CN114315504A - Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide - Google Patents
Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide Download PDFInfo
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Abstract
The invention relates to a method for converting 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into methyl cyclopentadiene in one step by using AxByOz type composite metal oxide to carry out hydrodeoxygenation reaction. The method can synthesize various AxByOz type composite metal oxides by using a simple and easy-to-operate deposition precipitation method, a hydrothermal method or a citric acid complexation method, has special selectivity for the hydrodeoxygenation reaction of 2, 5-hexanedione and 3-methyl-2-cyclopentene-1-ketone, and can synthesize the target product methyl cyclopentadiene in one step by an aldol condensation series hydrodeoxygenation reaction or a direct hydrodeoxygenation reaction in a fixed bed reactor at a large mass space velocity. The invention has simple process route, is environment-friendly, has simple catalyst preparation, and provides a brand new catalytic method for synthesizing the methyl cyclopentadiene.
Description
Technical Field
The invention relates to a method for synthesizing methyl cyclopentadiene from 2, 5-hexanedione and 3-methyl-2-cyclopentene-1-ketone.
Background
The methyl cyclopentadiene can be used for synthesizing high-energy rocket fuel, is a high-end fine chemical raw material with wide application, and can be used for synthesizing high-added-value products such as gasoline antiknock methyl cyclopentadiene manganese tricarbonyl (MMT), epoxy resin curing agent, dye additive, special adhesive, special spice and the like. At present, the methodThere are two main methods for the industrial production of MCPD: a process for separating C from the tar oil by distillation6The components are polymerized, distilled under reduced pressure, depolymerized and rectified for many times to prepare MCPD; another is the methylation of cyclopentadiene to prepare MCPD. However, whether the MCPD is produced by a separation method or a methylation synthesis method, the capacity is very limited, and the application requirements of various fields can not be met. Therefore, the method has important significance in finding a green and renewable synthesis process route for producing the methyl cyclopentadiene by using bulk chemicals as raw materials.
In recent years, with the growing concern of people on environmental and energy problems, the synthesis of high value-added chemicals by using carbon dioxide neutral and renewable biomass resources as raw materials has been receiving wide attention from countries in the world. For example, 2, 5-hexanedione (appl. Catal. A, 2015, 504, 664-671) can be obtained by subjecting cellulose to a catalytic hydrogenolysis reaction. 2, 5-hexanedione is used as a raw material, under the action of an alkaline catalyst Mg-Al-O, a water-toluene mixed solvent is used for carrying out aldol condensation reaction to obtain 3-methyl-2-cyclopentene-1-one (MCP), and the MCP is subjected to Pt/NbOPO catalyst4Under the action of (1), the product can be subjected to hydrodeoxygenation to obtain methylcyclopentane, which has lower carbon number and loses the capability of further polymerization (Green chem., 2015, 17, 2393-. MCP is used as a raw material, methyl cyclopentadiene can be obtained through one-step hydrodeoxygenation, the highest selectivity of the methyl cyclopentadiene is only 80%, the yield of a target product is low, and the problem that only a single substance, namely the MCP with relatively high price, can be used as the raw material exists.
Disclosure of Invention
Aiming at the technical problems, the invention provides a novel AxByOz type composite metal oxide catalyst by adopting a plurality of synthesis methods, efficiently converts 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into a target product methyl cyclopentadiene in one step, and provides a novel, simple and efficient synthesis method for synthesizing the methyl cyclopentadiene with high added value.
The invention is realized by the following technical scheme:
the technical scheme of the invention comprises a method 1 or a method 2, and the paths of the method 1 and the method 2 are as follows:
method 1
Method 2
The AxByOz type composite metal oxide catalyst comprises: CuMoO4、Cu3Mo2O9、ZnMoO4、Zn3Mo2O9、NiMoO4、CoMoO4、MnMoO4、FeMoO4、Fe2(MoO4)3、Cr2(MoO4)3、CuWO4、NiWO4、CoWO4、FeWO4、ZnWO4、Zn3(VO4)2One or more of (a).
The chemical structural formulas of the raw materials of the 2, 5-hexanedione, the 3-methyl-2-cyclopentene-1-ketone and the target product of the methylcyclopentadiene are shown in a table 1.
Based on the scheme, preferably, 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone is used as a raw material, and under the action of an AxByOz type composite metal oxide catalyst synthesized by a deposition precipitation method, a hydrothermal method or a citric acid complexation method, the aldol condensation series hydrodeoxygenation reaction or the direct hydrodeoxygenation reaction is carried out in a fixed bed continuous reactor at the reaction temperature of 300-600 ℃, the hydrogen pressure of 0.0001-1MPa (preferably 0.0001-0.9MPa, more preferably 0.0001-0.8MPa), the molar ratio of hydrogen to a substrate is 20-300: 1, and the mass space velocity of the substrate is 0.01-10h-1(preferably 0.05-9 h)-1More preferably 0.1 to 8 hours-1) And then, obtaining a methyl cyclopentadiene target product in one step.
Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst is prepared by a hydrothermal method, a precipitation method or a citric acid complexation method, and is subjected to a reduction treatment in hydrogen before use, wherein the reduction conditions are a hydrogen pressure of 0.001-2.0MPa (preferably 0.005-1.5MPa, more preferably 0.01-1MPa), a hydrogen flow rate of 2-300mL/min (preferably 5-250mL/min, more preferably 10-200mL/min), a reduction temperature of 200 ℃, (preferably 250 ℃, (more preferably 300 ℃), (more preferably 500 ℃), and a reduction time of 0.5-12h (preferably 0.7-10h, more preferably 1-8 h).
Based on the above scheme, preferably, the hydrothermal method specifically comprises the following preparation processes: mixing and dissolving a certain amount of metal salt A and metal salt B in deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 5-48h at 80-220 ℃, filtering and washing, drying the obtained powder for 3h at 80 ℃, and roasting at 800 ℃ for 1-6h at 300-.
Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst can also be synthesized by using a deposition precipitation method, which comprises the following specific steps: dissolving a certain amount of metal salt B in deionized water, adjusting the pH value of the solution to 8-12 by using an ammonia water solution with the concentration of 0.5-14 mol/L (preferably 1-8 mol/L, more preferably 1.5-6 mol/L) as a precipitator, dropwise adding the aqueous solution of the metal salt A, stirring for 0.5-4h (preferably 1-3h), filtering out the obtained precipitate, washing with deionized water and ethanol, drying in an oven at 100-200 ℃ for 4-48h, and roasting at 300-800 ℃ (preferably 350-750 ℃, more preferably 400-700 ℃) for 0.5-10h (preferably 1-8h, more preferably 1-6h) to obtain the AxByOz type composite metal oxide catalyst.
Based on the above scheme, preferably, the AxByOz type composite metal oxide catalyst can also be prepared by using a citric acid complexation method, which comprises the following specific processes: weighing the metalate of B, the metalate of A and citric acid according to a molar ratio M to citric acid of 1: 1-1: 3 (preferably 1: 1.05-1: 2, more preferably 1: 1.1-1: 1.5), wherein M is the molar sum of the metal B in the anion and the cation metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; after drying at 120 ℃ for 12h, roasting at 300-800 ℃ (preferably 350-750 ℃, more preferably 400-700 ℃) for 0.5-10h (preferably 1-8h, more preferably 1-6h) to obtain the AxByOz type composite metal oxide catalyst.
The method can synthesize a large amount of AxByOz type composite metal oxide catalysts, and has the advantages of simple preparation method and mild reaction conditions. Meanwhile, the catalyst can be used for converting 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into methyl cyclopentadiene in one step through aldol condensation series hydrodeoxygenation reaction or direct hydrodeoxygenation reaction on a fixed bed reactor under the solvent-free condition through reduction, the operation steps are few, the mass airspeed of a substrate is large, the conversion efficiency is high, the catalyst is a green and simple new synthesis route, and the catalyst can be used for actual industrial production and has good catalytic performance.
The invention has the beneficial effects that:
the invention can not only use MCP as a substrate, but also use 2, 5-hexanedione which is a source raw material for synthesizing MCP as the substrate to prepare the methyl cyclopentadiene by one step, and the obtained target product has higher selectivity.
The invention can synthesize various AxByOz type composite metal oxides by using a simple and easy-to-operate deposition precipitation method, a hydrothermal method or a citric acid complexation method, apply the hydrodeoxygenation reaction for the first time, and convert 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into a target product methyl cyclopentadiene in one step by aldol condensation series hydrodeoxygenation reaction or direct hydrodeoxygenation reaction in a fixed bed reactor at a larger mass airspeed under the condition of no solvent.
The invention has simple process route, is environment-friendly, has simple catalyst preparation, and provides a brand new catalytic method for synthesizing the methyl cyclopentadiene.
The invention adopts a fixed bed continuous flow reactor, can convert 2, 5-hexanedione or 3-methyl-2-cyclopentene-1-ketone into methyl cyclopentadiene in one step under the action of various AxByOz type composite metal oxide catalysts, and has the advantages of simple process route, high conversion efficiency, high operability, low energy consumption, simple catalyst preparation and little environmental pollution.
Drawings
FIG. 1 is a gas chromatogram of a product of synthesizing methylcyclopentadiene from 2, 5-hexanedione in example 6.
FIG. 2 is a gas chromatogram of a product of synthesizing methylcyclopentadiene from 3-methyl-2-cyclopenten-1-one in example 41.
FIG. 3 is a mass spectrum comparison chart of the target product methyl cyclopentadiene.
Figures 4-6 are XRD patterns of partially synthesized catalysts.
FIG. 7 is a reaction scheme provided by the present invention.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
(1) AxByOz type composite metal oxide catalyst CoMoO4The preparation of (1): 2.47g of ammonium molybdate was weighed and dissolved in 200mL of deionized water. Adjusting the pH value of the solution to 9.5 by using an ammonia water solution with the concentration of 2mol/L as a precipitator, dropwise adding a cobalt nitrate (4.07g dissolved in 100mL of deionized water) aqueous solution, stirring for 2h, filtering out the obtained precipitate, washing with deionized water and ethanol, drying in an oven at 100 ℃ for 5h, and roasting at 400 ℃ for 2h to obtain the CoMoO4A composite metal oxide catalyst.
(2) Mixing the above CoMoO40.3g of catalyst is uniformly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.2MPa, the hydrogen flow rate of 90mL/min and the reduction temperature of 400 ℃, then the reaction temperature is controlled to be 420 ℃, the reaction pressure is 0.05MPa, and the hourly space velocity of 2, 5-hexanedione is 2h-1The molar ratio of hydrogen to 2, 5-hexanedione was 70: 1, the conversion of 2, 5-hexanedione was 90% and the selectivity to methylcyclopentadiene was 80%.
Example 2
(1) NiMoO as AxByOz type composite metal oxide catalyst4The preparation method can use a citric acid complexation method, and comprises the following specific processes: ammonium molybdate 1.24g is weighed according to the molar ratio n (M)/n (citric acid) ═ 1/1.22.04g of nickel nitrate and 3.53g of citric acid, wherein M is the molar sum of metal B in anions and cationic metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 deg.C for 12 hr, and calcining at 600 deg.C for 5 hr to obtain NiMoO4A catalyst.
(2) Mixing the above NiMoO40.3g of catalyst is evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.08MPa, the hydrogen flow rate of 90mL/min and the reduction temperature of 400 ℃, then the reaction temperature is controlled to be 380 ℃, the reaction pressure is 0.05MPa, and the hourly space velocity of 2, 5-hexanedione is 2.3h-1The molar ratio of hydrogen to 2, 5-hexanedione was 70: 1, the conversion of 2, 5-hexanedione was 90% and the selectivity to methylcyclopentadiene was 84%.
Example 3
(1) ZnMoO of AxByOz type composite metal oxide catalyst4The preparation of (1): 2.47g of ammonium molybdate was weighed and dissolved in 200mL of deionized water. Adjusting the pH value of the solution to 8.9 by using an ammonia water solution with the concentration of 2mol/L as a precipitator, dropwise adding an aqueous solution of zinc nitrate (4.16g dissolved in 100mL of deionized water), stirring for 2h, filtering out the obtained precipitate, washing with deionized water and ethanol, drying in an oven at 100 ℃ for 5h, and roasting at 400 ℃ for 2h to obtain ZnMoO4A composite metal oxide catalyst.
(2) The ZnMoO is added40.2g of catalyst is uniformly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 1h under the conditions that the hydrogen pressure is 0.05MPa, the hydrogen flow is 150mL/min and the reduction temperature is 400 ℃, then the reaction temperature is controlled to be 400 ℃, the reaction pressure is 0.05MPa and the hourly space velocity of 2, 5-hexanedione is 3h-1The molar ratio of hydrogen to 2, 5-hexanedione was 70: 1, the conversion of 2, 5-hexanedione was 100% and the selectivity to methylcyclopentadiene was 89%.
Example 4
(1) AxByOz type composite metal oxide catalyst Cu3Mo2O9Can be prepared by a hydrothermal method, and comprises the following specific steps: mixing 0.50g of ketone acetate with 0.44gDissolving ammonium molybdate tetrahydrate in 40mL of deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 12h, filtering and washing, drying the obtained powder at 80 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain Cu3Mo2O9A catalyst.
(2) Mixing the above Cu3Mo2O90.2g of catalyst is evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 1h under the hydrogen pressure of 0.05MPa, the hydrogen flow rate of 150mL/min and the reduction temperature of 400 ℃, then the reaction temperature of 400 ℃, the reaction pressure of 0.05MPa and the hourly space velocity of 2, 5-hexanedione of 2.3h are controlled-1The molar ratio of hydrogen to 2, 5-hexanedione was 67: 1, the conversion of 2, 5-hexanedione was 100% and the selectivity to methylcyclopentadiene was 90%.
Example 5
(1) AxByOz type composite metal oxide catalyst Fe2(MoO4)3The preparation method can use a citric acid complexation method, and comprises the following specific processes: ammonium molybdate 1.24g, ferric nitrate nonahydrate 1.89g and citric acid 2.94g are weighed according to the molar ratio n (M)/n (citric acid) ═ 1/1.2, wherein M is the molar sum of metal B in anion and cation metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 ℃ for 12h, and roasting at 600 ℃ for 5h to obtain Fe2(MoO4)3A catalyst.
(2) Mixing the above Fe2(MoO4)30.3g of catalyst is uniformly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.08MPa, the hydrogen flow rate of 120mL/min and the reduction temperature of 400 ℃, then the reaction temperature is controlled to be 420 ℃, the reaction pressure is 0.05MPa, and the hourly space velocity of 2, 5-hexanedione is 2h-1The molar ratio of hydrogen to 2, 5-hexanedione was 90: 1, the conversion of 2, 5-hexanedione was 93% and the selectivity to methylcyclopentadiene was 86%.
Example 6
(1) AxByOz type composite metal oxygenNiWO catalyst4Can be prepared by a hydrothermal method, and comprises the following specific steps: dissolving 0.71g of nickel acetate and 1.32g of sodium tungstate dihydrate in 80mL of deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 12h, filtering and washing, drying the obtained powder at 80 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain NiWO4A catalyst.
(2) Mixing the above NiWO40.25g of catalyst is uniformly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2.5h under the conditions that the hydrogen pressure is 0.50MPa, the hydrogen flow is 160mL/min and the reduction temperature is 450 ℃, then the reaction temperature is controlled to be 400 ℃, the reaction pressure is 0.05MPa and the hourly space velocity of 2, 5-hexanedione is 1.8h-1The molar ratio of hydrogen to 2, 5-hexanedione was 80: 1, the conversion of 2, 5-hexanedione was 96% and the selectivity of methylcyclopentadiene was 88%.
Example 7
(1) AxByOz type composite metal oxide catalyst Cr2(MoO4)3The preparation method can use a citric acid complexation method, and comprises the following specific processes: ammonium molybdate 1.24g, chromium nitrate nonahydrate 1.87g and citric acid 2.94g are weighed according to the molar ratio n (M)/n (citric acid) ═ 1/1.2, wherein M is the molar sum of metal B in anions and cation metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 ℃ for 12h, and then roasting at 600 ℃ for 5h to obtain Cr2(MoO4)3A catalyst.
(2) Adding the above Cr2(MoO4)3Catalyst 0.1g ZnMoO synthesized in example 340.2g of catalyst is mechanically mixed and then evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.03MPa, the hydrogen flow rate of 150mL/min and the reduction temperature of 400 ℃, and then the reaction temperature of 400 ℃ is controlled, the reaction pressure of 0.03MPa and the hourly space velocity of 2, 5-hexanedione is 2.5h-1The molar ratio of hydrogen to 2, 5-hexanedione was 70: 1, the conversion of 2, 5-hexanedione was 100%, and the conversion of methylcyclopentadiene wasThe selectivity was 92%.
The results of the above experiments for examples 1-7 are shown in Table 2.
TABLE 2 Synthesis of methylcyclopentadienes by hydrodeoxygenation of 2, 5-hexanedione
With Cr in example 72(MoO4)3+ZnMoO40.2g of catalyst is uniformly mixed with 4mL of 40-70 mesh quartz sand, the mixture is filled in a fixed bed continuous reactor, 2, 5-hexanedione is taken as a substrate, then the mixture is reduced for 1h at the hydrogen pressure of 0.05MPa and the reduction temperature of 400 ℃, and the reaction is carried out under certain molar ratio of hydrogen to 2, 5-hexanedione, reaction temperature, reaction pressure and hourly space velocity.
TABLE 3 Cr2(MoO4)3+ZnMoO4Catalytic hydrodeoxygenation of 2, 5-hexanedione to synthesize methyl cyclopentadiene
Example 24
(1) AxByOz type composite metal oxide catalyst Zn3Mo2O9The preparation of (1): 2.47g of ammonium molybdate was weighed and dissolved in 200mL of deionized water. Adjusting the pH value of the solution to 9.2 by using an ammonia water solution with the concentration of 4mol/L as a precipitator, dropwise adding a zinc nitrate (4.16g dissolved in 100mL of deionized water) aqueous solution, stirring for 2h, filtering out the obtained precipitate, washing with deionized water and ethanol, drying in an oven at 100 ℃ for 5h, and roasting at 400 ℃ for 2h to obtain Zn3Mo2O9A composite metal oxide catalyst.
(2) The above Zn is added3Mo2O90.2g of catalyst is evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 1 hour under the conditions that the hydrogen pressure is 0.05MPa, the hydrogen flow is 150mL/min and the reduction temperature is 400 ℃, and then the control is carried outThe reaction temperature is 400 ℃, the reaction pressure is 0.05MPa, and the hourly space velocity of the 3-methyl-2-cyclopentene-1-ketone is 3h-1The molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 70: 1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 91%.
Example 25
(1) AxByOz type composite metal oxide catalyst CuMoO4The preparation method can use a citric acid complexation method, and comprises the following specific processes: weighing 1.24g of ammonium molybdate, 1.69g of copper nitrate and 3.53g of citric acid according to the molar ratio n (M)/n (citric acid) ═ 1/1.2, wherein M is the molar sum of metal B in anions and cationic metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 deg.C for 12h, and calcining at 600 deg.C for 5h to obtain CuMoO4A catalyst.
(2) Mixing the above CuMoO40.15g of catalyst is evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.5MPa, the hydrogen flow rate of 150mL/min and the reduction temperature of 400 ℃, then the reaction temperature of 400 ℃ is controlled, the reaction pressure of 0.05MPa and the hourly space velocity of 3-methyl-2-cyclopentene-1-ketone is 2.5h-1The molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 70: 1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 82%.
Example 26
(1) AxByOz type composite metal oxide catalyst Zn3(VO4)2Can be prepared by a hydrothermal method, and comprises the following specific steps: dissolving 1.10g of zinc acetate and 0.47g of ammonium metavanadate in 60mL of deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 12h, filtering and washing, drying the obtained powder at 80 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain Zn3(VO4)2A catalyst.
(2) The above Zn is added3(VO4)20.25g of catalyst is uniformly mixed with 4mL of quartz sand with 40-70 meshes, and the mixture is filled in a fixed bed for continuous reactionIn a reactor, reducing for 2.5h under the hydrogen pressure of 0.50MPa, the hydrogen flow of 160mL/min and the reduction temperature of 450 ℃, then controlling the reaction temperature of 400 ℃, the reaction pressure of 0.05MPa and the hourly space velocity of 3-methyl-2-cyclopenten-1-one of 2.5h-1The molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 70: 1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 86%.
Example 27
(1) AxByOz type composite metal oxide catalyst MnMoO4The preparation method can use a citric acid complexation method, and comprises the following specific processes: ammonium molybdate 1.24g, 50 wt% manganese nitrate aqueous solution 2.51g and citric acid 3.53g are weighed according to the molar ratio n (M)/n (citric acid) ═ 1/1.2, M is the molar sum of metal B in anion and cation metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 ℃ for 12h, roasting at 600 ℃ for 5h to obtain MnMoO4A catalyst.
(2) Mixing the MnMoO40.5g of catalyst is evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 2h under the hydrogen pressure of 0.5MPa, the hydrogen flow rate of 150mL/min and the reduction temperature of 400 ℃, then the reaction temperature of 400 ℃ is controlled, the reaction pressure of 0.05MPa and the hourly space velocity of 3-methyl-2-cyclopentene-1-ketone is 1.1h-1The molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 70: 1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 89%.
Example 28
(1) ZnWO of AxByOz type composite metal oxide catalyst4Can be prepared by a hydrothermal method, and comprises the following specific steps: dissolving 0.55g of zinc acetate and 0.99g of sodium tungstate dihydrate in 60mL of deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 12h, filtering and washing, drying the obtained powder at 80 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain ZnWO4A catalyst.
(2) The above ZnWO is added4Catalyst 0.1g and exampleZn synthesized in 83Mo2O90.1g of catalyst is mechanically mixed and then evenly mixed with 4mL of quartz sand with 40-70 meshes, the mixture is filled in a fixed bed continuous reactor, then the mixture is reduced for 1h under the hydrogen pressure of 0.01MPa, the hydrogen flow rate of 200mL/min and the reduction temperature of 450 ℃, and then the reaction temperature is controlled to be 400 ℃, the reaction pressure is controlled to be 0.01MPa, and the hourly space velocity of 3-methyl-2-cyclopentene-1-ketone is controlled to be 3.5h-1The molar ratio of hydrogen to 3-methyl-2-cyclopenten-1-one is 100: 1, the conversion of 3-methyl-2-cyclopenten-1-one is 100%, and the selectivity of methylcyclopentadiene is 95%.
The results of the experiments described in examples 24 to 28 are shown in Table 4.
TABLE 4 Synthesis of methylcyclopentadienes by hydrodeoxygenation of 3-methyl-2-cyclopenten-1-one
Using the ZnWO of example 284+Zn3Mo2O90.2g of catalyst is uniformly mixed with 4mL of 40-70 mesh quartz sand, the mixture is filled in a fixed bed continuous reactor, 2, 5-hexanedione is taken as a substrate, then the mixture is reduced for 1h at the hydrogen pressure of 0.05MPa and the reduction temperature of 400 ℃, and the reaction is carried out under certain molar ratio of hydrogen to 2, 5-hexanedione, reaction temperature, reaction pressure and hourly space velocity.
TABLE 5 ZnWO4+Zn3Mo2O9Catalytic hydrodeoxygenation synthesis of methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone
Claims (10)
1. A method for preparing methyl cyclopentadiene, which is characterized by comprising a method 1 or a method 2, wherein the method 1 and the method 2 are as follows:
method 1
Method 2
The AxByOz type composite metal oxide catalyst comprises: CuMoO4、Cu3Mo2O9、ZnMoO4、Zn3Mo2O9、NiMoO4、CoMoO4、MnMoO4、FeMoO4、Fe2(MoO4)3、Cr2(MoO4)3、CuWO4、NiWO4、CoWO4、FeWO4、ZnWO4、Zn3(VO4)2One or more of (a).
2. The process according to claim 1, wherein the reaction of the process 1 or the process 2 is carried out in a fixed bed continuous reactor; the reaction temperature is 300-600 ℃, the hydrogen pressure is 0.0001-1MPa, the molar ratio of the hydrogen to the substrate is 20-300: 1, and the mass space velocity of the substrate is 0.01-10h-1。
3. The method according to claim 2, wherein the hydrogen pressure is 0.0001 to 0.9 MPa; the mass space velocity of the substrate is 0.05-9h-1。
4. The process according to claim 3, wherein the hydrogen pressure is 0.0001 to 0.8MPa and the mass space velocity of the substrate is 0.1 to 8h-1。
5. The method according to claim 1, wherein the AxByOz type composite metal oxide catalyst is prepared by a hydrothermal method, a precipitation deposition method or a citric acid complexation method, and is subjected to a reduction treatment in hydrogen before use, wherein the reduction conditions are as follows: the hydrogen pressure is 0.001-2.0MPa, the hydrogen flow rate is 2-300mL/min, the reduction temperature is 200-.
6. The method of claim 5, wherein the reducing conditions are: the hydrogen pressure is 0.005-1.5MPa, the hydrogen flow rate is 5-250mL/min, the reduction temperature is 250-550 ℃, and the reduction time is 0.7-10 h.
7. The method as claimed in claim 6, wherein the hydrogen pressure is 0.01-1MPa, the hydrogen flow rate is 10-200mL/min, the reduction temperature is 300-500 ℃, and the reduction time is 1-8 h.
8. The method of claim 5,
the hydrothermal process comprises the steps of: mixing and dissolving the metal salt of A and the metal salt of B in deionized water, and performing ultrasonic treatment at room temperature to obtain a suspension; transferring the suspension into a reaction kettle, reacting for 5-48h at 80-220 ℃, then filtering, washing, drying for 3h at 80 ℃, and then roasting for 1-6h at 300-800 ℃ to obtain the AxByOz type composite metal oxide catalyst;
the deposition precipitation method comprises the following steps: dissolving the metal salt of B in deionized water, adjusting the pH value to 8-12 by using an ammonia water solution with the concentration of 0.5-14 mol/L as a precipitator, dropwise adding the aqueous solution of the metal salt of A, stirring for 0.5-4h, filtering out the obtained precipitate, washing with deionized water and ethanol, drying for 4-48h at the temperature of 100-200 ℃, and roasting for 0.5-10h at the temperature of 300-800 ℃ to obtain the AxByOz type composite metal oxide catalyst;
the citric acid complexation method comprises the following steps: weighing the metal salt of B, the metal salt of A and citric acid according to a molar ratio of M to citric acid of 1: 1-1: 3, wherein M is the molar sum of the metal B and the metal A; dissolving the three solutions in deionized water respectively, uniformly mixing the three solutions, and heating the mixture in an evaporation pan until only solid is generated; drying at 120 ℃ for 12h, and then roasting at 300-800 ℃ for 0.5-10h to obtain the AxByOz type composite metal oxide catalyst.
9. The method of claim 8,
in the deposition precipitation method, the concentration of the ammonia water solution is 1-8 mol/L; the stirring time is 1-3h, the roasting temperature is 350-750 ℃, and the roasting time is 1-8 h;
in the citric acid complexation method: the ratio of M to citric acid is 1: 1.05-1: 2; the roasting temperature is 350-750 ℃; the roasting time is 1-8 h.
10. The method of claim 9,
in the precipitation method: the concentration of the ammonia water solution is 1.5-6 mol/L; the roasting temperature is 400-700 ℃; the roasting time is 1-6 h;
in the citric acid complexation method: the ratio of M to citric acid is 1: 1.1-1: 1.5; the roasting temperature is 400-700 ℃, and the roasting time is 1-6 h.
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