CN107930634B - Nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol - Google Patents
Nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol Download PDFInfo
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- 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
- C07C45/73—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 hydrogenation
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a catalyst, belonging to the technical field of application and development of acetone downstream products, which takes nickel and zinc as main active components, boron and cerium as auxiliary components, selects alumina, silicon oxide or an alumina-silicon oxide composite carrier with abundant acidity and alkalinity to promote reaction, is used under mild reaction conditions, adopts an acetone one-step method production process, has higher yield of a product methyl isobutyl ketone than a palladium/resin catalyst used by the existing industrial device, and coproduces isopropanol. The catalyst of the invention shows ideal stability, the production cost is obviously lower than that of the existing palladium catalyst, and the catalyst has better economic benefit.
Description
Technical Field
The invention relates to a catalyst for ketone condensation, in particular to a catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol by using acetone as a raw material through a one-step method.
Background
Methyl isobutyl ketone (MIBK for short in english) is an important solvent and chemical intermediate, is of great interest due to its excellent performance, has aromatic ketone smell, is colorless and transparent, has a medium boiling point, has very strong dissolving power, can be mixed and dissolved with numerous organic solvents such as alcohol, benzene, diethyl ether and the like, can be used as raw materials of coating, ethyl cellulose, nitrocellulose, audio-video tape, paraffin, various natural or synthetic resin solvents, dewaxing agents, rare earth metal extracting agents, polymerization reaction initiating agents, surfactants, medicines, pesticide extracting agents and rubber anti-aging agents, is a current rather delicate fine petrochemical intermediate, has irreplaceability in many application fields, and is still imported annually in China.
As seen in the current market, methyl isobutyl ketone is produced mainly using acetone as a raw material. The method is divided into a three-step method and a one-step method according to the reaction process. The one-step method has the advantages of short process flow, low investment, high raw material conversion rate and the like, and becomes a main synthesis process route.
The process for producing methyl isobutyl ketone by using the acetone three-step method illustrates the reaction process of synthesizing methyl isobutyl ketone by using acetone: condensation, acid-catalyzed dehydration and selective hydrogenation. With the continuous development and progress of catalytic technology, people begin to research multifunctional catalysts integrating the three processes. The German Veba-Chemie company led to the construction of a one-step production plant in 1968, with a single-pass conversion of acetone of 34.4% and a selectivity for MIBK of 96.5%. The preparation of the catalyst is difficult by selecting strong acid cation exchange resin and Pd with hydrogenation function on double bonds of olefin as the catalyst by two companies, namely Veba and Taxaco in Germany. In recent years, Mobil corporation in the United states developed a Pd-NSM-5 modified zeolite catalyst which can be prepared by impregnation and calcination. In recent years, China also starts to research and develop multifunctional catalysts, such as industrial Pd/resin catalysts and molecular sieve catalysts, ZSM-5 molecular sieves synthesized by an amine-free method are used as carriers, metal Pd is used as an active component, and metal nickel is used as a promoter component to synthesize methyl isobutyl ketone. And the Liu self-strength and the like adopt an impregnation method to prepare the BaO/alumina catalyst. The Lihongxia takes HZSM-5 molecular sieve as carrier, loads multi-metal active components such as Pd, Cu, Zn, Ni and the like, and has the reaction temperature of 160 ℃ and the reaction pressure of 18Kg/cm2The conversion of acetone was 42.7% and the selectivity of MIBK was as high as 95.6% under the liquid phase reaction conditions of (1), but it was not industrialized. Preparation of Cu-MgO-Al by precipitation method2O3The catalyst has acetone conversion of 71.7% and MIBK selectivity of 51%, and the literature gives no catalyst life.
At present, industrial devices for preparing methyl isobutyl ketone from acetone by using palladium/resin catalysts do not have a profit space and are in a low-load operation or production stop state. The industry began to look for the co-production of acetone downstream product with methyl isobutyl ketone to improve the economics of the plant.
The isopropanol is an organic solvent with excellent performance, has wide application, is mainly used as an organic solvent in the fields of printing ink, coating and the like, and also has important application in the aspects of medicines, organic chemical raw materials, electronic industry and the like. In 2014, the demand of isopropanol in China reaches 32.5 ten thousand tons. The Chinese chemical information center forecasts that the demand of the isopropanol increases at a speed of 7-8% of the annual average growth rate. At present, two technical routes for industrially producing isopropanol in China are provided: the first is the hydration of propylene to make isopropanol, available from malkan petrochemical and Shandong Haichi corporation; the second one is the preparation of isopropanol by acetone hydrogenation, which is a new acetone hydrogenation catalyst from Beijing chemical research institute in Shandong Dezhou Henglu and Zhejiang. Therefore, the production of methyl isobutyl ketone and isopropanol also meet the market value orientation.
Throughout the literature and reports, the catalyst which is industrialized at present is still Pd/resin catalyst, the service life of the catalyst is 9-12 months, and the product produced by the catalyst is only methyl isobutyl ketone and is single. Other catalysts have not been reported industrially. The inventors have intensively studied and found that a critical factor for the stability of the catalyst is a condensate produced by condensation of acetone, and the resulting MIBK undergoes further condensation reaction to produce a larger condensate. These condensates coat the catalyst surface, causing deactivation of the catalytically active sites.
Disclosure of Invention
The palladium catalyst used in industry in the prior art has short service life and high cost, but the widely researched non-noble metal catalyst still cannot meet the industrial requirement, so that the enterprise hopes to improve the economic benefit of the methyl isobutyl ketone industrial device, the inventor carries out intensive research on the non-metal catalyst according to the enterprise requirement, and after years of experimental research, the ideal catalyst and process technology for synthesizing the methyl isobutyl ketone and co-producing the isopropanol are obtained.
The specific technical scheme of the invention is as follows:
the invention provides a nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol by using acetone as a raw material through a one-step method, which comprises a carrier and load components of nickel, zinc, boron and cerium, wherein the zinc, the boron and the cerium exist in the form of oxides.
The inventor screens out a catalyst with better performance through a large number of tests, and the catalyst comprises the following components by mass percent of 100 percent:
(1) nickel, wherein the nickel is calculated by metal state, and the mass percent content is 3.5% -12%;
(2) zinc, calculated by metal state, the mass percent content is 4-15%;
(3) boron, calculated by converting into simple substance boron, the mass percent content is 0.1-3%;
(4) cerium, calculated by metal state, with a mass percentage content of 0.1-4%;
(5) a support, the balance being other than the content of the supported component in the metallic state and in the oxidized state.
The catalyst prepared by the invention needs to be subjected to reduction treatment before use, most of nickel is reduced to be in a metal state, but some components such as boron, cerium and zinc cannot be reduced to be in the metal state.
In order to better disperse the supported component, the catalyst of the present invention uses a support, for example, alumina, silica, an alumina-silica composite support, or a molecular sieve. From the point of view of the condensation, dehydration and hydrogenation processes undergone by acetone, said alumina is more preferably an acid-modified alumina or a base-modified alumina, both of which promote the condensation and dehydration processes. Alternatively, acid-modified silica or alkali-modified silica may be used as the silica. The use of an alumina-silica composite support is more advantageous from the viewpoint of structural stability of the support, and of course, an acid-modified alumina-silica composite support or an alkali-modified alumina-silica composite support is more preferable. The so-called acid modification may be carried out by using phosphoric acid, sulfuric acid, hydrofluoric acid or boric acid at the time of molding the support. The alkali modification may be carried out by adding a basic metal salt such as lanthanum nitrate, an alkali metal salt, an alkaline earth metal salt or the like to the support during the molding thereof.
The nickel metal source in the catalyst can be selected from water-soluble metal salts such as nitrate, sulfate, chloride, acetate, oxalate and bromide, or selected from metal nickel, such as nickel metal plate, and the like. More specifically, the water-soluble metal salt is selected from one or more of nickel nitrate, nickel chloride, nickel oxalate, nickel sulfate and nickel acetate, and more preferably from one or more of nickel nitrate, nickel acetate and nickel oxalate.
Cerium is another important component in the catalyst, and the activity and the selectivity of the catalyst are greatly improved by adding a proper amount of cerium. After the addition of the auxiliary agent cerium, the indexes of the catalyst such as activity, selectivity and the like representing the reaction performance of the catalyst are greatly improved, wherein the reasons may be in various aspects: cerium improves the electronic morphology of nickel. The cerium plays a role in modulating the electronic structure of the reduced nickel catalyst, the reduced nickel is mainly zero-valent, the cerium is reduced from 4+ valent to 3+ valent, the two interact, electrons are deviated from the cerium by the nickel, the electronic unsaturation degree of the nickel is increased, and therefore the electronic change of the carbonyl of the acetone is influenced, and the reaction is promoted to be carried out.
The source of cerium is not limited and may be any known cerium-containing compound. Further optimized sources of cerium may be selected from all water soluble metal salts such as nitrates, acetates and oxalates, etc.
The zinc source in the catalyst can be selected from water-soluble metal salts such as nitrate, sulfate, chloride, acetate, oxalate and bromide, or selected from metal zinc, such as zinc metal plate, etc. More specifically, the water-soluble metal salt is selected from one or more of zinc nitrate, zinc chloride, zinc oxalate, zinc sulfate and zinc acetate, and more preferably one or more of zinc nitrate, zinc acetate and zinc oxalate.
As described above, the catalyst of the present invention further contains an oxide generally regarded as functioning as a carrier, and is not particularly limited herein, and is selected from one or more of silica, alumina, a silica-alumina composite, diatomaceous earth, calcium silicate, zirconia, and titania. In fact, these supports, which not only serve as supports, but also assist in dispersing the active components and promote acetone condensation and dehydration, affect the structural properties of the catalyst, diffusion of products and feedstocks therein, mechanical strength, activity and stability, among other critical parameters.
The carrier alumina may be selected from aluminas produced from aluminum hydroxide produced by a nitric acid process, a sulfuric acid process, a carbonic acid process, a bayer process, a rapid dehydration process, and the like. Since alumina is more commonly used, it will not be described further herein.
The silica powder can be obtained by a chemical deposition method, a water glass precipitation method, drying and ball milling after the water glass precipitation, or a silica sol spray drying method, and the like, and the size of the silica powder is 10nm to 500 μm, such as coarse pore microsphere silica (the average pore diameter is 8.0 to 12.0nm, the specific surface area is 300 to 600m2/g, the pore volume is 0.8 to 1.1ml/g) produced by Qingdao ocean chemical plants, such as precipitated silica (the content of silica (SiO2) is more than or equal to 95.0, the fineness (325 mesh screen residue)% is less than or equal to 1.8, the specific surface area is 400 to 600m2/g) produced by Guangzhou national chemical plants, or active white carbon black, such as fumed silica AEROSI L of Germany corporation, the specific surface area is 200m2/g, such as silica obtained by self-made spray drying, such as silica microspheres with a surface area of 400 to 500m2/g, such as silica gel precipitated silica gel, calcium nitrate, zirconium nitrate is directly added into a silica gel, or other glass precipitation method, or a silica gel, such as a silica gel, a silica gel is directly added into a silica gel, a zirconium nitrate precipitation method, a.
In order to improve the thermal stability, mechanical strength, pore structure and surface properties of alumina, some inorganic compounds may be added for modification. For example, the modification is carried out by adding silica to alumina. For example, the addition of silica gel or silica-alumina gel to an aluminum hydroxide hydrogel can significantly change the texture properties of the alumina and the acidity or basicity of the support. Rare earth oxide can also be added to obviously improve the thermal stability of the alumina and change the acidity and alkalinity of the carrier. Molecular sieves, barium oxide, magnesium oxide, boric acid, phosphoric acid, sulfuric acid, and hydrofluoric acid may also be added to improve the carrier properties.
The support silica or alumina may also be added as a binder in the catalyst prepared as a melt-suction filtration process, so that the resulting catalyst powder can be shaped into the desired form according to the invention.
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 bed pressure is met. These knowledge are well known to those skilled in the art.
The catalyst preparation method can be obtained by the existing catalyst preparation technology, such as impregnation method, ion exchange method, blending method, kneading method, coprecipitation, deposition-precipitation, ammonium evaporation precipitation, melting-suction filtration, ball milling, sol-gel and other methods. More preferred methods include one or more of impregnation, co-precipitation, deposition-precipitation, sol-gel and ball-milling methods, most of which are well known to those skilled in the art as well known in the art, such as < industrial catalyst design and development > by the general Tao Huang, and "Preparation of Solid Catalysts" by the professor Gerhard Ertl et al.
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 90 vol%, or pure hydrogen gas may be used. From the viewpoint of temperature control of the catalyst reduction, the larger the space velocity of the gas, the better the reduction. 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 a space velocity of hydrogen of300～5000m3/m3·h-1. The reduction temperature can be determined according to the composition of the specific catalyst, and for the catalyst provided by the invention, the temperature of the catalyst bed layer can be gradually increased at the speed of 5-20 ℃/h, preferably 5-10 ℃/h, the catalyst bed layer stays at 200 ℃ for 2-8 hours, then the temperature of the catalyst bed layer is gradually increased at the speed of 5-20 ℃/h, preferably 5-10 ℃/h until the temperature reaches 450-500 ℃, and the catalyst bed layer is kept at the temperature for 2-48 hours. And then slowly cooling to room temperature, for example, the cooling rate is 5-20 ℃/h. 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 catalyst of the invention can be used in a fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 100-190 ℃, the reaction pressure is 0.8-2.5 MPa, and the acetone airspeed is 0.1-1.5 h-1And the mass ratio of the hydrogen to the acetone is 1-6: 1. The increase of the reaction temperature is beneficial to improving the conversion rate of the acetone and the condensation reaction and the dehydration reaction of the acetone. The reaction pressure is increased, so that the hydrogenation reaction intensity is increased, and the isopropanol selectivity is increased. The influence of the acetone airspeed in the range is small, the airspeed is too large, the acetone conversion rate is reduced, and the one-way yield is reduced. The hydrogen has little influence on the reaction under the condition of enough hydrogen, but the hydrogen is not too much, and the hydrogen influences the retention time of the materials in the catalyst bed layer.
Compared with the existing industrial palladium/resin catalyst, the catalyst has low cost, the price of the palladium catalyst per ton is as high as dozens of ten thousand yuan, even millions of yuan, and the price of the catalyst is one tenth of the price; secondly, the preparation process is relatively simple and convenient and is easy to control, the palladium catalyst is polymerized to prepare granular resin firstly, then the palladium is loaded by exchange, organic matters on the resin are easy to lose, reaction products are polluted, the product chromaticity is increased, and the catalyst of the invention cannot lose; and thirdly, the process operation window of the palladium/resin catalyst is narrow, the catalyst is easy to deactivate due to overhigh temperature, the acid amount is reduced, and the catalyst has a wider temperature operation window. The structural stability and operational applicability of the catalyst of the present invention determine its high stability and lifetime. And fourthly, only one product, namely methyl isobutyl ketone, is produced by the palladium catalyst, the catalyst disclosed by the invention can be used for producing the methyl isobutyl ketone and the isopropanol, and an industrial production device has stronger market adaptability and increased loss resistance.
Detailed Description
The catalysts according to the invention are further illustrated below by way of examples, without the invention being restricted thereto.
Example 1
148.6 g of nickel nitrate, 204.7 g of zinc nitrate, 13.9 g of cerium nitrate and 3.4 g of boric acid were dissolved in 860 g of water in a beaker to prepare an aqueous solution I, which was titrated with a 30 wt% aqueous solution of sodium carbonate at 70 ℃ with stirring until the pH of the reaction solution became 7.0. 295 grams of pseudo-boehmite powder was then added. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 306m2The pore volume is 1.08m L/g.
Followed by aging at 75 ℃ for 3 hours, then suction filtration and washing until the sodium ion content is below 0.05%. The wet cake was dried, granulated and then calcined at 420 c to decompose. Finally, the mixture is made into granules with the grain diameter of
The catalyst was then reduced with hydrogen at a temperature programmed to a maximum of 480 ℃. Reducing at 480 ℃ for 2 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is calculated in a metal state, and the mass percentage content of the nickel is 10%; (2) zinc, calculated by metal state, the mass percent content is 15%; (3) boron, calculated by converting into simple substance boron, the percentage content is 0.2%; (4) cerium, calculated by metal state, with a mass percent content of 1.5%; (5) alumina carrier, the balance excluding the content of metallic and oxidic support components.
Comparative example 1
An industrially useful palladium/resin catalyst obtained from Zhejiang Utilization chemical Co., Ltd.
Example 2
An aqueous solution I was prepared by dissolving 89.1 g of nickel nitrate, 136.5 g of zinc nitrate, 32.5 g of cerium nitrate and 1.7 g of boric acid in 600 g of water in a beaker, and titrated with a 30 wt% aqueous solution of sodium carbonate at 75 ℃ with stirring until the pH of the reaction solution became 7.5. Then 330 g of pseudo-boehmite powder was added. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 290m2The pore volume is 0.99m L/g.
Followed by aging at 75 ℃ for 3 hours, then suction filtration and washing until the sodium ion content is below 0.05%. The wet cake was dried, granulated and then calcined at 380 ℃ for decomposition. Finally, the mixture is made into granules with the grain diameter of
The catalyst was then reduced with hydrogen at a temperature of up to 450 ℃ according to a temperature program. Reducing at 450 ℃ for 2 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) the nickel is calculated in a metal state, and the mass percent content of the nickel is 6 percent; (2) zinc, calculated by metal state, the mass percent content is 10%; (3) boron, calculated by converting into simple substance boron, the percentage content is 0.1%; (4) cerium, calculated by metal state, the mass percentage content is 3.5%; (5) alumina carrier, the balance excluding the content of metallic and oxidic support components.
Example 3
Aqueous solution I was prepared by dissolving 178.3 g of nickel nitrate, 109.2 g of zinc nitrate, 8.4 g of cerium nitrate and 34.3 g of boric acid in 770 g of water in a beaker, and titrated with 30 wt% aqueous sodium carbonate solution at 75 ℃ with stirring until the pH of the reaction solution was 7.2. Then 302 grams of pseudo-boehmite powder was added. Pseudo-boehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 275m2The pore volume is 1.12m L/g.
Followed by aging at 75 ℃ for 3 hours, then suction filtration and washing until the sodium ion content is below 0.05%. Drying the wet filter cake, granulating, and roasting at 360 deg.C for decomposition. Finally, the mixture is made into granules with the grain diameter of
The catalyst was then reduced with hydrogen at a temperature of up to 450 ℃ according to a temperature program. Reducing at 450 ℃ for 4 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is calculated in a metal state, and the mass percent content of the nickel is 12%; (2) zinc, calculated by metal state, with a mass percent of 8%; (3) boron, calculated by converting into simple substance boron, the percentage content is 2%; (4) cerium, calculated by metal state, the mass percentage content is 0.9%; (5) alumina carrier, the balance excluding the content of metallic and oxidic support components.
Example 4
An aqueous solution I was prepared by dissolving 133.7 g of nickel nitrate, 204.7 g of zinc nitrate, 29.7 g of cerium nitrate and 25.8 g of boric acid in 920 g of water in a beaker, and titrated with 30 wt% aqueous sodium carbonate solution at 72 ℃ with stirring until the pH of the reaction solution was 7.0. 763 grams of silica sol was then added. The silica sol stone is produced by Qingdao ocean chemical Co.Ltd, and the model is JN-25.
Followed by aging at 75 ℃ for 2 hours, then suction filtration and washing until the sodium ion content is below 0.05%. The wet cake was dried, granulated and then calcined at 400 ℃ for decomposition. Finally, the mixture is made into granules with the grain diameter of
The catalyst was then reduced with hydrogen at a temperature programmed to a maximum of 480 ℃. Reducing at 480 ℃ for 3 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is in a metal state, and the mass percent content of the nickel is 9%; (2) zinc, calculated by metal state, the mass percent content is 15%; (3) boron, calculated by converting into simple substance boron, the percentage content is 1.5%; (4) cerium, calculated by metal state, the mass percentage content is 3.2%; (5) a silica support, the balance excluding the content of metallic and oxidic support components.
Example 5
Aqueous solution I was prepared by dissolving 53.5 g of nickel nitrate, 61.4 g of zinc nitrate, 1.9 g of cerium nitrate and 51.5 g of boric acid in water in a beaker, and titrated with 30 wt% aqueous sodium carbonate solution at 70 ℃ with stirring until the pH of the reaction solution was 7.2. 173 g of pseudo-boehmite powder and 486 g of silica sol were then added. The pseudoboehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 285m2(iv)/g, pore volume 0.89m L/g silica sol stone manufactured by Qingdao ocean chemical Co., Ltd., model JN-25.
Followed by aging at 75 ℃ for 2 hours, then suction filtration and washing until the sodium ion content is below 0.05%. The wet cake was dried, granulated and then calcined at 380 ℃ for decomposition. Finally, the mixture is made into granules with the grain diameter of
The catalyst was then reduced with hydrogen at a temperature of up to 450 ℃ according to a temperature program. Reducing at 450 ℃ for 4 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is calculated in a metal state, and the mass percent content of the nickel is 3.6%; (2) zinc, calculated by metal state, the mass percent content is 4.5%; (3) boron, calculated by converting into simple substance boron, the percentage content is 3%; (4) cerium, calculated by metal state, the mass percentage content is 0.2%; (5) the mass ratio of the alumina to the silica is 1:1, and the balance is the balance except the content of the metallic state and oxidation state load components.
Example 6
In a beaker, 104 g of nickel nitrate, 95.5 g of zinc nitrate, 18.6 g of cerium nitrate and 3.4 g of boric acid were dissolved in 500 g of water to prepare an aqueous solution I.
500 g of pseudo-boehmite was kneaded in accordance with a conventional kneading method, and 10 ml of phosphoric acid and 20 ml of sulfuric acid were added at the time of kneading to carry out carrier acid modification. Extruding into 4mm thick strips, drying, and roasting at 500 ℃ to obtain the acid modified alumina carrier. The pseudoboehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 297m2(ii)/g, pore volume 0.95m L/g.
The 350 g of acid modified alumina carrier is taken, the aqueous solution I prepared above is dipped on the carrier for two times, and after each dipping, the carrier is dried and roasted and decomposed at 350 ℃.
The catalyst was then reduced with hydrogen at a temperature of up to 450 ℃ according to a temperature program. Reducing at 450 ℃ for 3 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is calculated in a metal state, and the mass percent content of the nickel is 7%; (2) zinc, calculated by metal state, with a mass percent content of 7%; (3) boron, calculated by converting into simple substance boron, the percentage content is 0.2%; (4) cerium, calculated by metal state, with a mass percent content of 2%; (5) alumina carrier, the balance excluding the content of metallic and oxidic support components.
Example 7
In a beaker, 104 g of nickel nitrate, 95.5 g of zinc nitrate, 18.6 g of cerium nitrate and 3.4 g of boric acid were dissolved in 500 g of water to prepare an aqueous solution I.
400 g of pseudo-boehmite and 200 g of silica sol were mixed and kneaded in accordance with a conventional kneading method, and 10 ml of hydrofluoric acid and 20 ml of sulfuric acid were added during kneading to carry out carrier acid modification. Extruding into 4mm thick strips, drying, and roasting at 500 ℃ to obtain the acid modified alumina carrier. The pseudoboehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 297m2(iv)/g, pore volume 0.95m L/g. silica sol stone manufactured by Qingdao ocean chemical Co., Ltd., model number JN-25.
The 350 g of acid modified alumina carrier is taken, the aqueous solution I prepared above is dipped on the carrier for two times, and after each dipping, the carrier is dried and roasted and decomposed at 350 ℃.
The catalyst was then reduced with hydrogen at a temperature of up to 450 ℃ according to a temperature program. Reducing at 450 ℃ for 3 hours. After cooling, the catalyst of this example was obtained. The catalyst contained the following composition by instrumental analysis:
(1) nickel, wherein the nickel is calculated in a metal state, and the mass percent content of the nickel is 7%; (2) zinc, calculated by metal state, with a mass percent content of 7%; (3) boron, calculated by converting into simple substance boron, the percentage content is 0.2%; (4) cerium, calculated by metal state, with a mass percent content of 2%; (5) alumina carrier, the balance excluding the content of metallic and oxidic support components.
Example 8
This example is an example of catalyst evaluation.
The method comprises the following steps of filling a catalyst in an oil bath controlled isothermal fixed bed reactor, mixing acetone metered by a metering pump and hydrogen metered by a gas mass flow meter, feeding the mixture into a preheater, vaporizing the acetone, feeding the acetone into a reactor, flowing through a catalyst bed layer, and carrying out condensation, dehydration and hydrogenation series reactions under the catalytic action of the catalyst, wherein the reaction conditions are as follows: the reaction temperature is 160 ℃, the reaction pressure is 1.0MPa, and the space velocity is 0.5h-1And the mass ratio of hydrogen to acetone was 3: 1.
The catalyst of comparative example 1 was evaluated as: the reaction temperature is 110 ℃, the reaction pressure is 1.0MPa, and the space velocity is 0.5h-1And the mass ratio of hydrogen to acetone was 3: 1.
The test results are shown in table 1 below.
TABLE 1 test results
As can be seen from the evaluation results in table 1, the catalyst of the present invention has higher acetone conversion rate and can co-produce isopropanol while synthesizing methyl isobutyl ketone in high yield, compared to the palladium/resin catalyst of comparative example 1. The isopropanol generated by the reaction is a good low molecular solvent, and heavy components generated in the reaction process can be washed off from the catalyst bed layer, so that the stability of the catalyst is maintained. The yield of methyl isobutyl ketone from the single pass conversion is higher than the palladium on resin catalyst of comparative example 1. In addition, the catalyst of the invention is subjected to a stability assessment test for 600h, and shows ideal stability.
Claims (5)
1. The nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol by using acetone through a one-step method is characterized by comprising a carrier and load components of nickel, zinc, boron and cerium, wherein the zinc, the boron and the cerium exist in the form of oxides;
the catalyst comprises the following components in percentage by mass of 100 percent:
(1) the nickel accounts for 3.5-12% of the metal state by mass percent;
(2) zinc, calculated by metal state, with a mass percent content of 4-15%;
(3) boron, calculated by converting into simple substance boron, with the mass percent content of 0.1% -3%;
(4) the cerium accounts for 0.1-4% by mass when being converted into a metal state;
(5) a support, the balance being other than the content of the supported component in the metallic state and in the oxidized state.
2. The nickel-based catalyst of claim 1, wherein the support is alumina, silica, an alumina-silica composite support, or a molecular sieve.
3. The nickel-based catalyst of claim 2, wherein the alumina is an acid-modified alumina or a base-modified alumina.
4. The nickel-based catalyst of claim 2, wherein the silica is acid-modified silica or base-modified silica.
5. The nickel-based catalyst according to claim 2, wherein the alumina-silica composite support is an acid-modified alumina-silica composite support or a base-modified alumina-silica composite support.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB656405A (en) * | 1947-12-09 | 1951-08-22 | Distillers Co Yeast Ltd | Manufacture of methyl-isobutyl ketone |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102806086A (en) * | 2012-08-15 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB656405A (en) * | 1947-12-09 | 1951-08-22 | Distillers Co Yeast Ltd | Manufacture of methyl-isobutyl ketone |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102806086A (en) * | 2012-08-15 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation |
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