CN109701539B - Catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone and preparation method and application thereof - Google Patents
Catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone, a preparation method and application thereof, belonging to the field of catalysts. The catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone is measured by taking the whole weight of the catalyst as 100 parts, and comprises the following components: a. 0.5 to 5 parts of at least one from nickel or nickel oxide; b. 0.5 to 10 parts of at least one of cobalt and cobalt oxide; c. 82-99 parts of a carrier, wherein the carrier is at least one selected from titanium-modified silicon oxide, aluminum oxide and zirconium oxide subjected to high-temperature roasting. The catalyst is used under mild reaction conditions, the yield of the methyl isobutyl ketone is higher than that of a palladium/resin catalyst commonly used in the existing industrial device, and the methyl isobutyl alcohol is simultaneously co-produced. The catalyst of the invention has the cost obviously lower than that of the existing palladium catalyst and has better economic benefit.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone, and a preparation method and application thereof.
Background
Methyl isobutyl ketone (MIBK for short), an important solvent and chemical intermediate, is of great interest because of its excellent performance, has aromatic ketone smell, is colorless and transparent, has a boiling point of medium boiling point, has very strong dissolving power, can be miscible with numerous organic solvents such as alcohol, benzene, ether, and the like, can be used as a raw material of coating, ethyl cellulose, nitrocellulose, audio-video tape, paraffin, various natural or synthetic resin solvents, dewaxing agents, rare earth metal extractants, polymerization initiators, surfactants, medicines, pesticide extractants and rubber antioxidants, is a current rather delicate fine petrochemical intermediate, and has irreplaceability in many application fields.
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 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.
Methyl isobutyl carbinol (MIBC for short), which is an excellent medium boiling point solvent, is mainly used as a solvent for dyes, petroleum, rubber, resins, paraffin, nitrocellulose, ethyl cellulose and the like, is used as an inert solvent for nitrocellulose lacquer, can increase the gloss and the smoothness of the coating, improves the reddening property, is used as a solvent in the manufacture of lubricating oil additives and the like. Used as raw material for organic synthesis, mineral flotation lotion, such as extracted silicon and nickel sulfate ore, and brake fluid. In recent years, the demand of methyl isobutyl alcohol 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, one of the important products being MIBC, which has a good market value.
Throughout the literature and reports, the catalyst industrialized in the field is still a Pd/resin catalyst, the service life of the catalyst is 9-12 months, the acetone conversion rate is low, the product of the catalyst is single, and the market flexibility is poor. Other catalysts have not been reported industrially.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone. In particular to a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol by acetone, a preparation method and application thereof.
One of the purposes of the invention is to provide a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone, which comprises the following components by taking the total weight of the catalyst as 100 parts:
a. 0.5-5 parts of at least one active component from nickel or nickel oxide;
b. 0.5-10 parts of at least one active component from cobalt or cobalt oxide;
c. 82-99 parts of carrier, wherein the carrier is selected from high-temperature roasted titanium modified silicon oxide, aluminum oxide and
at least one of zirconia.
Wherein, the content of the component a is preferably 2 to 4 parts, the content of the component b is preferably 2 to 5 parts, and the content of the component c is preferably 91 to 96 parts.
The content of the titanium dioxide in the carrier can be 5-15 parts by taking the whole weight of the catalyst as 100 parts.
Another object of the present invention is to provide a method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone, which comprises the following steps:
firstly, adding a modified titanium precursor into a solvent to prepare a mixed material I;
secondly, adding the carrier precursor into the mixture I to prepare a mixture II;
thirdly, mixing the mixed material II with a proper amount of inorganic acid and water, reacting the mixture II with the inorganic acid and water uniformly, and drying the mixture to obtain a mixed material III;
fourthly, roasting the mixed material III to prepare titanium modified carrier powder;
dissolving soluble salts of nickel and cobalt which are active components in water to prepare a mixed solution IV;
dissolving the template agent and the pore-expanding agent to prepare a solution V;
seventhly, placing the carrier powder in the mixed solution IV, the solution V and the solution IV into a crystallization kettle for aging, adjusting the pH value of the crystallization kettle to 6-10, preferably 7-9, by using ammonium bicarbonate or urea after aging, and filtering and washing the carrier powder;
and (viii) drying the prepared material, roasting, and reducing to obtain the catalyst for preparing the methyl isobutyl ketone and the methyl isobutyl alcohol from the acetone.
Wherein the content of the first and second substances,
in the step I, the modified titanium precursor is selected from at least one of nano titanium dioxide, butyl titanate or metatitanic acid; the concentration of the modified titanium precursor in the mixed material I is 0.001-0.1 mol/mL; the solvent in the step (i) can be at least one of ethanol, isopropanol and butanol.
In the second step, the carrier precursor is selected from at least one of silicon dioxide, aluminum oxide and zirconium oxide powder; the molar use ratio of the modified titanium precursor to the carrier precursor is 0.01-5.0: 1, preferably 0.02-3.0: 1;
in the third step, the inorganic acid may be at least one of dilute nitric acid, dilute sulfuric acid and hydrochloric acid.
The roasting temperature in the step (IV) is 950-1200 ℃, and preferably 970-1150 ℃;
in the fifth step, the concentration of the solution of the soluble salt of nickel is 1.0-5.5 mol/L, preferably 1.0-2.1 mol/L, and the concentration of the solution of the soluble salt of cobalt is 0.5-8.5 mol/L, preferably 1.3-2.5 mol/L;
the soluble salt of nickel is selected from at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel oxalate, preferably at least one of nickel nitrate, nickel sulfate and nickel oxalate; the soluble salt of cobalt is selected from at least one of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate and cobalt oxalate, preferably at least one of cobalt nitrate, cobalt sulfate and cobalt oxalate.
Dissolving the template agent and the pore-expanding agent in ethanol to prepare a solution V; the concentration of the template agent and the pore-expanding agent in the solution V is 0.1-1.5 g/ml; the template agent and the pore-expanding agent can be at least one of ethylenediamine, n-butylamine, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and 3,3',5,5' -Tetramethylbenzidine (TMB).
Seventhly, aging at 40-90 ℃ for 3-6 h;
in the step eight, the drying temperature of the material is 100-150 ℃, and the roasting temperature is 300-600 ℃.
The invention also provides an application method of the catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone, which comprises the following steps: acetone and hydrogen are used as raw materials, the reaction temperature is 120-230 ℃, the reaction pressure is 0-2.5 MPa, and the volume space velocity of the acetone is 0.1-3.0 h-1And passing the catalyst through a bed layer under the condition that the molar ratio of hydrogen to acetone is (2-10): 1 to generate a reactant flow containing methyl isobutyl ketone and methyl isobutyl alcohol.
Wherein the reaction temperature is preferably 140-190 ℃, and the reaction pressure is preferablyIs 0.5 to 1.5MPa, and the volume space velocity of the acetone can be preferably 0.5 to 1.5h-1The molar ratio of the hydrogen to the acetone is preferably (3-7): 1.
The inventors have intensively studied and found that a key factor for restricting the stability of the Pd/resin catalyst is a condensate generated by condensation of acetone, and MIBK and diisobutyl ketone (DIBK) generated further undergo condensation reaction to generate a more complicated condensation byproduct. These by-products coat the catalyst surface and plug the catalyst channels, causing deactivation of the catalytically active sites.
Titanium is another important component in the catalyst, and the activity and the selectivity of the catalyst can be greatly improved by adding a proper amount of titanium. The reasons for this are manifold: the addition of titanium improves the electronic morphology of nickel and cobalt; the titanium plays a role in modulating the electronic structure of nickel and cobalt in the reduced catalyst, thereby influencing the electronic change of carbonyl of acetone and promoting the reaction.
More surprisingly, the inventors have found that the titanium modified support after high temperature calcination contributes more to the improvement of the catalyst reactivity.
The catalyst of the invention is reduced before use, active components of nickel and cobalt are partially reduced into simple substance nickel and cobalt, the reducing gas can be hydrogen gas, mixed gas of hydrogen gas and nitrogen gas, the content of hydrogen gas in the mixed gas of hydrogen and nitrogen gas can be any content, for example, 2 vol% to 80 vol%, and gas with higher content can also be used. From the viewpoint of temperature control of catalyst reduction, a mixed gas having a low hydrogen content is preferred. The larger the space velocity of the gas, the better. The air speed is large, the heat generated by the reaction can be quickly removed in time, the temperature of the catalyst bed is kept stable, and the catalyst is not damaged by temperature runaway. For example, the space velocity of the mixed gas is 300-5000 m3/m3·h-1. The 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 a rate of 5-20 ℃/h, preferably 5-10 ℃/h, the catalyst bed layer stays at the temperature of about 150 ℃ for 2-8 hours, and then the temperature of the catalyst bed layer is gradually increased at a rate of 5-20 ℃/h, preferably 5-10 ℃/h until the temperature reaches 250 DEG CThe temperature is 500 ℃ below zero and kept for 2 to 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 content of the hydrogen is gradually increased so as to increase the content of the hydrogen in the mixed gas. The content 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 situ in the reactor, the temperature of the reduced catalyst is reduced to the reaction temperature, and then the catalyst can be fed for use.
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 cost of the catalyst of the invention is one tenth of the cost. Secondly, the preparation process is relatively simple and convenient, the operation is easy, the active components are not easy to lose, the palladium catalyst is polymerized to prepare granular resin firstly, then palladium is loaded on the palladium catalyst through exchange, and organic matters on the resin are easy to lose, so that reaction products are polluted and the product chromaticity is increased. And thirdly, the catalyst has a wider temperature operation window, the process operation window of the palladium/resin catalyst is narrow, and the catalyst is easily deactivated due to overhigh temperature. The catalyst of the invention can be used for producing methyl isobutyl ketone and methyl isobutyl alcohol, the industrial production device has stronger market adaptability, the enterprise profitability and controllability are enhanced, and the palladium/resin catalyst only produces one product, namely methyl isobutyl ketone, and the acetone conversion rate is lower.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
Example 1
Dissolving 22g of nano titanium dioxide in 18.0mL of ethanol to prepare a mixed material I, weighing 115g of alumina powder, adding the alumina powder into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 6.2mL of dilute nitric acid and 70mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1000 ℃ to obtain titanium modified carrier powder; weighing 16.87g of nickel nitrate and 19.22g of cobalt nitrate, and dissolving in 20ml of water to prepare a solution IV; a solution was prepared by weighing 3.2g of ethylenediamine and 4.5g of P123 in 10ml of ethanolV, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle for aging for 5 hours at the aging temperature of 80 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging is finished to adjust the pH of the crystallization kettle to 7.0, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 350 ℃, and introducing hydrogen at the airspeed of 500m3/m3·h-1And (2) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 2.95 parts of nickel, 0.72 part of nickel oxide, 3.57 parts of cobalt, 0.62 part of cobalt oxide, 14.8 parts of titanium dioxide and 77.34 parts of alumina.
Example 2
Dissolving 20g of nano titanium dioxide in 15mL of ethanol to prepare a mixed material I, weighing 85g of silicon dioxide and 25g of alumina powder, adding the weighed materials into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 7.5mL of dilute nitric acid and 80mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1050 ℃ to prepare titanium modified carrier powder; weighing 14.54g of nickel sulfate and 24.16g of cobalt nitrate, and dissolving in 25ml of water to prepare a solution IV; weighing 3.0g of n-butylamine and 6.0g of TMB, dissolving in 20ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 3 hours at the temperature of 90 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging is finished to adjust the pH of the crystallization kettle to 7.5, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 400 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1The temperature is programmed to 400 ℃ under the condition, the temperature is kept for 5 hours, the catalyst is prepared after the temperature is reduced, and the catalyst is analyzed by an X-fluorescence test and comprises 2.62 parts of nickel, 0.58 part of nickel oxide, 4.23 parts of cobalt, 0.95 part of cobalt oxide, 14.1 parts of titanium dioxide, 59.91 parts of silicon dioxide and 17.61 parts of alumina.
Example 3
Dissolving 13g of butyl titanate in 10mL of ethanol to prepare a mixed material I, weighing 30g of zirconium oxide and 95g of alumina powder, adding the mixed material I into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 6.8mL of dilute sulfuric acid and 85mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1150 ℃ to prepare titanium modified carrier powder; weighing 10.57g of nickel nitrate and 23.9g of cobalt oxalate, and dissolving in 20ml of water to prepare a solution IV; 1.5g of ethylenediamine and 9.0g of TMB were weighed out and dissolved in 25ml of ethanolPreparing solution V, placing solution IV, solution V and 90g of the prepared carrier powder in a crystallization kettle for aging for 4h at 80 ℃, adding 0.05mol/L urea aqueous solution to adjust the pH of the crystallization kettle to 8.5, washing and filtering, drying the filter cake at 120 ℃, decomposing the filter cake at 500 ℃, introducing hydrogen at the airspeed of 500m, and drying the filter cake3/m3·h-1The temperature is programmed to 400 ℃ under the condition, the temperature is kept for 5 hours, the catalyst is prepared after the temperature is reduced, and the catalyst is analyzed by an X-fluorescence test and comprises 2.01 parts of nickel, 0.32 part of nickel oxide, 4.34 parts of cobalt, 0.78 part of cobalt oxide, 8.72 parts of titanium dioxide, 20.12g of zirconium oxide and 63.71 parts of alumina.
Example 4
Dissolving 8.5g of nano titanium dioxide in 6mL of ethanol to prepare a mixed material I, weighing 45g of silicon dioxide and 80g of zirconia powder, adding the weighed materials into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 9.5mL of dilute hydrochloric acid and 90mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 970 ℃ to prepare titanium modified carrier powder; weighing 19.35g of nickel nitrate and 18.32g of cobalt nitrate, and dissolving in 20ml of water to prepare a solution IV; weighing 2.5g of n-butylamine and 3.0g of P123, dissolving in 12ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 6 hours at the temperature of 40 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging is finished to adjust the pH of the crystallization kettle to 7.0, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 380 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1And (3) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.62 parts of nickel, 0.56 part of nickel oxide, 3.3 parts of cobalt, 0.87 part of cobalt oxide, 5.84 parts of titanium dioxide, 30.89 parts of silicon dioxide and 54.92 parts of zirconium oxide.
Example 5
Dissolving 15g of nano titanium dioxide in 11mL of ethanol to prepare a mixed material I, weighing 55g of silicon dioxide and 60g of alumina powder, adding the weighed materials into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 5.3mL of dilute nitric acid and 75mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1090 ℃ to prepare titanium modified carrier powder; weighing 19.08g of nickel sulfate and 11.89g of cobalt nitrate, and dissolving in 20ml of water to prepare a solution IV; weigh 4.0g ofDissolving diamine and 3.5g P123 in 16ml ethanol to prepare solution V, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle for aging for 6 hours at the aging temperature of 60 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution to adjust the pH of the crystallization kettle to 7.0 after the aging is finished, then washing and filtering, drying a filter cake at 120 ℃, decomposing the filter cake at 420 ℃, and introducing hydrogen at the airspeed of 500m3/m3·h-1And (2) programming the temperature to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.49 parts of nickel, 0.65 part of nickel oxide, 2.27 parts of cobalt, 0.35 part of cobalt oxide, 10.76 parts of titanium dioxide, 39.45 parts of silicon dioxide and 43.03 parts of alumina.
Example 6
Dissolving 18g of nano titanium dioxide in 14mL of isopropanol to prepare a mixed material I, weighing 15g of alumina and 95g of zirconia powder, adding the weighed materials into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 8.2mL of dilute nitric acid and 64mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1150 ℃ to obtain titanium modified carrier powder; weighing 14.23g of nickel sulfate and 14.19g of cobalt oxalate, and dissolving in 23ml of water to prepare a solution IV; weighing 5.0g of ethylenediamine and 4.0g of TMB, dissolving in 18ml of ethanol to obtain a solution V, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle, aging for 4 hours at 85 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging to adjust the pH of the crystallization kettle to 9.0, then washing and filtering, drying the filter cake at 120 ℃, decomposing the filter cake at 370 ℃, introducing hydrogen at an airspeed of 500m3/m3·h-1And (2) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 2.64 parts of nickel, 0.62 part of nickel oxide, 2.65 parts of cobalt, 0.52 part of cobalt oxide, 13.16 parts of titanium dioxide, 10.96 parts of alumina and 69.45 parts of zirconia.
Example 7
Dissolving 8.0g of metatitanic acid in 6mL of butanol to prepare a mixed material I, weighing 105g of silicon dioxide and 25g of alumina powder, adding the weighed materials into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 10mL of dilute nitric acid and 82mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1020 ℃ to prepare titanium modified carrier powder; 12.03g of nickel nitrate and 23.02g of cobalt nitrate were weighed out and dissolved inPreparing 25ml of water into a solution IV; weighing 2.8g of n-butylamine and 1.5g of TMB, dissolving in 11ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle, aging for 6 hours at the temperature of 50 ℃, adding 0.08mol/L urea aqueous solution to adjust the pH of the crystallization kettle to 8.0 after the aging is finished, washing and filtering again, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 390 ℃, and introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1And (2) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 2.22 parts of nickel, 0.39 part of nickel oxide, 4.12 parts of cobalt, 0.89 part of cobalt oxide, 5.36 parts of titanium dioxide, 70.28 parts of silicon dioxide and 16.74 parts of alumina.
Example 8
Dissolving 20g of nano titanium dioxide in 16.5mL of isopropanol to prepare a mixed material I, weighing 110g of zirconia powder, adding the zirconia powder into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 7.0mL of dilute nitric acid and 76mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1100 ℃ to obtain titanium modified carrier powder; weighing 16.97g of nickel oxalate and 21.74g of cobalt nitrate, and dissolving in 22ml of water to prepare a solution IV; weighing 4.5g of n-butylamine and 1.5g of P123, dissolving in 14ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 5 hours at the temperature of 70 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging is finished to adjust the pH of the crystallization kettle to 7.0, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 350 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1And (3) programming the temperature to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.13 parts of nickel, 0.68 part of nickel oxide, 3.86 parts of cobalt, 0.89 part of cobalt oxide, 14.07 parts of titanium dioxide and 77.37 parts of zirconium oxide.
Example 9
Dissolving 16g of nano titanium dioxide in 12mL of ethanol to prepare a mixed material I, weighing 70g of silicon dioxide and 45g of zirconia powder, adding the silicon dioxide and the zirconia powder into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 9.0mL of dilute nitric acid and 65mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1060 ℃ to prepare titanium modified carrier powder; 18.64g of nickel nitrate and 13.34g of cobalt sulfate were weighed outDissolving in 65ml water to obtain solution IV; weighing 2.2g of n-butylamine and 4.0g of P123, dissolving in 15ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 4 hours at the temperature of 90 ℃, adding 0.06mol/L urea aqueous solution after the aging to adjust the pH of the crystallization kettle to 7.2, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing at the temperature of 450 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V, adding the solution IV, the solution V and the prepared 90g of carrier powder in the crystallization kettle, adjusting the pH of the crystallization kettle to be 7.2, washing and filtering, drying the filter cake at the temperature of 120 ℃, decomposing at the temperature of 450 ℃, and introducing hydrogen3/m3·h-1And (3) programming the temperature to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.45 parts of nickel, 0.59 part of nickel oxide, 2.44 parts of cobalt, 0.59 part of cobalt oxide, 11.40 parts of titanium dioxide, 49.63 parts of silicon dioxide and 31.90 parts of zirconium oxide.
Example 10
Dissolving 9.0g of nano titanium dioxide in 6.0mL of butanol to prepare a mixed material I, weighing 120g of silicon dioxide powder, adding the silicon dioxide powder into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 7.8mL of dilute sulfuric acid and 84mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1050 ℃ to prepare titanium modified carrier powder; weighing 19.6g of nickel nitrate and 24.42g of cobalt nitrate, and dissolving in 20ml of water to prepare a solution IV; weighing 1.5g of ethylenediamine and 2.8g of TMB, dissolving in 13ml of ethanol to obtain a solution V, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle, aging for 6 hours at 55 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution to adjust the pH of the crystallization kettle to 8.5 after the aging is finished, washing and filtering, drying the filter cake at 120 ℃, decomposing the filter cake at 410 ℃, introducing hydrogen at the airspeed of 500m3/m3·h-1And (3) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.57 parts of nickel, 0.75 part of nickel oxide, 4.7 parts of cobalt, 0.47 part of cobalt oxide, 6.31 parts of titanium dioxide and 84.2 parts of silicon dioxide.
Example 11
Dissolving 15g of nano titanium dioxide in 11.5mL of ethanol to prepare a mixed material I, weighing 35g of silicon dioxide, 45g of alumina and 40g of zirconia powder, adding the weighed mixed material I into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 6.5mL of dilute nitric acid and 77mL of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 1080 ℃ to prepare titanium modified carrier powder; weighing 15.72g MirabilitumDissolving nickel acid and 21.94g of cobalt nitrate in 18ml of water to prepare a solution IV; weighing 2.9g of n-butylamine and 6.0g of TMB, dissolving in 23ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 5 hours at the temperature of 80 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging is finished to adjust the pH of the crystallization kettle to 7.5, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing the filter cake at the temperature of 370 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1The temperature is programmed to 400 ℃ under the condition, the temperature is kept for 5 hours, the catalyst is prepared after the temperature is reduced, and the catalyst is analyzed by an X-fluorescence test and comprises 2.84 parts of nickel, 0.49 part of nickel oxide, 3.94 parts of cobalt, 0.75 part of cobalt oxide, 10.22 parts of titanium dioxide, 23.85 parts of silicon dioxide, 30.66 parts of alumina and 27.25 parts of zirconium oxide.
Comparative example 1
An industrially useful palladium/resin catalyst obtained from Zhejiang Utilization chemical Co., Ltd.
Comparative example 2
The preparation process and the amount of each component are the same as those of example 2, except that the calcination temperature of the carrier is changed to 600 ℃, and hydrogen is introduced at a space velocity of 500m3/m3·h-1And (2) programming to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test to obtain the catalyst, wherein the catalyst comprises 2.49 parts of nickel, 0.69 part of nickel oxide, 4.35 parts of cobalt, 0.88 part of cobalt oxide, 14.08 parts of titanium dioxide, 59.88 parts of silicon dioxide and 17.63 parts of alumina.
Comparative example 3
Dissolving 9.0g of nano titanium dioxide in 6.0ml of butanol to prepare a mixed material I, weighing 120g of silicon dioxide powder, adding the silicon dioxide powder into the mixed material I, fully and uniformly mixing to prepare a mixed material II, adding 7.8ml of dilute sulfuric acid and 84ml of water into the mixed material II, stirring, uniformly mixing, reacting, drying, and roasting at 450 ℃ to prepare titanium modified carrier powder; weighing 19.6g of nickel nitrate and 24.42g of cobalt nitrate, and dissolving in 20ml of water to prepare a solution IV; weighing 1.5g of ethylenediamine and 2.8g of TMB, dissolving in 13ml of ethanol to obtain a solution V, placing the solution IV, the solution V and 90g of the prepared carrier powder in a crystallization kettle, aging for 6 hours at 55 ℃, adding 0.05mol/L ammonium bicarbonate aqueous solution after the aging to adjust the pH of the crystallization kettle to 8.5, washing and filtering, and filtering a filter cakeDrying at 120 deg.C, decomposing at 410 deg.C, introducing hydrogen at space velocity of 500m3/m3·h-1And (3) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.55 parts of nickel, 0.73 part of nickel oxide, 4.71 parts of cobalt, 0.46 part of cobalt oxide, 6.33 parts of titanium dioxide and 84.22 parts of silicon dioxide.
Comparative example 4
Weighing 70g of silicon dioxide and 45g of zirconia powder, fully and uniformly mixing to prepare a mixed material II, adding 7.6ml of dilute nitric acid and 75ml of water into the mixed material II, uniformly stirring, uniformly reacting, drying, and roasting at 1050 ℃ to obtain carrier powder; weighing 18.64g of nickel nitrate and 13.34g of cobalt sulfate, and dissolving in 20ml of water to prepare a solution IV; weighing 2.2g of n-butylamine and 4.0g of P123, dissolving in 18ml of ethanol to prepare a solution V, placing the solution IV, the solution V and 90g of carrier powder prepared previously in a crystallization kettle, aging for 4 hours at the temperature of 90 ℃, adding 0.06mol/L urea aqueous solution after the aging to adjust the pH of the crystallization kettle to 7.2, then washing and filtering, drying a filter cake at the temperature of 120 ℃, decomposing at the temperature of 450 ℃, introducing hydrogen at the airspeed of 500m to prepare a solution V3/m3·h-1And (3) carrying out programmed temperature rise to 400 ℃ under the condition, keeping the temperature for 5 hours, cooling to obtain the catalyst, and analyzing by an X-fluorescence test, wherein the catalyst comprises 3.42 parts of nickel, 0.61 part of nickel oxide, 2.57 parts of cobalt, 0.49 part of cobalt oxide, 56.56 parts of silicon dioxide and 36.35 parts of zirconium oxide.
Example 12
This example illustrates the application of the catalysts prepared in examples 1-11 in the one-step synthesis of methyl isobutyl ketone from acetone.
The reduced catalyst is filled in an isothermal fixed bed reactor controlled by an oil bath, acetone is metered by a metering pump and is mixed with hydrogen metered by a gas mass flow meter to enter a preheater, the acetone is vaporized and then enters a reactor to flow through a catalyst bed layer, and the reaction conditions are as follows: the reaction temperature is 140 ℃, the reaction pressure is 0.8MPa, and the space velocity is 1.0h-1And the mass ratio of hydrogen to acetone was 3: 1. The test results are shown in Table 1.
Example 13
The catalysts obtained in comparative examples 1 to 4 were evaluated under the same catalyst reduction and evaluation conditions as in example 12. The evaluation results are shown in Table 1.
Example 14
The reduced catalyst of example 11 was loaded in an oil bath controlled isothermal fixed bed reactor at a loading of 25mL, and the performance of the catalyst under different process conditions was examined, and the results are shown in Table 2.
As can be seen from the data in tables 1 and 2, the catalyst prepared by the invention has good catalytic performance for the reaction of synthesizing methyl isobutyl ketone and methyl isobutyl alcohol from acetone. The yield of the methyl isobutyl ketone is higher than that of the palladium/resin catalyst commonly used in the prior industrial device, and simultaneously the methyl isobutyl alcohol is produced. In addition, the long period of 1000h of the catalyst in the laboratory can be observed, and the catalyst of the invention shows quite good stability.
Table 1 evaluation of catalyst test results
TABLE 2 catalytic Properties under different process conditions
Claims (14)
1. The catalyst for preparing the methyl isobutyl ketone and the methyl isobutyl alcohol by the acetone is measured by taking the whole weight of the catalyst as 100 parts, and comprises the following components:
a. active components: 0.5 to 5 parts of at least one from nickel or nickel oxide;
b. active components: 0.5 to 10 parts of at least one of cobalt and cobalt oxide;
c. carrier: 82-99 parts of a carrier, wherein the carrier is at least one selected from titanium-modified silicon oxide, aluminum oxide and zirconium oxide subjected to high-temperature roasting; the high-temperature roasting temperature is 950-1200 ℃.
2. The catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 1, wherein the content of component a is 2-4 parts, the content of component b is 2-5 parts, and the content of component c is 91-96 parts, based on 100 parts of the total weight of the catalyst.
3. The catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 1 or 2, wherein the titanium dioxide is contained in the carrier in an amount of 5 to 15 parts by weight, based on 100 parts by weight of the entire catalyst.
4. The method for preparing the catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to any one of claims 1 to 3, comprising the following steps:
firstly, adding a modified titanium precursor into a solvent to prepare a mixed material I;
secondly, adding the carrier precursor into the mixture I to prepare a mixture II;
thirdly, mixing the mixed material II with inorganic acid and water, reacting, and drying to obtain a mixed material III;
fourthly, roasting the mixed material III to prepare titanium modified carrier powder;
dissolving soluble salts of nickel and cobalt which are active components in water to prepare a mixed solution IV;
dissolving the template agent and the pore-expanding agent to prepare a solution V;
seventhly, placing the carrier powder in the mixed solution IV, the solution V and the solution IV into a crystallization kettle for aging, adjusting the pH value of the crystallization kettle to 6-10 after aging, and filtering and washing the crystallization kettle;
and (viii) drying the prepared material, roasting, and reducing to obtain the catalyst for preparing the methyl isobutyl ketone and the methyl isobutyl alcohol from the acetone.
5. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 4, comprising the steps of:
in the step I, the modified titanium precursor is selected from at least one of nano titanium dioxide, butyl titanate or metatitanic acid; the concentration of the modified titanium precursor in the mixed material I is 0.001-0.1 mol/mL;
in the step I, the solvent is at least one of ethanol, isopropanol and butanol.
6. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 4, comprising the steps of:
in the second step, the carrier precursor is selected from at least one of silicon dioxide, aluminum oxide and zirconium oxide powder; the molar use ratio of the modified titanium precursor to the carrier precursor is 0.01-5.0: 1;
in the step (c), the inorganic acid is at least one of dilute nitric acid, dilute sulfuric acid and hydrochloric acid.
7. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 6, comprising the steps of:
in the second step, the molar ratio of the modified titanium precursor to the carrier precursor is 0.02-3.0: 1.
8. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 4, comprising the steps of:
in the fifth step, the concentration of the solution of the soluble salt of nickel is 1.0-5.5 mol/L, and the concentration of the solution of the soluble salt of cobalt is 0.5-8.5 mol/L; the soluble salt of nickel is selected from at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel oxalate; the soluble salt of cobalt is at least one selected from cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate and cobalt oxalate.
9. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 8, comprising the steps of:
the soluble salt of nickel is at least one of nickel nitrate, nickel sulfate and nickel oxalate.
10. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 8, comprising the steps of:
the soluble salt of cobalt is at least one selected from cobalt nitrate, cobalt sulfate and cobalt oxalate.
11. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 4, comprising the steps of:
dissolving the template agent and the pore-expanding agent in ethanol to prepare a solution V; the concentration of the template agent and the pore-expanding agent in the solution V is 0.1-1.5 g/ml;
the template agent and the pore-expanding agent are at least one of ethylenediamine, n-butylamine, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 3,3',5,5' -tetramethyl benzidine.
12. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 4, comprising the steps of:
the roasting temperature in the fourth step is 950-1200 ℃;
seventhly, aging at 40-90 ℃ for 3-6 h;
in the step eight, the drying temperature of the material is 100-150 ℃, and the roasting temperature is 300-600 ℃.
13. The method for preparing a catalyst for preparing methyl isobutyl ketone and methyl isobutyl alcohol from acetone according to claim 12, comprising the steps of:
the roasting temperature in the step (IV) is 970-1150 ℃.
14. The use of the catalyst for the preparation of methylisobutyl ketone and methylisobutyl alcohol from acetone according to any one of claims 1 to 3 or the preparation process according to any one of claims 4 to 13, characterized in that it comprises: acetone and hydrogen are used as raw materials, the reaction temperature is 120-230 ℃, and the reaction pressure is0 to 2.5MPa and the volume airspeed of acetone is 0.1 to 3.0h-1And passing the catalyst through a bed layer under the condition that the molar ratio of hydrogen to acetone is (2-10): 1 to generate a reactant flow containing methyl isobutyl ketone and methyl isobutyl alcohol.
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