CN109701570B - Catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone and preparation method and application thereof - Google Patents
Catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by using acetone, a preparation method and application thereof, belonging to the field of catalysts. The catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone is measured by taking the whole weight of the catalyst as 100 parts, and comprises the following components: a. 0.5 to 10 parts of at least one selected from nickel or nickel oxide; b. 0.5 to 10 parts of at least one selected from cobalt or cobalt oxide; c. 80-99 parts of bismuth-modified basic calcium phosphate. The preparation process of the catalyst is relatively simple and convenient, the operation and the control are easy, and active components are not easy to lose; the catalyst of the invention can be used for producing methyl isobutyl ketone and diisobutyl ketone, the industrial production device has stronger market adaptability, the cost of the bimetallic catalyst of the invention is obviously lower than that of the existing palladium catalyst, and the bimetallic catalyst has better economic benefit.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to a catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone, and a preparation method and application thereof.
Background
Methyl isobutyl ketone, also known as 4-methyl-2-pentanone (MIBK for short), is an important solvent and chemical intermediate, has attracted attention 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, ether and the like, can be used as a raw material of coating, ethyl cellulose, nitrocellulose, audio and video tapes, paraffin, various 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 antioxidant, is a current pretty fine petrochemical intermediate, has irreplaceability in many application fields, and is still imported in China every year.
In the market, methyl isobutyl ketone is produced by 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 has become a main synthetic process route of the methyl isobutyl ketone.
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 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.
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 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 of poor activity and high cost of the catalyst in the prior art, the invention provides a catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by using acetone. In particular to a catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone, a preparation method and application thereof.
One of the purposes of the invention is to provide a catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone. The catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by 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 10 parts of at least one active component selected from nickel or nickel oxide;
b. active components: 0.5 to 10 parts of at least one active component selected from cobalt or cobalt oxides;
c. carrier: 80-99 parts of bismuth-modified basic calcium phosphate.
Wherein,
the content of the component a is preferably 2 to 5 parts, the content of the component b is preferably 2 to 5 parts, and the content of the component c is preferably 90 to 96 parts, based on 100 parts by weight of the whole catalyst.
The bismuth-modified basic calcium phosphate is characterized in that the bismuth oxide content is 0.5-5 parts by weight based on 100 parts by weight of the catalyst.
The invention also aims to provide a preparation method of the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by using acetone, which comprises the following steps:
mixing dilute acid solution of bismuth salt and calcium nitrate water solution to prepare solution I, and dissolving soluble hydrogen phosphate in water to prepare solution II;
slowly dropping the solution II into the solution I, simultaneously dropping a urea aqueous solution (the concentration can be 0.05mol/L) to adjust the pH value to 8-11, controlling the Ca/P molar ratio to be 1-4, and stirring at 25-80 ℃ to prepare slurry III;
slowly dripping soluble salts of nickel and soluble salts of cobalt into the slurry III, dripping aqueous solution of urea (the concentration can be 0.05mol/L) to adjust the pH value, and controlling the pH value of the precipitation end point to be 6.0-10.0 to prepare slurry IV;
fourthly, washing and filtering the aged slurry IV to prepare a filter cake;
and fifthly, drying the filter cake obtained in the fourth step, and reducing the filter cake after roasting to obtain the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone.
Wherein,
the dilute acid solution of bismuth salt in the step (i) may be at least one selected from a hydrochloric acid solution of bismuth chloride and a nitric acid solution of bismuth nitrate.
The hydrogen phosphate in the step (I) can be at least one selected from diamine hydrogen phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate; the concentration of the hydrogen phosphate in the solution II is 0.05-0.15 mol/L.
The soluble salt of nickel in the third step 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 acetate; 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 acetate.
And the pH value of the precipitation reaction end point in the step (III) is 7.0-9.0.
The aging temperature in the step (IV) is 25-100 ℃, preferably 40-100 ℃, and the aging time is 5-20 h.
In the fifth step, the drying temperature is 100-150 ℃, and the roasting temperature is 300-500 ℃.
The invention also provides the methyl synthesized by the acetoneA method for using a catalyst of isobutyl ketone and diisobutyl ketone, comprising: acetone and hydrogen are used as raw materials, the reaction temperature is 100-220 ℃, the reaction pressure is 0-3.0 MPa, and the volume space velocity of the acetone is 0.1-3.0 h-1And the molar ratio of hydrogen to acetone is (1-6): 1, and the reaction product flows through the bed layer filled with the catalyst to generate a reaction product flow containing methyl isobutyl ketone and diisobutyl ketone.
Wherein the reaction temperature is preferably 120-180 ℃, the reaction pressure is preferably 0.5-1.5 MPa, and the volume space velocity of acetone is preferably 0.5-2.0 h-1The molar ratio of hydrogen to acetone is preferably (2-5): 1.
The inventors have intensively studied and found that a critical factor for the stability of the Pd/resin catalyst is a condensate generated by condensation of acetone, and MIBK and DIBK generated further undergo condensation reaction to generate a more complex condensation byproduct. These by-products coat the catalyst surface and plug the catalyst channels, causing deactivation of the catalytically active sites.
The catalyst of the present invention is reduced before use, the reducing gas may be hydrogen gas, a mixture of hydrogen gas and nitrogen gas, the hydrogen content in the mixture of hydrogen and nitrogen gas may be any content, for example, 2 vol% to 80 vol%, or a higher content gas may be used. From the viewpoint of temperature control of catalyst reduction, a mixed gas having a low hydrogen content is preferred. The larger the space velocity of the gas, the better. The air speed is large, the heat generated by the reaction can be quickly removed in time, the temperature of the catalyst bed is kept stable, and the catalyst is not damaged by temperature runaway. For example, the space velocity of the mixed gas is 300-5000 m3/m3·h-1. The temperature of reduction 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 150 ℃ for 2-8 hours, then the temperature of the catalyst bed layer is gradually increased at a rate of 5-20 ℃/h, preferably 5-10 ℃/h until reaching 250-500 ℃, and the catalyst bed layer is kept at the temperature for 2-48 hours. And then slowly cooling to room temperature, for example, the cooling rate is 5-20 ℃/h. Cooling to room temperature, switching to nitrogen, and gradually adding hydrogen into nitrogenAnd gradually increasing the hydrogen content to increase the hydrogen content 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, 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 of the catalyst is relatively simple and convenient, the operation and the control are easy, and active components are not easy to lose; the palladium catalyst is polymerized to prepare a granular resin, then the palladium is loaded on the resin by exchange, and organic matters on the resin are easy to lose, so that reaction products are polluted and the product color 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 diisobutyl ketone, the industrial production device has stronger market adaptability, the enterprise profitability is enhanced, and the palladium catalyst only produces one product, namely methyl isobutyl ketone, and the acetone conversion rate is lower.
In addition, the active components of nickel and cobalt are loaded on the bismuth modified basic calcium phosphate carrier by an ammonia evaporation method, and the basic calcium phosphate carrier has stronger ion exchange effect, so that the strong interaction between the metal components and the carrier is facilitated, the uniform distribution of the nickel and cobalt metal on the specific surface of the carrier is promoted, and the activity and the stability of the catalyst are greatly improved.
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
Mixing 10ml hydrochloric acid solution containing 7.44g bismuth chloride with 100ml water solution containing 150g calcium nitrate to obtain solution I, dissolving 40.25g diammonium hydrogen phosphate in water to obtain solution II with concentration of 0.12mol/L, and mixing the solutionsII, slowly dropwise adding the solution I into the solution I, adjusting the pH value to 8.5 by dropwise adding 0.05mol/L urea aqueous solution at the same time, and stirring for 5 hours at 40 ℃ to obtain slurry III, wherein the Ca/P molar ratio is 3; weighing 19.6g of nickel nitrate and 24.42g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 7.0, aging the prepared slurry IV at 50 ℃ for 10 hours, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 450 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 3.71 parts nickel, 0.41 part nickel oxide, 4.47 parts cobalt, 0.52 part cobalt oxide, 4.66 parts bismuth oxide and 86.23 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 2
Uniformly mixing 10ml of hydrochloric acid solution containing 3.38g of bismuth chloride with 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 32.2g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.10mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 9.0 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 60 ℃ for 5 hours to prepare slurry III; weighing 21.7g of nickel sulfate and 20.03g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 7.5, aging the prepared slurry IV at 90 ℃ for 5 hours, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 400 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 4.51 parts nickel, 0.45 part nickel oxide, 3.81 parts cobalt, 0.41 part cobalt oxide, 2.70 parts bismuth oxide and 88.12 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 3
Mixing 10ml hydrochloric acid solution containing 5.41g bismuth chloride and 100ml water solution containing 140g calcium nitrate to obtain solution I, dissolving 97.35g dipotassium hydrogen phosphate in water to obtain solution II with concentration of 0.1mol/L, slowly dripping solution II into solution I with Ca/P molar ratio of 2.0, and simultaneously dripping 0.05mol/L of solution IIAdjusting the pH value of the urea aqueous solution to 10.0, and stirring for 4 hours at 70 ℃ to prepare slurry III; weighing 19.6g of nickel nitrate and 24.42g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 8.5, aging the prepared slurry IV for 3 hours at 100 ℃, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 320 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 4.60 parts nickel, 0.36 part nickel oxide, 2.62 parts cobalt, 0.59 part cobalt oxide, 2.49 parts bismuth oxide and 89.34 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 4
Uniformly mixing 15ml of hydrochloric acid solution containing 11.5g of bismuth chloride with 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 75.14g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.08mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 8.5 by adding 0.05mol/L of urea aqueous solution dropwise at the same time, and stirring at 80 ℃ for 4 hours to prepare slurry III; weighing 19.35g of nickel nitrate and 17.7g of cobalt sulfate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 8.0, aging the prepared slurry IV at 75 ℃ for 15h, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 4h, decomposing at 360 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 3.12 parts nickel, 0.50 part nickel oxide, 3.07 parts cobalt, 0.66 part cobalt oxide, 3.96 parts bismuth oxide and 88.69 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 5
Uniformly mixing 10ml of hydrochloric acid solution containing 8.80g of bismuth chloride with 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 45.08g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.15mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 9.0 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 40 ℃ for 8 hours to prepare slurry III;weighing 11.99g of nickel nitrate and 21.51g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 7.2, aging the prepared slurry IV at 40 ℃ for 20h, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 475 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 2.03 parts nickel, 0.60 parts nickel oxide, 4.04 parts cobalt, 0.54 parts cobalt oxide, 5.0 parts bismuth oxide and 87.79 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 6
Uniformly mixing 10ml of hydrochloric acid solution containing 0.68g of bismuth chloride with 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 35.22g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.12mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 11 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 55 ℃ for 8 hours to prepare slurry III; weighing 13.12g of nickel acetate and 11.95g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 8.4, aging the prepared slurry IV at 70 ℃ for 15h, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 390 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 3.98 parts nickel, 0.66 parts nickel oxide, 2.05 parts cobalt, 0.48 parts cobalt oxide, 0.52 parts bismuth oxide and 92.31 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 7
Uniformly mixing 10ml of nitric acid solution containing 10.83g of bismuth nitrate and 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 43.35g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.15mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 8.0 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring for 6 hours at 80 ℃ to prepare slurry III; 12.03g of nickel nitrate and 23.02g of cobalt nitrate were weighed into the slurry III, and 0 was added dropwise.Adjusting the pH value of the solution by 05mol/L urea aqueous solution, controlling the pH value of the precipitation end point to be 8.0, aging the prepared slurry IV at 90 ℃ for 15h, and then filtering and washing to prepare a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 340 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 2.65 parts nickel, 0.55 part nickel oxide, 3.57 parts cobalt, 0.60 part cobalt oxide, 4.19 parts bismuth oxide and 88.44 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 8
Uniformly mixing 10ml of nitric acid solution containing 9.37g of bismuth nitrate and 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 55.05g of disodium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.06mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 8.0 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 25 ℃ for 10 hours to prepare slurry III; weighing 10.07g of nickel nitrate and 20.04g of cobalt acetate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 7.6, aging the prepared slurry IV at 95 ℃ for 12 hours, and then filtering and washing to obtain a wet filter cake; drying the filter cake at 120 deg.C for 2h, decomposing at 400 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 2.0 parts nickel, 0.22 parts nickel oxide, 4.62 parts cobalt, 0.36 parts cobalt oxide, 3.10 parts bismuth oxide and 89.70 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 9
Uniformly mixing 10ml of nitric acid solution containing 14.58g of bismuth nitrate and 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 70.44g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.10mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 9.5 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 60 ℃ for 8 hours to prepare slurry III; 16.04g of nickel nitrate and 9.88g of cobalt nitrate are weighed and added into the slurry III, 0.05mol/L of urea aqueous solution is dripped to adjust the pH value of the solution, and the pH value of the end point of precipitation is controlled to be7.4, aging the prepared slurry IV at 85 ℃ for 20h, and then filtering and washing to prepare a wet filter cake; drying the filter cake at 120 deg.C for 3h, decomposing at 425 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 2.83 parts nickel, 0.72 part nickel oxide, 2.01 parts cobalt, 0.32 part cobalt oxide, 3.55 parts bismuth oxide and 90.57 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 10
Uniformly mixing 10ml of nitric acid solution containing 5.21g of bismuth nitrate and 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 45.08g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.08mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 8.2 by dropwise adding 0.05mol/L of urea aqueous solution at the same time, and stirring at 50 ℃ for 7 hours to prepare slurry III; weighing 11.74g of nickel nitrate and 11.7g of cobalt nitrate, adding the nickel nitrate and the cobalt nitrate into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 8.6, aging the prepared slurry IV for 16h at 60 ℃, and then filtering and washing to prepare a wet filter cake; drying the filter cake at 120 deg.C for 4h, decomposing at 430 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 2.15 parts nickel, 0.41 part nickel oxide, 2.18 parts cobalt, 0.47 part cobalt oxide, 2.03 parts bismuth oxide and 92.76 parts calcium phosphate basic as analyzed by X-fluorescence test.
Example 11
Uniformly mixing 10ml of nitric acid solution containing 2.50g of bismuth nitrate and 100ml of aqueous solution containing 140g of calcium nitrate to prepare solution I, weighing 37.57g of diammonium hydrogen phosphate to be dissolved in water to prepare solution II with the concentration of 0.1mol/L, slowly dropwise adding the solution II into the solution I, adjusting the pH value to 9.0 by dropwise adding 0.05mol/L of urea aqueous solution at the same time with the Ca/P molar ratio of 3, and stirring for 9 hours at 40 ℃ to prepare slurry III; weighing 20.36g of nickel nitrate and 18.36g of cobalt nitrate, adding into the slurry III, dropwise adding 0.05mol/L urea aqueous solution to adjust the pH value of the solution, controlling the pH value of the precipitation end point to be 7.5, aging the prepared slurry IV at 76 ℃ for 18h, filtering and washing to obtain the nickel cobalt nitrate cobalt is added into the slurry III, wherein the copper nitrate nickel nitrate cobalt nitrateA wet cake; drying the filter cake at 130 deg.C for 2h, decomposing at 410 deg.C, introducing hydrogen at space velocity of 1500m3/m3·h-1And (3) under the condition, raising the temperature to 400 ℃ by a program, keeping the temperature for 10 hours, and cooling to obtain the catalyst. The catalyst was 3.79 parts nickel, 0.49 parts nickel oxide, 3.43 parts cobalt, 0.55 parts cobalt oxide, 1.14 parts bismuth oxide and 90.6 parts calcium phosphate basic as analyzed by X-fluorescence test.
Comparative example 1
An industrially useful palladium/resin catalyst obtained from Zhejiang Utilization chemical Co., Ltd.
Example 12
This example illustrates the application of the catalysts prepared in examples 1-11 in the synthesis of methyl isobutyl ketone and diisobutyl 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 150 ℃, the reaction pressure is 1.1MPa, 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.
Table 1 evaluation of catalyst test results
Example 13
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.
TABLE 2 evaluation results under different process conditions
As can be seen from the evaluation 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 diisobutyl ketone from acetone. Within the process condition range of the invention, the methyl isobutyl ketone and the diisobutyl ketone have higher selectivity. 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.
Claims (12)
1. The catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by using acetone is characterized by comprising the following components in parts by weight based on 100 parts by weight of the whole catalyst:
a. active components: 0.5 to 10 parts of at least one selected from nickel or nickel oxide;
b. active components: 0.5 to 10 parts of at least one selected from cobalt or cobalt oxide;
c. carrier: 80-99 parts of bismuth-modified basic calcium phosphate;
the content of bismuth oxide in the bismuth-modified basic calcium phosphate is 0.5-5 parts by weight based on 100 parts by weight of the whole catalyst.
2. The catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 1, wherein the content of the component a is 2 to 5 parts, the content of the component b is 2 to 5 parts, and the content of the component c is 90 to 96 parts, based on 100 parts by weight of the entire catalyst.
3. The method for preparing the catalyst for the acetone synthesis of methyl isobutyl ketone and diisobutyl ketone according to any one of claims 1 to 2, comprising the steps of:
mixing dilute acid solution of bismuth salt and calcium nitrate water solution to prepare solution I, and dissolving soluble hydrogen phosphate in water to prepare solution II;
slowly dropwise adding the solution II into the solution I, adjusting the pH value to 8-11, controlling the Ca/P molar ratio to be 1-4, and stirring at 25-80 ℃ to obtain slurry III;
thirdly, slowly dripping soluble salt of nickel and soluble salt of cobalt into the slurry III, adjusting the pH value, and controlling the pH value of the precipitation end point to be 6.0-10.0 to prepare slurry IV;
fourthly, washing and filtering the aged slurry IV to prepare a filter cake;
and fifthly, drying the filter cake obtained in the fourth step, and reducing the filter cake after roasting to obtain the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone.
4. The method for preparing a catalyst for the synthesis of methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 3, wherein the dilute acid solution of bismuth salt in step (i) is at least one selected from the group consisting of a hydrochloric acid solution of bismuth chloride and a nitric acid solution of bismuth nitrate.
5. The method for preparing a catalyst for the synthesis of methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 3, wherein the hydrogen phosphate in step (r) is at least one selected from the group consisting of diamine hydrogen phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate; the concentration of the hydrogen phosphate in the solution II is 0.05-0.15 mol/L.
6. The method for preparing catalyst of methyl isobutyl ketone and diisobutyl ketone synthesized from acetone according to claim 3, wherein the soluble salt of nickel in the step (iii) is at least one selected from 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.
7. The method for preparing the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 3, wherein the pH of the precipitation reaction end point in the step (iii) is 7.0-9.0; the aging temperature in the step IV is 25-100 ℃, and the aging time is 5-20 h.
8. The method for preparing catalyst for acetone synthesis of methyl isobutyl ketone and diisobutyl ketone according to claim 3, wherein the drying temperature is 100-150 ℃ and the calcination temperature is 300-500 ℃ in the fifth step.
9. The method for preparing a catalyst used in the synthesis of methylisobutylketone and diisobutyl ketone from acetone according to claim 6, wherein the soluble salt of nickel in the step (iii) is at least one selected from nickel nitrate, nickel sulfate and nickel acetate.
10. The method for preparing catalyst of methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 6, wherein the soluble salt of cobalt is at least one selected from cobalt nitrate, cobalt sulfate and cobalt acetate.
11. The preparation method of the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone from acetone according to claim 7, wherein the aging temperature in the step (iv) is 40 to 100 ℃.
12. The application method of the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone according to any one of claims 1 to 2 or the catalyst prepared by the preparation method of the catalyst for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone according to any one of claims 3 to 11, which comprises the following steps: acetone and hydrogen are used as raw materials, the reaction temperature is 100-220 ℃, the reaction pressure is 0-3.0 MPa, and the volume space velocity of the acetone is 0.1-3.0 h-1And the molar ratio of hydrogen to acetone is (1-6): 1, and the reaction product flows through the bed layer filled with the catalyst to generate a reaction product flow containing methyl isobutyl ketone and diisobutyl ketone.
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| JP2002275116A (en) * | 2001-03-14 | 2002-09-25 | Asahi Kasei Corp | Method for producing aldehyde or ketone using palladium-immobilized hydroxyapatite |
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