CN107812531B - Catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, preparation method and application thereof - Google Patents
Catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The invention discloses a catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, a preparation method and application thereof. The catalyst comprises 1-30 wt% of silver, 0.1-10 wt% of copper, 0.01-1 wt% of rhenium, 0.01-1 wt% of molybdenum and 30-50 wt% of TiO220-40 wt% of Ir5(PO4)6(OH)2. The catalyst is particularly suitable for preparing 3-methyl-2-butene-1-aldehyde by oxidizing 3-methyl-2-butene-1-alcohol. The catalyst of the invention has the characteristics of high reaction activity, strong high-temperature sintering resistance, good stability and the like, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, in particular to a catalyst for preparing 3-methyl-2-butene-1-aldehyde by oxidizing 3-methyl-2-butene-1 alcohol and a preparation method thereof.
Background
3-methyl-2-butene-1-aldehyde, also called as isopropenal, is a raw material for synthesizing isophytol, can also be used as a starting material for synthesizing citral to further produce vitamin A, vitamin E and β -carotene, and can also be used for synthesizing spices such as damascenone, irone and the like.
In JPS60246340, it is reported that 3-methyl-2-butene-1-aldehyde is prepared by oxidizing 3-methyl-2-butene-1-ol with oxygen at 400-500 ℃ by using a silver and copper composite catalyst loaded on a carrier, and the selectivity of a target product can reach 96%. The reaction needs to be carried out under a higher temperature condition, and the catalyst is very easy to sinter in the continuous reaction operation, so that the service life of the catalyst is shortened.
The patent DE2715209 reports the oxidative dehydrogenation of 3-methyl-2-buten-1-ol in an oxygen atmosphere with silver/copper crystals as a catalyst. The patent describes that a catalyst with higher activity can be obtained only when the particle size distribution of the silver catalyst is relatively uniform or the silver catalyst has a certain particle size distribution in a layered structure, and the repeatability of the catalyst in actual production is poor. Meanwhile, the reaction can be carried out only under the high-temperature condition of more than 300 ℃, and the problems of easy sintering of the catalyst, short service life and the like exist.
Patent DE2517859 reports that 3-methyl-2-butene-1-aldehyde is synthesized by copper-catalyzed oxidation of 3-methyl-2-butene-1-ol in a tubular reactor at the temperature of 150 ℃ and 300 ℃ in an excess oxygen atmosphere, although the catalyst is not easy to sinter, a large amount of byproducts are generated in the reaction process, and the selectivity of 3-methyl-2-butene-1-aldehyde is poor.
From the above patents, it can be found that pure metals of noble metals such as silver and copper and the corresponding supported catalysts are considered to be good catalysts for gas phase oxidative dehydrogenation of unsaturated alcohols to aldehydes or ketones using air or oxygen as an oxidant. The catalytic performance of the catalyst on the oxidative dehydrogenation of unsaturated alcohols has been reported in many patents and literatures, but these metal catalysts all have their own disadvantages. The copper catalyst has poor activity on the oxidation reaction of unsaturated alcohol, has low selectivity and can not meet the requirement of industrialization; although the silver catalyst has good activity for the oxidation reaction of unsaturated alcohol and high yield and selectivity, silver nanoparticles are easy to aggregate and grow under the high-temperature condition, so that the silver catalyst is easy to sinter, and the service life of the catalyst is short. Meanwhile, the surface of the catalyst is easy to deposit carbon in the sintering process, so that the pore channel of the catalyst is blocked, the internal pressure of the reactor is increased, and the process safety problem is caused. Therefore, it is necessary to develop a catalyst having both high activity and strong anti-sintering property.
Disclosure of Invention
The invention aims to provide a supported composite metal catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, in particular for preparing 3-methyl-2-butene-1-aldehyde by oxidizing 3-methyl-2-butene-1-alcohol. The catalyst has high activity and high-temperature sintering resistance.
The invention also aims to provide a preparation method of the supported composite metal catalyst, which has simple process and low cost.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a supported composite metal catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, which comprises the following components in percentage by weight based on the total weight of the catalyst:
preferably, the catalyst comprises, based on the total weight of the catalyst:
in the present invention, the total weight of the catalyst is the weight of the finally prepared catalyst product.
In the invention, the rhenium element, the molybdenum element and other auxiliaries can effectively improve the reaction performance of the catalyst.
In the present invention, the carrier of the catalyst is Ir5(PO4)6(OH)2And TiO2In the composite support, Ir5(PO4)6(OH)2Mainly plays a role in stabilizing the size of silver nano particles, so that the catalyst has high-temperature sintering resistance, and TiO2Mainly plays a role in stabilizing the catalytic structure, so that the catalyst has better stability under the high-temperature condition.
The invention also provides a method for preparing the catalyst, which comprises the following steps: according to the proportion,
(1) to TiO 22Adding Ir into the ammonia water suspension5(PO4)6(OH)2Stirring for 1-8 h, preferably 3-6 h at 40-100 ℃, preferably 50-90 ℃, standing and aging for 8-14 h, preferably 10-12 h at room temperature, centrifugally washing the obtained precipitate, roasting for 3-8 h, preferably 4-6 h at 100-800 ℃, preferably 200-600 ℃ after freeze drying to obtain a carrier for later use;
(2) precipitating a soluble silver salt solution by using a precipitating agent, and adding an amine solution to dissolve the soluble silver salt solution to form a silver-amine solution;
(3) adding soluble copper salt, soluble rhenium salt and soluble molybdenum salt into the silver-amine solution obtained in the step (2) to obtain a mixed solution;
(4) and (3) spraying or dipping the carrier prepared in the step (1) by using the mixed solution obtained in the step (3), and then drying and roasting to obtain the catalyst.
TiO in the step (1) of the present invention2The mass ratio of the ammonia to the ammonia water is 0.2-2.0: 1, preferably 0.5-1.5: 1.
The concentration of the ammonia water in the step (1) is 10-50 wt%, preferably 20-30 wt%.
The precipitating agent in step (2) of the present invention is selected from ammonium oxalate and/or ammonium carbonate, preferably ammonium oxalate. The molar ratio of the precipitant to the silver element in the soluble silver salt is 1.25-2: 1, and preferably 1.5-1.7: 1. The precipitant is preferably used in the form of a solution, and the concentration of the solution is 0.1-25 mol/L, preferably 1-10 mol/L; the solvent of the solution is preferably water.
The amine of the amine solution in step (2) of the present invention is selected from ethylenediamine and/or propylenetriamine, preferably ethylenediamine. The molar ratio of the amine in the amine solution to the silver element in the soluble silver salt is 1.2-3: 1, and preferably 1.5-2: 1. The concentration of the amine solution is 0.1-15 mol/L. The solvent of the amine solution is preferably water.
The soluble silver salt is selected from one or more of silver fluoride, silver perchlorate and silver nitrate, and preferably silver nitrate. The concentration of the soluble silver salt solution is 0.1-50 mol/L, preferably 1-20 mol/L. The solvent of the soluble silver salt solution is preferably water.
The soluble copper salt is selected from one or more of copper nitrate, copper chloride and copper sulfate, and is preferably copper nitrate.
The soluble rhenium salt is one or more of rhenium nitrate, rhenium sulfate and rhenium carbonate, and preferably rhenium nitrate.
The soluble molybdenum salt is one or more of molybdenum nitrate, molybdenum sulfate and molybdenum carbonate, and molybdenum nitrate is preferred.
The drying in the step (4) can be performed in air or inert gas atmosphere, and the drying temperature is 50-120 ℃, preferably 60-100 ℃.
The roasting temperature in the step (4) is 200-600 ℃, preferably 300-450 ℃, and the roasting atmosphere can be air, nitrogen and the like. The roasting time is 0.1-3 h, preferably 0.5-1 h.
The catalyst of the invention is particularly suitable for preparing 3-methyl-2-butene-1-aldehyde by 3-methyl-2-butene-1-alcohol gas phase oxidation reaction, and the reaction comprises the following steps: the reaction temperature of the raw material gas is 250-450 ℃, the preferable temperature is 320-420 ℃, and the space velocity is 3000-40000 h under the catalysis of the catalyst-1Preferably 10000-25000 h-1The reaction is carried out. In the raw material gas, the molar ratio of the 3-methyl-2-butene-1-ol to the oxygen is 1: 0.01-0.5, preferably 1: 0.2-0.4. The carrier gas may be any inert gas, preferably nitrogen.
The space velocity in the present invention means the volume of gas per unit time and per unit volume of catalyst passing through the standard state.
The reactor for the gas phase oxidation reaction of the present invention may employ any reactor known in the art, preferably a tubular reactor.
The catalyst of the invention combines the advantages of silver and copper catalysts, and simultaneously has the characteristic of high activity due to the addition of rhenium, molybdenum and other element auxiliaries. At the same time, Ir in the carrier5(PO4)6(OH)2Can stabilize the size of silver nano particles, and enables the catalyst to have the characteristic of high-temperature sintering resistance. When the method is applied to the oxidation reaction of 3-methyl-2-butene-1-ol, the conversion rate of the 3-methyl-2-butene-1-ol is up to 70-75%, and the selectivity of the 3-methyl-2-butene-1-aldehyde is high97-99%, reaction time is 4000 hours, and catalyst activity is stable. The preparation method of the catalyst is simple, and the used raw materials are cheap and easy to obtain, so that the catalyst is suitable for large-scale industrial application.
Detailed description of the invention
Gas chromatography conditions:
the Shimadzu GC-2014 online analysis gas chromatography is provided with a ten-way high-temperature injection valve, two six-way valves, two hydrogen Flame Ionization Detectors (FID) and a thermal conductivity cell detector (TCD), a DB-17 chromatographic column and the FID are adopted to detect organic matters generated by reaction, and a 13X molecular sieve column and a damping column are combined with the TCD and the FID detector to detect constant and trace amounts of CO, CO2, O2, N2 and the like.
A chromatographic column: shimadzu DB-17 (specification of 50m 0.32mm 0.25mm)
Sample inlet temperature: 280 deg.C
The split ratio is as follows: 30: 1
Column flow rate: 1.5ml/min
Temperature program of chromatographic column: keeping the temperature at 50 ℃ for 1min, and increasing the temperature at 5 ℃/min to 280 DEG C
Hydrogen flow rate: 35ml/min
Air flow rate: 350 ml/min.
Example 1:
preparation of catalyst a: to 43.24g of 25 wt% aqueous ammonia, 5.25g of TiO was added with stirring2This was suspended in water and 3.99g of Ir was added to the suspension5(PO4)6(OH)2Reacting at 60 ℃ for 5h, standing at room temperature for aging for 11h, centrifuging and washing the obtained precipitate, freeze-drying, and roasting at 400 ℃ for 5h to be used as a carrier; 0.17g of AgNO3 was dissolved in 0.2mL of water, 0.20g of (NH4)2C2O4 was dissolved in 0.32mL of water, and the two solutions were reacted in a water bath at 40 ℃ with stirring. Washing the precipitate after 1 hr, washing for 2-3 times, adding 0.34mL of 5mol/L ethylenediamine aqueous solution into the precipitate to obtain silver-amine complex solution, and adding 3.08g Cu (NO) into the obtained silver-amine complex solution3)2、0.002gRe(NO3)3、0.38gMo(NO3)4Dissolving into uniform solution, adding the prepared carrierThe solution was stirred for about 1 hour, the solvent was distilled off at 100 ℃ and calcined at 350 ℃ for 0.7 hour to obtain 10.5g of catalyst A. Wherein, silver accounts for 1 wt%, copper accounts for 10 wt%, rhenium accounts for 0.01 wt%, molybdenum accounts for 1 wt%, TiO250% of Ir5(PO4)6(OH)2Accounting for 37.99wt percent.
Catalyst a reaction activity test: crushing the catalyst to 30-60 meshes, putting 2ml of the crushed catalyst into a reaction tube with the inner diameter of 1cm, feeding 10g of raw material 3-methyl-2-butene-1-ol, 0.9L of oxygen and 2.1L of nitrogen every hour, setting the reaction starting temperature to be 350 ℃, setting the reaction hot point to be 375 ℃, and analyzing reaction products by gas chromatography to obtain the reaction conversion rate of 70 percent and the selectivity of the 3-methyl-2-butene-1-aldehyde of 98 percent.
Testing the service life of the catalyst A: the continuous operation is carried out under the process conditions, the sampling analysis is carried out every 4h, the reaction activity is not reduced within 4000h, the conversion rate is maintained at 69-72%, the selectivity is maintained at 97-98%, the reaction conversion rate begins to be reduced after 4300 h, and the conversion rate is reduced to below 50% after 5000 h.
Example 2:
preparation of catalyst B: except that 3.06g of AgNO was used3、2.16g Cu(NO3)2、0.01g Re(NO3)3、0.30gMo(NO3)4、3.68g TiO2、4.06g Ir5(PO4)6(OH)23.57g (NH4)2C2O4, 6.12ml of a 5mol/L aqueous ethylenediamine solution, and 30.26g of 25 wt% aqueous ammonia were added to the above mixture, and the mixture was referred to example 1. In the obtained catalyst B, silver was 18.50 wt%, copper was 7 wt%, rhenium was 0.05 wt%, molybdenum was 0.80 wt%, TiO235% of Ir5 (PO)4)6(OH)238.65 wt% is contained.
Catalyst B reaction activity test: the reaction conversion was 72% and the selectivity for 3-methyl-2-butene-1-aldehyde was 97%, which were measured by referring to the method of example 1.
Testing the service life of the catalyst B: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is maintained between 69 and 72 percent, the selectivity is maintained between 97 and 98 percent, the reaction conversion rate begins to reduce after 4200 hours until the conversion rate is reduced to below 50 percent after 5000 hours.
Example 3:
preparation of catalyst C: except that 4.13g of AgNO was used3、0.15g Cu(NO3)2、0.09g Re(NO3)3、0.16gMo(NO3)4、4.20g TiO2、3.53g Ir5(PO4)6(OH)2Example 1 was repeated, except for 4.82g (NH4)2C2O4, 8.27ml of a 5mol/L aqueous ethylenediamine solution and 34.59g of 25 wt% aqueous ammonia. In the obtained catalyst C, silver was 25 wt%, copper was 0.5 wt%, rhenium was 0.43 wt%, molybdenum was 0.43 wt%, TiO240% of Ir5(PO4)6(OH)233.65 wt% is contained.
Catalyst C reactivity test: the reaction conversion was 75% and the selectivity to 3-methyl-2-butene-1-aldehyde was 99% as tested with reference to the procedure of example 1.
Testing the service life of the catalyst C: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is kept between 73 and 75 percent, the selectivity is kept between 97 and 99 percent, the reaction conversion rate begins to reduce after 4100 hours, and the conversion rate is reduced to below 50 percent after 5000 hours.
Example 4:
preparation of catalyst D: except that 1.98g of AgNO was used3、1.16g Cu(NO3)2、0.17g Re(NO3)3、0.02gMo(NO3)4、4.73g TiO2、4.03g Ir5(PO4)6(OH)2Example 1 was repeated, except for 2.31g of (NH4)2C2O4, 3.96ml of a 5mol/L aqueous ethylenediamine solution and 38.91g of 25 wt% aqueous ammonia. In the obtained catalyst D, silver was 12 wt%, copper was 3.75 wt%, rhenium was 0.80 wt%, molybdenum was 0.05 wt%, TiO245% of Ir5(PO4)6(OH)2Accounting for 38.40wt percent.
Catalyst D reaction activity test: the reaction conversion was 70% and the selectivity for 3-methyl-2-butene-1-aldehyde was 98%, as tested with reference to the method of example 1.
Testing the service life of the catalyst D: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is maintained at 69-72%, the selectivity is maintained at 97-98%, the reaction conversion rate begins to reduce after 4100 hours, and the conversion rate is reduced to below 50% after 5000 hours.
Example 5:
preparation of catalyst E: except that 4.96g of AgNO was used3、0.03g Cu(NO3)2、0.21g Re(NO3)3、0.004gMo(NO3)4、3.15g TiO2、4.08g Ir5(PO4)6(OH)25.79g of (NH4)2C2O4, 9.93ml of a 5mol/L aqueous ethylenediamine solution, and 25.94g of 25 wt% aqueous ammonia were added to the above mixture, and the balance was found to be in example 1. In the obtained catalyst E, 30 wt% of silver, 0.10 wt% of copper, 1.0 wt% of rhenium, 0.01 wt% of molybdenum, TiO230% of Ir5(PO4)6(OH)2Accounting for 38.89wt percent.
Catalyst E reaction activity test: the reaction conversion was 73% and the selectivity for 3-methyl-2-butene-1-aldehyde was 97%, which were measured by referring to the method of example 1.
Testing the service life of the catalyst E: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is kept between 70 and 73 percent, the selectivity is kept between 97 and 98 percent, the reaction conversion rate begins to reduce after 4300 hours, and the conversion rate is reduced to below 50 percent after 5000 hours.
Example 6:
preparation of catalyst F: except that 4.96g of AgNO was used3、3.08g Cu(NO3)2、0.17g Re(NO3)3、0.02gMo(NO3)4、4.11g TiO2、2.10g Ir5(PO4)6(OH)25.79g of (NH4)2C2O4, 9.93ml of a 5mol/L aqueous ethylenediamine solution, and 33.85g of 25 wt% aqueous ammonia were added to the above mixture, and the balance was found to be in example 1. In the obtained catalyst F, silver was 30 wt%, copper was 10 wt%, rhenium was 0.8 wt%, molybdenum was 0.05 wt%, TiO239.15% and Ir5(PO4)6(OH)2Accounting for 20wt percent.
Catalyst F reaction activity test: the reaction conversion was 74% and the selectivity for 3-methyl-2-butene-1-aldehyde was 98% as tested with reference to the method of example 1.
Catalyst F life test: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is kept between 72 and 75 percent, the selectivity is kept between 97 and 98 percent, the reaction conversion rate begins to reduce after 4200 hours until the conversion rate is reduced to below 50 percent after 5000 hours.
Example 7:
preparation of catalyst G: except that 4.96g of AgNO was used3、1.16g Cu(NO3)2、0.17g Re(NO3)3、0.02gMo(NO3)4、4.24g TiO2、2.63g Ir5(PO4)6(OH)25.79g of (NH4)2C2O4, 9.93ml of a 5mol/L aqueous ethylenediamine solution, and 34.93g of 25 wt% aqueous ammonia were added to the above mixture, and the mixture was referred to example 1. In the obtained catalyst G, silver was 30 wt%, copper was 3.75 wt%, rhenium was 0.8 wt%, molybdenum was 0.05 wt%, TiO240.40% and Ir5(PO4)6(OH)2Accounting for 25wt percent.
Catalyst G reaction activity test: the reaction conversion was 75% and the selectivity for 3-methyl-2-butene-1-aldehyde was 97% as tested with reference to the procedure of example 1.
Testing the service life of the catalyst G: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is kept between 72 and 75 percent, the selectivity is kept between 97 and 98 percent, the reaction conversion rate begins to reduce after 4100 hours, and the conversion rate is reduced to below 50 percent after 5000 hours.
Example 8:
preparation of catalyst H: except that 3.06g of AgNO was used3、2.16g Cu(NO3)2、0.01g Re(NO3)3、0.30gMo(NO3)4、4.58g TiO2、3.15g Ir5(PO4)6(OH)23.57g (NH4)2C2O4, 6.13ml of ethylenediamine water with the concentration of 5mol/LThe solution was prepared in accordance with example 1 except that 37.74g of 25 wt% aqueous ammonia was used. In the obtained catalyst H, silver was 18.50 wt%, copper was 7 wt%, rhenium was 0.05 wt%, molybdenum was 0.80 wt%, TiO243.65% of Ir5(PO4)6(OH)2Accounting for 30wt percent.
Catalyst H reactivity test: the reaction conversion was 70% and the selectivity for 3-methyl-2-butene-1-aldehyde was 98%, as tested with reference to the method of example 1.
Testing the service life of the catalyst H: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is maintained between 69 and 72 percent, the selectivity is maintained between 97 and 98 percent, the reaction conversion rate begins to reduce after 4200 hours until the conversion rate is reduced to below 50 percent after 5000 hours.
Example 9:
preparation of catalyst I: except that 1.98g of AgNO was used3、3.08g Cu(NO3)2、0.002g Re(NO3)3、0.38gMo(NO3)4、4.41g TiO2、3.68g Ir5(PO4)6(OH)2Example 1 was repeated, except for 2.31g of (NH4)2C2O4, 3.96ml of a 5mol/L aqueous ethylenediamine solution and 36.31g of 25 wt% aqueous ammonia. In the obtained catalyst I, silver was 12 wt%, copper was 10 wt%, rhenium was 0.01 wt%, molybdenum was 1 wt%, TiO241.99% of Ir5(PO4)6(OH)2Accounting for 35wt percent.
Catalyst I reaction activity test: the reaction conversion was 70% and the selectivity for 3-methyl-2-butene-1-aldehyde was 97%, which were measured by referring to the method of example 1.
Catalyst I life test: when the method is tested according to the method of example 1, the reaction activity is not reduced within 4000 hours, the conversion rate is maintained between 69 and 72 percent, the selectivity is maintained between 97 and 98 percent, the reaction conversion rate begins to reduce after 4200 hours until the conversion rate is reduced to below 50 percent after 5000 hours.
Comparative example 1:
preparation of catalyst J: except that 4.96g of AgNO was used3、3.08g Cu(NO3)2、0.210g Re(NO3)3、0.38gMo(NO3)4、6.09g TiO25.79g (NH4)2C2O4, 9.93ml of a 5mol/L ethylenediamine aqueous solution, 50.15g of 25 wt% aqueous ammonia, and no Ir5(PO4)6(OH)2Otherwise, reference is made to example 1. In the obtained catalyst J, silver was 30 wt%, copper was 10 wt%, rhenium was 1.0 wt%, molybdenum was 1.0 wt%, TiO2Accounting for 58 percent.
Catalyst J reactivity test: the reaction conversion was 70% and the selectivity for 3-methyl-2-butene-1-aldehyde was 97%, which were measured by referring to the method of example 1.
Catalyst J life test: the reaction conversion started to decrease after 1000 hours and decreased to below 50% after 1500 hours, tested according to the method of example 1.
Comparative example 2:
preparation of catalyst K: except that 1.98g of AgNO was used3、1.16g Cu(NO3)2、4.73g TiO2、4.12g Ir5(PO4)6(OH)22.31g (NH4)2C2O4, 3.96ml of a 5mol/L ethylenediamine aqueous solution, 38.91g of 25 wt% aqueous ammonia, and NO Re (NO)3)3And Mo (NO)3)4Otherwise, reference is made to example 1. In the obtained catalyst K, silver was 12 wt%, copper was 3.75 wt%, and TiO245% of Ir5(PO4)6(OH)239.25 wt%.
And (3) testing the reaction activity of the catalyst K: the reaction conversion was 52% and the selectivity for 3-methyl-2-butene-1-aldehyde was 70% as tested with reference to the procedure of example 1.
Comparative example 3:
preparation of catalyst L: except that 1.98g of AgNO was used3、1.16g Cu(NO3)2、0.21g Re(NO3)3、4.73gTiO2、4.02g Ir5(PO4)6(OH)22.31g (NH4)2C2O4, 3.96ml of a 5mol/L ethylenediamine aqueous solution, 38.91g of 25 wt% aqueous ammonia, and NO Mo (NO) was used3)4Outer coverOtherwise, refer to example 1. In the obtained catalyst L, silver was 12 wt%, copper was 3.75 wt%, rhenium was 1.0 wt%, TiO245% of Ir5(PO4)6(OH)2Accounting for 38.25wt percent.
Catalyst L reaction activity test: the reaction conversion was 60% and the selectivity for 3-methyl-2-butene-1-aldehyde was 85%, as tested with reference to the method of example 1.
Claims (19)
1. A catalyst for preparing ethylenically unsaturated aldehyde from ethylenically unsaturated alcohol, characterized in that the catalyst comprises, based on the total weight of the catalyst:
2. the catalyst of claim 1, wherein the catalyst comprises, based on the total weight of the catalyst:
3. a method of preparing the catalyst of claim 1, comprising the steps of:
(1) to TiO 22Adding Ir into the ammonia water suspension5(PO4)6(OH)2Stirring, standing at room temperature for aging, washing the obtained precipitate, freeze-drying, and roasting to obtain a carrier for later use;
(2) precipitating a soluble silver salt solution by using a precipitating agent, and adding an amine solution to dissolve the soluble silver salt solution to form a silver-amine solution;
(3) adding soluble copper salt, soluble rhenium salt and soluble molybdenum salt into the silver-amine solution obtained in the step (2) to obtain a mixed solution;
(4) and (3) spraying or dipping the carrier prepared in the step (1) by using the mixed solution obtained in the step (3), and then drying and roasting to obtain the catalyst.
4. The method according to claim 3, wherein the stirring temperature in the step (1) is 40-100 ℃; the stirring time is 1-8 h.
5. The method according to claim 4, wherein the stirring temperature in the step (1) is 50 to 90 ℃.
6. The method according to claim 3, wherein the roasting temperature in the step (1) is 100-800 ℃; the roasting time is 3-8 h.
7. The method according to claim 6, wherein the roasting temperature in the step (1) is 200-600 ℃; the roasting time is 4-6 h.
8. A process according to claim 3, wherein the precipitating agent is ammonium oxalate and/or ammonium carbonate; the molar ratio of the precipitant to silver element in the soluble silver salt is 1.25-2: 1.
9. the method of claim 8, wherein the precipitating agent is ammonium oxalate.
10. The method according to claim 8, wherein the molar ratio of the precipitating agent to elemental silver in the soluble silver salt is 1.5-1.7: 1.
11. the method according to any one of claims 3 to 10, wherein the amine in the amine solution is ethylenediamine and/or propylenetriamine; the molar ratio of the amine in the amine solution to the silver element in the soluble silver salt is 1.2-3: 1.
12. the method according to claim 11, wherein the molar ratio of the amine in the amine solution to the silver element in the soluble silver salt is 1.5-2: 1.
13. a method according to any one of claims 3 to 10, wherein the soluble silver salt is selected from one or more of silver fluoride, silver perchlorate, silver nitrate;
the soluble copper salt is selected from any one or more of copper nitrate, copper chloride and copper sulfate;
the soluble rhenium salt is selected from one or more of rhenium nitrate, rhenium sulfate and rhenium carbonate;
the soluble molybdenum salt is selected from one or more of molybdenum nitrate, molybdenum sulfate and molybdenum carbonate.
14. The method according to any one of claims 3 to 10, wherein the drying temperature in the step (4) is 50 to 120 ℃; the roasting temperature in the step (4) is 200-600 ℃; the roasting time is 0.1-3 h.
15. The method according to claim 14, wherein the drying temperature in the step (4) is 60-100 ℃; the roasting temperature in the step (4) is 300-450 ℃; the roasting time is 0.5-1 h.
16. A method for preparing 3-methyl-2-butene-1-aldehyde by oxidizing 3-methyl-2-butene-1 alcohol comprises the following steps of using the catalyst of claim 1 or 2 or the catalyst prepared by the method of any one of claims 3 to 7, wherein the reaction temperature of the 3-methyl-2-butene-1-alcohol and oxygen is 250-450 ℃, and the space velocity is 3000-40000 h-1The reaction is carried out.
17. The method of claim 16, wherein the reaction temperature of 3-methyl-2-buten-1-ol with oxygen is 320 to 420 ℃ and the space velocity is 10000 to 25000 hours-1The reaction is carried out.
18. The process according to claim 16 or 17, characterized in that the molar ratio of 3-methyl-2-buten-1-ol to oxygen is 1: 0.01 to 0.5.
19. The process according to claim 18, wherein the molar ratio of 3-methyl-2-buten-1-ol to oxygen is 1: 0.2 to 0.4.
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| CN111298808B (en) * | 2020-04-02 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method and application of core-shell catalyst |
| CN114534787B (en) * | 2020-11-24 | 2023-12-19 | 万华化学集团股份有限公司 | Gas-phase dehydrogenation catalyst and method for isopentenol |
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