CN107930640B - Catalyst for coproduction of 4-methyl-2-pentanone and 4-methyl-2-pentanol by one-step method - Google Patents
Catalyst for coproduction of 4-methyl-2-pentanone and 4-methyl-2-pentanol by one-step method Download PDFInfo
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- CN107930640B CN107930640B CN201610892292.3A CN201610892292A CN107930640B CN 107930640 B CN107930640 B CN 107930640B CN 201610892292 A CN201610892292 A CN 201610892292A CN 107930640 B CN107930640 B CN 107930640B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- 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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- 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
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Abstract
The invention discloses a catalyst, which belongs to the technical field of application and development of acetone downstream products, and discloses a method for promoting reaction by using copper, alkaline earth metal, cerium and chromium as load components and selecting alumina, silicon oxide or an alumina-silicon oxide composite carrier with rich acidity and alkalinity under mild reaction conditions, wherein the yield of 4-methyl-2-pentanone is higher than that of a palladium/resin catalyst used in the conventional industrial device, and meanwhile, economic 4-methyl-2-pentanol is byproduct. The catalyst exhibits desirable stability. The catalyst 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 coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by using acetone as a raw material through a one-step method.
Background
4-methyl-2-pentanone, commonly called as methyl isobutyl ketone (MIBK for short), is an important solvent and chemical intermediate, is of great interest due to 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 a plurality of organic solvents such as alcohol, benzene, ether and the like, can be used as raw materials of coating, ethyl cellulose, nitrocellulose, audio and video tapes, paraffin, a plurality of natural or synthetic resin solvents, a dewaxing agent, a rare earth metal extracting agent, a polymerization initiator, a surfactant, a medicine, a pesticide extracting agent and a rubber anti-aging agent, is a current pretty fine petrochemical intermediate, has irreplaceability in a plurality of application fields, and is still imported in China every year.
As seen in the current market, 4-methyl-2-pentanone 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 the acetone three-step method illustrates the reaction process of synthesizing 4-methyl-2-pentanone by 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 copper is used as a cocatalyst component to synthesize 4-methyl-2-pentanone. 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.
4-methyl-2-pentanol, commonly called as methyl isobutyl carbinol (MIBC for short), is an excellent medium-boiling point solvent, is mainly used as a solvent for dyes, petroleum, rubber, resin, paraffin, nitrocellulose, ethyl cellulose and the like, is used as an inert solvent for nitrocellulose lacquer, can increase the luster and the smoothness of paint, improves the reddening property, is used as a solvent in the manufacture of lubricating oil additives and the like. Raw materials for organic synthesis, mineral flotation detergents, such as for example extracted silicon and copper sulphate ores, and brake fluids. In recent years, the demand of 4-methyl-2-pentanol is continuously increased, the market prospect is very optimistic, and the price is high.
With the continuous construction of domestic MIBK devices, the devices for simply producing MIBK do not have the profitability, and most devices are in a production stop or low-load operation state. Industry has begun to look for downstream products of MIBK to improve the profitability and risk resistance of the device, and one important product is MIBC, which is also expensive and has a good market value. Based on this market demand, the inventors developed the catalyst of the present invention.
Throughout the literature and reports, the catalyst currently commercialized in this field is still a Pd/resin catalyst, the lifetime of the catalyst is 9-12 months, and the catalyst cannot produce or by-produce 4-methyl-2-pentanol (MIBC). 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, while the widely researched non-noble metal catalyst still can not meet the industrialization requirement, the inventor carries out deep and detailed research on the non-metal catalyst according to the enterprise requirement, and obtains more ideal catalyst and process technology through years of experimental research.
The specific technical scheme of the invention is as follows:
the invention provides a catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by a one-step method, which is characterized by comprising a carrier and supported components of copper, alkaline earth metal, cerium and chromium, wherein the alkaline earth metal exists in the form of oxide.
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) copper, wherein the copper is calculated in a metal state, and the mass percentage content of the copper is 5% -15%;
(2) the alkaline earth metal accounts for 0.05 to 2 percent in mass percentage by weight when the conversion is in a metal state;
(3) cerium, wherein the mass percent of the cerium is 0.1-4% in terms of metal state;
(4) chromium, calculated by metal state, with a mass percent content of 2-15%;
(5) a support, the balance being other than the content of the supported component in the metallic state and the metallic oxidation state.
The catalyst prepared by the invention needs to be subjected to reduction treatment before use, most of copper is reduced to be in a metal state, but some components such as alkaline earth metal cannot be reduced to be in a metal state.
The alkaline earth metal in the copper-based catalyst can be one or a combination of more than two of magnesium, calcium and barium, and is more preferably one or two of magnesium and calcium from the perspective of catalytic synthesis of methyl isobutyl ketone by the catalyst.
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 source of copper metal in the catalyst can be selected from water-soluble metal salts such as nitrates, sulfates, chlorides, acetates, oxalates, and bromides, or from metallic copper, such as copper metal sheets, and the like. More specifically, the water-soluble metal salt is selected from one or more of copper nitrate, copper chloride, copper oxalate, copper sulfate and copper acetate, and more preferably one or more of copper nitrate, copper acetate and copper 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 copper. The cerium plays a role in modulating the electronic structure of the reduced copper catalyst, the reduced copper is mainly zero-valent, the cerium is reduced from 4+ valent to 3+ valent, the copper and the cerium play an interaction role, electrons deviate from the cerium by the copper, the electronic unsaturation degree of the copper is increased, the electronic change of the carbonyl of the acetone is influenced, and the reaction is promoted to be carried out.
More surprisingly, the inventor finds that the effect of improving the reaction performance of the catalyst by the aid of cerium is more obvious in the copper-based catalyst prepared by dipping, spraying, coprecipitation, deposition-precipitation, ammonia evaporation precipitation, sol-gel and suction filtration and ball milling after being dissolved into alloy.
The source of cerium is not limited and may be any known cerium-containing compound. Further preferable sources of cerium include ammonium cerium nitrate, cerium sulfate, ammonium cerium sulfate, cerium chloride, cerium nitrate, cerium carbonate, cerium fluoride, cerium acetate, cerium oxalate, and the like.
The alkaline earth metal in the catalyst of the invention is selected from one or more of calcium, magnesium and barium. The alkaline earth metal source may be water soluble nitrate, carbonate, chloride, phosphate, sulfate, acetate, fluoride, hydroxide, and the like. More specifically, for example, the source thereof is selected from one or more of calcium nitrate, monocalcium phosphate, magnesium nitrate, magnesium phosphate, and barium nitrate.
The addition mode of the alkaline earth metal element can be selected from any one of the following modes: dissolving the copper salt in the processes of dipping, kneading, precipitation, deposition-precipitation or sol-gel, and then adding the solution; adding the copper salt together or step by step in the methods of blending, ball milling, melting and the like; adding the copper salt and the copper salt in the processes of dipping, precipitation, deposition-precipitation or sol-gel respectively or step by step; adding the catalyst precursor into a dried filter cake or xerogel obtained by precipitation, deposition-precipitation or sol-gel, or a material after roasting and decomposition; or in the forming stage of sheet beating or strip extruding and the like.
The source of chromium in the catalyst may be selected from water-soluble metal salts such as chromium nitrate, chromium sulfate, chromates, chromium chloride, dichromates, and the like. More particularly the water soluble metal salt is selected from one or more of chromium nitrate, ammonium dichromate, chromium sulphate and chromium chloride.
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 carrier silica may be selected from water glass precipitation, silica powder, hydrolysis of ethyl orthosilicate, silica sol, and the like. The silicon dioxide powder can be prepared by chemical deposition method, water glass precipitation and dryingBall milling or spray drying silica sol to obtain the size of 10 nm-500 micron; such as coarse-pore microspherical silicon dioxide (average pore diameter is 8.0-12.0nm, specific surface area is 300-600 m) produced by Qingdao ocean chemical plant2The pore volume is 0.8-1.1 ml/g), and the specific surface area is 400-600 m, wherein the content of precipitated silica (SiO 2)) produced by Guangzhou national chemical plant is more than or equal to 95.0, the fineness (325-mesh screen residue) is less than or equal to 1.82/g) or activated carbon black, e.g. fumed silica AEROSIL200 from Degussa having a specific surface of 200m2The specific surface area of the silica microspheres is 400-500 m2The particle size is 2-30 μm. The silica powder may be added as a carrier in a precipitation or precipitation-precipitation process. The direct precipitation method of water glass is characterized in that water glass is used as a raw material, and an acidic precipitator or an ionic precipitator, such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, calcium nitrate, zirconyl chloride, magnesium nitrate, cobalt nitrate and the like, is added into the water glass. The precipitant is added to form white jelly, and the white jelly is used after being washed for several times or is added on the basis of the white jelly by a precipitation method of other components. Tetraethoxysilane is used in the preparation of the catalyst of the present invention by a sol-gel process. The silica sol as liquid silicon source may be used directly in the precipitation system of precipitation and deposition-precipitation process.
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 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 pressure of a bed layer 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 as described in detail in the literature, such as "Preparation of Solid Catalysts", written by the general sources of Huangtao, "Industrial catalyst design and development", professor Gerhard Ertl et al.
For example, soluble copper salt, alkaline earth metal salt, cerium salt and chromium salt can be dissolved into aqueous solution, and loaded on the carrier by adopting an impregnation method, and the carrier can be impregnated for multiple times according to the water absorption rate, or the salts can be respectively dissolved into aqueous solution and impregnated step by step, and then the carrier is dried, roasted, decomposed, reduced, and the decomposition and reduction temperature and program are carried out, and the technicians in the field can carry out the reduction and reduction characterization results according to the temperature programming of the prepared catalyst.
For example, the soluble copper salt, the alkaline earth metal salt, the cerium salt and the chromium salt are dissolved into an aqueous solution, the temperature is raised to a certain temperature, the aqueous solution of sodium carbonate is added under stirring until the pH value is 7-8, then the carrier powder is added, the mixture is subjected to heat preservation and aging for a certain time, and the mixture is filtered, washed, dried, granulated, roasted, decomposed and formed.
The catalyst of the invention is reduced before use, the reducing gas can be hydrogen gas, a mixed gas of hydrogen gas and nitrogen gas, and the content of the hydrogen gas in the mixed gas of hydrogen and nitrogen gas can be any content, such as 2 vol% to 80 vol%, or can be any contentTo use higher levels of gas. 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 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 100 ℃ 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 reaching 250-300 ℃, 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. 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 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 of the invention has low cost, and the price of the palladium catalyst per ton is as high as dozens of ten thousand yuan, even millions of yuan, which is one tenth of the price of the palladium catalyst per ton. The preparation process is relatively simple and easy to operate, the palladium catalyst is polymerized to prepare granular resin firstly, then palladium is loaded on the resin through 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. The palladium/resin catalyst has narrow process operation window, easy catalyst deactivation and acid amount reduction caused by overhigh temperature, and the catalyst of the invention has wider temperature operation window. The structural stability and operational applicability of the catalyst determine the high stability and lifetime of the catalyst of the present invention. The palladium catalyst only produces one product, namely methyl isobutyl ketone, but the catalyst of the invention not only can produce methyl isobutyl ketone, but also can produce 4-methyl-2-pentanol, and industrial production devices have 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
An aqueous solution I was prepared by dissolving 58.2 g of copper nitrate, 57 g of magnesium nitrate and 36.3 g of cerium nitrate in 350 g of water in a beaker. In a separate beaker, 29 grams of ammonium dichromate was dissolved in 68 grams of water to make aqueous solution II. An aqueous solution II of ammonium dichromate was poured into a beaker of the aqueous solution I with stirring and at a solution temperature of 70 ℃ and then titrated with an aqueous 30 wt% sodium carbonate solution until the pH of the reaction solution became 7.0. 357 g 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 290m2The pore volume is 0.9 mL/g.
Followed by aging at 75 ℃ for 4 hours, then suction filtration and washing until the sodium ion content is below 0.05%.
Drying, granulating, and calcining at 350 deg.C for decomposition. Finally, the mixture is made into granules with the grain diameter of
Then, the catalyst was reduced by a mixed gas of 5 vol% hydrogen and 95 vol% nitrogen at a temperature of 260 ℃ as a maximum temperature program. Reducing at 260 ℃ for 4 hours. And cooling to obtain the catalyst. The composition was analyzed by an instrument and the catalyst composition was as follows:
(1) copper, wherein the copper is 5.1 percent in mass percentage by weight in a metallic state; (2) magnesium, calculated by metal state, with a mass percent content of 1.8%; (3) cerium, calculated by metal state, the mass percentage content is 3.9%; (4) chromium, which is converted into a metal state and has a mass percent content of 2.0 percent; (5) alumina carrier, the balance being in addition to the content of the supporting components in the metallic state and in the metallic oxidation state.
Comparative example 1
An industrially useful palladium/resin catalyst obtained from Zhejiang Utilization chemical Co., Ltd.
Example 2
Aqueous solution I was prepared by dissolving 168.9 grams of copper nitrate, 1.9 grams of magnesium nitrate, and 18.6 grams of cerium nitrate in 442 grams of water in a beaker. In a separate beaker, 215.3 grams of ammonium dichromate was dissolved in 500 grams of water to make aqueous solution II. An aqueous solution II of ammonium dichromate was poured into a beaker of the aqueous solution I with stirring at 70 ℃ and then titrated with an aqueous 30 wt% sodium carbonate solution until the pH of the reaction solution became 7.1. 542 g of silica sol were then added. The silica sol is manufactured by Shandong ocean chemical industry Co., Ltd, and the model is JN-30.
Followed by aging at 80 ℃ for 4 hours, then suction filtration and washing until the sodium ion content is below 0.05%.
Drying, granulating, and calcining at 380 deg.C for decomposition. Finally, the mixture is made into granules with the grain diameter of
Then, the catalyst was reduced by a mixed gas of 5 vol% hydrogen and 95 vol% nitrogen at a temperature of 260 ℃ as a maximum temperature program. Reducing at 260 ℃ for 4 hours. And cooling to obtain the catalyst. The composition was analyzed by an instrument and the catalyst composition was as follows:
(1) copper, wherein the copper is calculated in a metal state, and the mass percentage content of the copper is 14.8%; (2) magnesium, calculated by metal state, with a mass percent content of 0.06%; (3) cerium, calculated by metal state, with a mass percent content of 2.0%; (4) chromium, which is converted into a metal state and has a mass percent content of 14.8%; (5) a silica support, the balance being in addition to the content of the supported component in the metallic state and in the metallic oxidation state.
Example 3
Aqueous solution I was prepared by dissolving 114 g of copper nitrate, 12.3 g of calcium nitrate and 0.93 g of cerium nitrate in 297 g of water in a beaker. In a separate beaker 145.4 g of ammonium dichromate were dissolved in 340 g of water to make aqueous solution II. An aqueous solution II of ammonium dichromate was poured into a beaker of the aqueous solution I with stirring at 70 ℃ and then titrated with an aqueous 30 wt% sodium carbonate solution until the pH of the reaction solution became 7.3. 148.6 grams of pseudo-boehmite and 346.7 grams of silica sol were then added. 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. The silica sol is manufactured by Shandong ocean chemical industry Co., Ltd, and the model is JN-30.
Followed by aging at 85 ℃ for 4 hours, then suction filtration and washing until the sodium ion content is below 0.05%.
Drying, granulating, and calcining at 380 deg.C for decomposition. Finally, the mixture is made into granules with the grain diameter of
Then, the catalyst was reduced by a mixed gas of 5 vol% hydrogen and 95 vol% nitrogen at a temperature of 260 ℃ as a maximum temperature program. Reducing at 260 ℃ for 4 hours. And cooling to obtain the catalyst. The composition was analyzed by an instrument and the catalyst composition was as follows:
(1) copper, wherein the copper is calculated in a metal state, and the mass percentage content of the copper is 10%; (2) calcium, calculated by metal state, with a mass percent content of 1.0%; (3) cerium, calculated by metal state, the mass percent content is 0.1%; (4) the chromium is converted into a metal state, and the mass percent content of the chromium is 10 percent; (5) the mass ratio of the alumina-silica composite carrier to the alumina-silica composite carrier is about 1:1, and the balance is the balance except the content of the load components in a metal state and a metal oxidation state.
Example 4
In a beaker, 79.9 g of copper nitrate, 31.7 g of magnesium nitrate, 18.6 g of cerium nitrate and 101.8 g of ammonium dichromate were dissolved in 350 g of water to prepare an aqueous solution.
Kneading with 500 g of pseudo-boehmite, extruding into 4mm thick strips, drying, and roasting at 500 ℃ to obtain the alumina carrier. 10 ml of phosphoric acid and 20 ml of sulfuric acid were added during kneading to perform carrier acid modification. 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.
The 230 g carrier is taken, the aqueous solution prepared above is dipped on the carrier for two times, after each dipping, the carrier is dried and roasted at 350 ℃ for decomposition.
Then, the catalyst was reduced by a mixed gas of 5 vol% hydrogen and 95 vol% nitrogen at a temperature of 260 ℃ as a maximum temperature program. Reducing at 260 ℃ for 4 hours. And cooling to obtain the catalyst. The composition was analyzed by an instrument and the catalyst composition was as follows:
(1) copper, wherein the copper is calculated in a metal state, and the mass percentage content of the copper is 7%; (2) magnesium, calculated by metal state, with a mass percent content of 1.0%; (3) cerium, calculated by metal state, with a mass percent content of 2%; (4) chromium, which is converted into a metal state and accounts for 7 percent by mass; (5) alumina carrier, the balance being in addition to the content of the supporting components in the metallic state and in the metallic oxidation state.
Example 5
This example is an example of catalyst evaluation.
Filling the catalyst in an oil bath controlled isothermal fixed bed reactor, mixing the acetone measured by a metering pump and the hydrogen measured by a gas mass flowmeter, and preheatingThe acetone is vaporized and then enters a reactor, flows through a catalyst bed layer, and undergoes condensation, dehydration and hydrogenation series reactions under the catalytic action of the catalyst, and 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 results in Table 1, compared with the palladium/resin catalyst in comparative example 1, the catalyst of the present invention has higher conversion rate, and can produce methyl isobutyl ketone and by-product methyl isobutyl carbinol and isopropanol, and the isopropanol is a better low molecular solvent, and can wash the generated heavy components from the bed layer, thereby maintaining the stability of the catalyst. 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 1000 hours, and shows ideal stability.
Claims (6)
1. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by a one-step method is characterized by comprising a carrier and supported components of copper, alkaline earth metal, cerium and chromium, wherein the alkaline earth metal exists in the form of oxide;
the catalyst comprises the following components in percentage by mass of 100 percent:
(1) copper, wherein the mass percent of the copper is 5% -15% in a metallic state;
(2) the alkaline earth metal accounts for 0.05-2% of the metal state in terms of mass percentage;
(3) cerium, wherein the mass percentage of the cerium is 0.1% -4% in a metal state;
(4) the chromium is calculated by the metal state, and the mass percent content is 2-15%;
(5) a support, the balance being other than the content of the supported component in the metallic state and the metallic oxidation state.
2. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by the one-step method according to claim 1, wherein the alkaline earth metal in the catalyst is one or both of magnesium and calcium.
3. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by the one-step method according to claim 1, wherein the carrier is alumina, silica, an alumina-silica composite carrier or a molecular sieve.
4. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol in the one-step method according to claim 3, wherein the alumina is acid-modified alumina or alkali-modified alumina.
5. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol in the one-step method according to claim 3, wherein the silicon oxide is acid-modified silicon oxide or alkali-modified silicon oxide.
6. The catalyst for coproducing 4-methyl-2-pentanone and 4-methyl-2-pentanol by the one-step process according to claim 3, wherein the alumina-silica composite carrier is an acid-modified alumina-silica composite carrier or a base-modified alumina-silica composite carrier.
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