CN107930661B - Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method - Google Patents
Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method Download PDFInfo
- Publication number
- CN107930661B CN107930661B CN201610892348.5A CN201610892348A CN107930661B CN 107930661 B CN107930661 B CN 107930661B CN 201610892348 A CN201610892348 A CN 201610892348A CN 107930661 B CN107930661 B CN 107930661B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- alumina
- silica
- acetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- C07C45/73—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst, belonging to the technical field of application and development of acetone downstream products, which takes nickel as a main active component, takes phosphorus, lanthanum and/or neodymium as an auxiliary component, 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 simultaneously coproduces isopropanol and diisobutyl ketone with high added value. 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 diisobutyl ketone 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 search for more downstream products of methyl isobutyl ketone to improve the economics of the equipment.
Diisobutyl ketone (DIBK) is a high-boiling-point solvent and an organic synthetic intermediate with excellent performance, has the advantages of high boiling point, good intermiscibility and the like, is widely applied to industries such as vacuum plating, leather coating, medicine, plastic paint, mineral processing, chemical engineering and the like, can be used as a solvent of paint vehicle, food refining, vinyl resin coating and other synthetic resin coatings, can be used as an extractant of rare earth metal, can be used as a dispersing agent to produce organic aerosol, and can be used as an intermediate for producing medicine and pesticide. In recent years, the demand of diisobutyl ketone is continuously increased, the market prospect is very optimistic, and the price is high.
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 industrialized requirement, so that the inventor carries out intensive research on the non-metal catalyst according to the requirement of enterprises in order to meet the requirement of enterprises on downstream products of methyl isobutyl ketone, and obtains more ideal catalyst and process technology after years of experimental research.
The specific technical scheme of the invention is as follows:
the invention provides a nickel-based catalyst for synthesizing acetone downstream condensation products by using acetone as a raw material through a one-step method, which comprises a carrier and load components of nickel, phosphorus and lanthanide metal elements, wherein the lanthanide metal elements exist in the form of oxides, and the phosphorus exists in the form of oxygen-containing compounds.
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 of the nickel is 4% -14%;
(2) the phosphorus is calculated by converting into simple substance phosphorus, and the mass percent content is 0.05-3%;
(3) lanthanide series metal element, calculated by metal state, with a mass percentage content of 0.2% -3%;
(4) a carrier, the balance excluding the supported component.
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 lanthanide metal and phosphorus cannot be reduced to be in a zero valence state.
The lanthanide metal in the nickel-based catalyst may be one or a combination of two or more of lanthanum, cerium and neodymium, and more preferably one or two of lanthanum and neodymium.
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.
Lanthanum and neodymium are another important component in the catalyst of the invention, and the addition of a proper amount of lanthanum and neodymium greatly improves the activity and selectivity of the catalyst. After the addition of the auxiliary agents lanthanum and neodymium, 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 many aspects: lanthanum and neodymium improve the electronic morphology of nickel. The neodymium plays a role in modulating the electronic structure of the reduced nickel catalyst, the reduced nickel is mainly zero-valent, the nickel and the reduced nickel have interaction, electrons are deflected to the neodymium by the nickel, the electronic unsaturation degree of the nickel is increased, the electronic change of the carbonyl of the acetone is influenced, and the reaction is promoted to be carried out.
The source of lanthanum and neodymium is not limited and can be all known lanthanum and neodymium containing compounds. Further optimized sources of lanthanum and neodymium can be selected from all water-soluble metal salts such as nitrates, acetates and oxalates, etc.
In the preparation process of the catalyst, a proper amount of phosphorus element is added, so that the acid amount and acid strength distribution of the catalyst carrier can be adjusted, and the dispersion degree of the metal active components can be increased. In addition, studies have shown that phosphorus can also improve the hydrothermal stability of the catalyst.
The source of phosphorus in the catalyst may be selected from phosphoric acid and water soluble phosphates, and the like. More specifically, the water-soluble salt is selected from one or more of ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, and ammonium phosphate, and more preferably one or both of ammonium dihydrogen phosphate and ammonium monohydrogen phosphate.
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 obtained by a chemical deposition method, a ball milling method after drying after water glass precipitation, or a method of silica sol spray drying and the like, and the size of the silicon dioxide powder is selected from 10 nm-500 mu m; such as coarse-pore microspherical silica (the average pore diameter is 8.0-12.0nm, the specific surface area is 300-600 m2/g, and the pore volume is 0.8-1.1 ml/g) produced by Qingdao ocean chemical plants, precipitated silica (the content of silica (SiO 2)% is more than or equal to 95.0, the fineness (325-mesh residue)% is less than or equal to 1.8, and the specific surface area is 400-600 m2/g) produced by Guangzhou civil chemical plants, or active white carbon black, or AEROSIL200 of fumed silica of Texaco corporation, the specific surface area is 200m2/g, or silica microspheres obtained by self-made spray drying, the specific surface is 400-500 m2/g, and the size is 2-30 mu m. 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, nickel 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 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, the space velocity of hydrogen is 300-5000 m3/m3·h-1. The temperature of reduction can be determined according to the composition of the specific catalyst, and for the catalyst, the catalyst can be gradually improved at the speed of 5-20 ℃/hour, preferably 5-10 ℃/hourAnd (3) keeping the catalyst bed layer at the temperature of 200 ℃ for 2-8 hours, and then gradually increasing the temperature of the catalyst bed layer at the speed of 5-20 ℃/hour, preferably 5-10 ℃/hour until the temperature is 450-500 ℃, and keeping 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 of the invention 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 of the invention 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 can not 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 of the invention not only can produce methyl isobutyl ketone, but also can produce diisobutyl ketone, 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
500 g of pseudo-boehmite was kneaded in accordance with a conventional kneading method, and 20 ml of sulfuric acid was added at the time of kneading to carry out carrier acid modification. Is extruded into
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 297m2The pore volume is 0.95 mL/g.
Aqueous solution I was prepared by dissolving 49.5 grams of nickel nitrate, 4.7 grams of lanthanum nitrate, and 1.9 grams of phosphoric acid in 180 grams of water in a beaker.
The 124 g 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 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) the phosphorus accounts for 0.5 percent by mass when converted into the simple substance phosphorus; (3) lanthanum, calculated by metal state, with a mass percent content of 1.5%; (4) alumina carrier and the rest.
Comparative example 1
An industrially useful palladium/resin catalyst obtained from Zhejiang Utilization chemical Co., Ltd.
Example 2
Kneading 500 g of pseudo-boehmite according to a conventional kneading method, and adding 5ml of hydrofluoric acid and 15 ml of sulfuric acid during the kneadingTo carry out the carrier acid modification. Is extruded into
Drying and roasting at 550 ℃ 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 297m2The pore volume is 0.95 mL/g.
Aqueous solution I was prepared by dissolving 20.8 grams of nickel nitrate, 0.6 grams of lanthanum nitrate, and 10.4 grams of phosphoric acid in 190 grams of water in a beaker.
The 124 g 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 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 by metal state, and the mass percent content of the nickel is 4.2%; (2) phosphorus, calculated as elemental phosphorus, accounts for 2.8% by mass; (3) lanthanum, calculated by metal state, with a mass percent content of 0.2%; (4) alumina carrier and the rest.
Example 3
500 g of pseudo-boehmite was kneaded in accordance with a conventional kneading method, and 8 g of calcium nitrate was added at the time of kneading to perform alkali modification of the carrier. Is extruded into
Drying and roasting at 500 ℃ to obtain the alkali modified alumina carrier. The pseudoboehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 297m2The pore volume is 0.95 mL/g.
An aqueous solution I was prepared by dissolving 66.9 grams of nickel nitrate, 8.9 grams of neodymium nitrate, and 0.4 grams of phosphoric acid in 180 grams of water in a beaker.
The 118 g of alkali 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 at 350 ℃ for decomposition.
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 accounts for 13.5 percent of the weight of the alloy in a metallic state; (2) phosphorus, calculated as elemental phosphorus, accounts for 0.1% by mass; (3) neodymium, calculated by converting into a metal state, and the mass percentage content is 2.8%; (4) alumina carrier and the rest.
Example 4
400 g of pseudo-boehmite and 200 g of silica sol were mixed and kneaded by a conventional kneading method, and 12 ml of sulfuric acid was added during kneading to carry out carrier acid modification. Is extruded into
Drying and roasting at 500 ℃ to obtain the acid modified alumina-silica composite carrier. The pseudoboehmite is produced by Jiangsu three-agent industry Co., Ltd, and has a specific surface area of 297m2The pore volume is 0.95 mL/g. The silica sol stone is produced by Qingdao ocean chemical Co.Ltd, and the model is JN-25.
Aqueous solution I was prepared by dissolving 39.6 grams of nickel nitrate, 3.1 grams of lanthanum nitrate, and 3.7 grams of phosphoric acid in 190 grams of water in a beaker.
The above 125 g acid modified alumina carrier was taken, the above prepared aqueous solution I was impregnated on the carrier twice, after each impregnation, dried, and decomposed by calcination at 350 ℃.
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 percent content of the nickel is 8%; (2) phosphorus, calculated by simple substance phosphorus, with the mass percent content of 1%; (3) lanthanum, calculated by metal state, with a mass percent content of 1%; (4) alumina-silica composite carrier, the rest.
Example 5
500 g of pseudo-boehmite was kneaded in accordance with a conventional kneading method, and 10 ml of sulfuric acid was added at the time of kneading to carry out carrier acid modification. Is extruded into
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 297m2The pore volume is 0.95 mL/g.
Aqueous solution I was prepared by dissolving 49.5 grams of nickel nitrate, 1.5 grams of lanthanum nitrate, 4.9 grams of neodymium nitrate, and 3 grams of phosphoric acid in 180 grams of water in a beaker.
The above 122 g of acid modified alumina carrier was taken, and the above prepared aqueous solution I was impregnated on the carrier twice, after each impregnation, dried, and decomposed by calcination at 350 ℃.
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) the phosphorus is calculated by converting into a simple substance state, and the mass percent content is 0.8%; (3) lanthanum, calculated by metal state, with a mass percentage content of 0.5%; (4) neodymium, calculated by metal state, with a mass percent content of 1.5%; (5) alumina carrier and the rest.
Example 6
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 ℃ and the reaction pressure isForce 1.0MPa and airspeed 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 than the palladium/resin catalyst of comparative example 1, and can co-produce isopropanol and high value-added diisobutyl ketone while synthesizing methyl isobutyl ketone in high yield. 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 (6)
1. A nickel-based catalyst for synthesizing acetone downstream condensation products by a one-step method, which is characterized by comprising a carrier and supported components of nickel, phosphorus and lanthanide metal elements, wherein the lanthanide metal elements exist in the form of oxides, and the phosphorus exists in the form of oxygen-containing compounds;
the catalyst comprises the following components in percentage by mass of 100 percent:
(1) nickel, wherein the nickel is calculated by metal state, and the mass percent content of the nickel is 4% -14%;
(2) the phosphorus is calculated by converting into simple substance phosphorus, and the mass percent content is 0.05-3%;
(3) lanthanide series metal element, calculated by metal state, with a mass percentage content of 0.2% -3%;
(4) carrier, the balance of the load component.
2. The nickel-based catalyst of claim 1 wherein the lanthanide metal in the nickel-based catalyst is one or both of lanthanum and neodymium.
3. The nickel-based catalyst of claim 1, wherein the support is alumina, silica, an alumina-silica composite support, or a molecular sieve.
4. The nickel-based catalyst of claim 3, wherein the alumina is an acid-modified alumina or a base-modified alumina.
5. The nickel-based catalyst of claim 3, wherein the silica is acid-modified silica or base-modified silica.
6. The nickel-based catalyst according to claim 3, wherein the alumina-silica composite support is an acid-modified alumina-silica composite support or a base-modified alumina-silica composite support.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610892348.5A CN107930661B (en) | 2016-10-13 | 2016-10-13 | Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610892348.5A CN107930661B (en) | 2016-10-13 | 2016-10-13 | Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107930661A CN107930661A (en) | 2018-04-20 |
| CN107930661B true CN107930661B (en) | 2020-02-18 |
Family
ID=61928896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610892348.5A Active CN107930661B (en) | 2016-10-13 | 2016-10-13 | Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107930661B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014033413A1 (en) * | 2012-09-03 | 2014-03-06 | Arkema France | Method for producing methacrolein and/or methacrylic acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9102583B2 (en) * | 2011-02-25 | 2015-08-11 | China Petroleum & Chemical Corporation | Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction |
| CN102806086B (en) * | 2012-08-15 | 2014-06-04 | 中国海洋石油总公司 | Preparation method of catalyst for coproducing isopropanol and methyl isobutyl ketone by acetone hydrogenation |
| CN104275207B (en) * | 2014-07-24 | 2016-08-17 | 中国石油大学(华东) | Non-precious metal reforming catalyst and application thereof |
| CN105642324B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of base metal selective hydrocatalyst and its preparation method and application |
-
2016
- 2016-10-13 CN CN201610892348.5A patent/CN107930661B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014033413A1 (en) * | 2012-09-03 | 2014-03-06 | Arkema France | Method for producing methacrolein and/or methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107930661A (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107930635B (en) | Catalyst for co-production of methyl isobutyl ketone and diisobutyl ketone | |
| CN101927168B (en) | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof | |
| CN102302934A (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN106391028A (en) | Methanation catalyst for fluidized bed and preparation method of methanation catalyst for fluidized bed | |
| CN103638963A (en) | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof | |
| CN107519881B (en) | Preparation method of cyclohexyl acetate hydrogenation catalyst, prepared hydrogenation catalyst and cyclohexyl acetate hydrogenation method | |
| CN107930657B (en) | Cobalt-based catalyst for synthesizing methyl isobutyl ketone from acetone | |
| CN114450086A (en) | Copper-based catalyst and preparation method thereof | |
| CN101983765A (en) | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof | |
| CN103664586B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN101168124A (en) | Catalyst used for alcohol dehydration producing ethylene and preparation method | |
| CN107930661B (en) | Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method | |
| CN107930634B (en) | Nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol | |
| CN107930640B (en) | Catalyst for coproduction of 4-methyl-2-pentanone and 4-methyl-2-pentanol by one-step method | |
| CN107930638B (en) | Copper-based catalyst for synthesizing methyl isobutyl ketone by acetone one-step method | |
| CN103331160A (en) | Preparation method of high-dispersion copper-based catalyst based on non-precious metal | |
| CN109701536B (en) | Catalyst for synthesizing methyl isobutyl alcohol and isopropanol from acetone and preparation method and application thereof | |
| CN108863706B (en) | Selective hydrogenation method for alkyne-containing four-fraction | |
| CN108865243B (en) | Pre-hydrogenation treatment method of carbon tetra-alkylation raw material | |
| CN102794178A (en) | Selective hydrogenation catalyst and preparation thereof | |
| CN111250098B (en) | Water hydrogenation catalyst for Fischer-Tropsch synthesis reaction and preparation method and application thereof | |
| CN115121270A (en) | Catalyst for synthesizing 2-ethylhexanal by selective hydrogenation and application method thereof | |
| CN108722409A (en) | Mesoporous copper-based aluminium oxide catalyst, preparation method and application | |
| CN101176850B (en) | Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage | |
| CN105709786B (en) | A kind of selectively hydrogenating butadiene, 1 butylene heterogeneous catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |