80-120 ℃, and the roasting temperature is 400-950 ℃.
10. The catalyst for the preparation of methylisobutylketone and diisobutyl ketone by acetone condensation according to any one of claims 1 to 5 and the use of the catalyst prepared by the preparation method according to any one of claims 6 to 9 in the reaction of methylisobutylketone and diisobutyl ketone by acetone condensation.
CN201811166040.8A 2018-10-08 2018-10-08 Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation, and preparation method and application thereof Pending CN111001432A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1116037A (en) * 1966-06-24 1968-06-06 Exxon Research Engineering Co Preparation of mesityl oxide and/or methyl isobutyl ketone
EP0271182A1 (en) * 1986-11-08 1988-06-15 Sumitomo Chemical Company, Limited Alumina catalyst for catalytic production of methyl isobutyl ketone from acetone
CN1273231A (en) * 2000-06-09 2000-11-15 边俊民 Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst
CN104355975A (en) * 2014-11-07 2015-02-18 中国海洋石油总公司 Method for synthesizing methyl isobutyl ketone from acetone by two-step process
CN107930635A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 The catalyst of coproducing methyl isobutyl ketone and diisobutyl ketone
CN107930657A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 By the cobalt-base catalyst of methylisobutanone synthesized from acetone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1116037A (en) * 1966-06-24 1968-06-06 Exxon Research Engineering Co Preparation of mesityl oxide and/or methyl isobutyl ketone
EP0271182A1 (en) * 1986-11-08 1988-06-15 Sumitomo Chemical Company, Limited Alumina catalyst for catalytic production of methyl isobutyl ketone from acetone
CN1273231A (en) * 2000-06-09 2000-11-15 边俊民 Reaction process for preparing both methylisobutl ketone and diisobutyl ketone and its catalyst
CN104355975A (en) * 2014-11-07 2015-02-18 中国海洋石油总公司 Method for synthesizing methyl isobutyl ketone from acetone by two-step process
CN107930635A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 The catalyst of coproducing methyl isobutyl ketone and diisobutyl ketone
CN107930657A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 By the cobalt-base catalyst of methylisobutanone synthesized from acetone

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Application publication date: 20200414