Hydrogenation catalyst for 2-propyl-2-heptenal and preparation and application thereof

Abstract

The invention discloses a hydrogenation catalyst for 2-propyl-2-heptenal as well as preparation and application of the hydrogenation catalyst. The hydrogenation catalyst comprises an active component and an auxiliary component, the active components are Cu, Zn and Al, and the content of the Cu is 20-50%, the content of the Zn is 20-50%, and the content of the Al is 4-10% by mass; the auxiliary agent component comprises a non-noble metal auxiliary agent; the non-noble metal auxiliary agent is a combination of Mg and one or more of Ca, Cr and Mo; the hydrogenation catalyst comprises the following components in percentage by mass: 1-3% of Mg, 0.5-1% of Ca, 1-5% of Cr and 0.1-1.5% of Mo. When the hydrogenation catalyst is applied to the reaction of 2-propyl-2-heptenal, the hydrogenation catalyst has higher catalytic activity, and the yield of the product is improved.

Description

Technical Field

[0001] The present invention belongs to the field of hydrogenation catalysts and their preparation, and particularly relates to a hydrogenation catalyst for 2-propyl-2-heptenal, its preparation and application. Background Art

[0002] 2-Propylheptanol (decyl alcohol, 2-PH) is an important organic chemical raw material, mainly used in the production of plasticizers. The plasticizer phthalic acid (2-propyl-1-heptyl) ester produced from 2-PH has excellent physical properties, high safety and economy. Therefore, the production and application of 2-PH have received increasing attention.

[0003] In early studies, traditional catalysts such as oxide-supported Ni catalysts used in liquid-phase aldehyde hydrogenation were difficult to simultaneously meet the requirements of high activity and high selectivity, and were prone to runaway temperature during the reaction, resulting in an increase in by-products, bringing problems to production. At the same time, in order to make the product qualified, a large amount of steam was required for impurity separation.

[0004] In the prior art, liquid-phase enal hydrogenation mostly uses nickel catalysts, copper-chromium catalysts, copper-zinc catalysts and noble metal (palladium, ruthenium, cobalt, platinum) catalysts, but the general yield is not very ideal. The nickel-based catalyst has too high activity and low selectivity, the copper-based catalyst has low activity and short catalyst life, and the noble metal catalyst has high cost and is not suitable for industrial application, and the product competitiveness has no advantage. Therefore, there are contradictions in the activity, selectivity, pollution, cost, etc. of the current liquid-phase hydrogenation catalyst, and there is no catalyst with particularly excellent selectivity so far. Selectivity is particularly important for cost. The lower the selectivity, the higher the impurity content. In order to make the product quality qualified, a large amount of steam separation is required subsequently, resulting in high cost. Therefore, it is particularly important to develop a catalyst with high activity, high selectivity and high stability for the 2-propylheptanol synthesis process. Summary of the Invention

[0005] The present invention provides a hydrogenation catalyst for 2-propyl-2-heptenal, its preparation and application. When the hydrogenation catalyst is applied to the reaction of 2-propyl-2-heptenal, it has higher catalytic activity, higher selectivity and higher stability, and improves the yield of the product.

[0006] The technical solution of the present invention is as follows:

[0007] A hydrogenation catalyst for 2-propyl-2-heptenal, comprising an active component and an auxiliary component;

[0008] The active component is Cu, Zn and Al. By mass, the Cu content is 20-50%, the Zn content is 20-50%, and the Al content is 4-10%;

[0009] The described promoter component contains a non-noble metal promoter;

[0010] The non-noble metal promoter is a combination of one or more of Ca, Cr, Mo and Mg;

[0011] By mass, the content of Mg is 1-3%, the content of Ca is 0.5-1%, the content of Cr is 1-5%, and the content of Mo is 0.1-1.5%.

[0012] As a further preference, the non-noble metal promoter is composed of four components: Mg, Ca, Cr and Mo.

[0013] In the present invention, alkaline earth metal promoters such as Mg and Ca may stabilize the active species on the catalyst surface by providing electrons to promote the reaction. At the same time, Mg and Ca usually have alkalinity, which can neutralize the acidic sites on the catalyst surface and reduce the occurrence of side reactions. By changing the surface morphology of the catalyst and the distribution of active sites, the addition of some promoters may lead to the formation of more defect sites or active centers on the catalyst surface, increasing the contact area between the reactants and the catalyst and improving the reaction activity. Cr and Mo can enhance the activity of the catalyst in an oxidation or reduction atmosphere. They often have multiple coordination modes and can form complex structures with other elements, thereby adjusting the geometric shape of the active centers of the catalyst and improving the selectivity and activity of the reaction.

[0014] As a preference, the described promoter component further contains a noble metal promoter;

[0015] The noble metal promoter is one or more of Pt, Pd, Co, and the content of the noble metal promoter is 0.1%-0.5%.

[0016] As a further preference, the noble metal promoter is Pt, Pd and Co.

[0017] In the present invention, noble metal promoters such as Pt and Pd usually have a high electron affinity, can attract electrons, change the electron cloud density of the active centers of the catalyst, and thus improve the adsorption ability and activation ability of the catalyst for reactants.

[0018] In the present invention, the non-noble metal promoter is prepared by the sodium carbonate co-precipitation method, and the noble metal promoter is adsorbed and loaded by the impregnation method. The present invention also provides a preparation method of the described hydrogenation catalyst, including the following steps:

[0019] (1) Dissolve the salts or oxides containing the active combination and the salts containing the non-noble metal promoter in water to obtain a metal salt solution. Then, add the metal salt solution and the alkali solution to the water under stirring at the same time. After the addition is completed, heat and age, then filter, wash, dry and calcine to obtain the preliminary catalyst powder;

[0020] (2) The as-prepared catalyst powder is directly subjected to tabletting and sieving, or after being stirred and impregnated with a salt containing a noble metal promoter, it is aged with an alkali solution and then subjected to tabletting and sieving to obtain the hydrogenation catalyst described above.

[0021] Preferably, the salt containing the active combination is Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O and pseudo-boehmite;

[0022] The salt of the non-noble metal promoter is Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 )2·4H 2 O, Cr(NO 3 ) 3 ·9H 2 O, H 8 MoN 2 O 4 one or more of;

[0023] The salt of the noble metal catalyst is Pt(NO 3 ) 2 , Pd(NO 3 ) 2 or Co(NO 3 ) 2 ·6H 2 O one or more of.

[0024] Preferably, in step (1), the pH value during feeding is 7.5 - 8.5;

[0025] The temperature for heating and aging is 60 - 70°C, and the time for stirring and aging is 10 - 15 h;

[0026] The drying temperature is 110 - 130°C, and the drying time is 10 - 15 h;

[0027] The calcination temperature is 350 - 450°C, and the calcination time is 3 - 5 h;

[0028] In step (2), the pH value is controlled to be 8 - 9 by adding an alkali solution.

[0029] The alkali solution is: Na 2 CO 3 , NaOH, NaHCO 3 , NH 3 .H 2Alkali solutions such as O and KOH, preferably NaCO 3 The alkali solution is an aqueous solution with a concentration of 3-5% (mass percentage).

[0030] Furthermore, the specific process of step (1) is as follows: Prepare salt solutions of Cu, Zn, Mg, Ca, Cr, and Mo and pseudoboehmite powder at a certain concentration in proportion. Mix 3 or more of them and add pure water and pseudoboehmite to stir to obtain a mixed salt solution. Prepare an alkali solution at a certain concentration. At room temperature, use a peristaltic pump to drop the mixed salt solution and the alkali solution into the stirred pure aqueous solution respectively, keep the pH value at 8 until the feeding is completed, raise the temperature to 65 °C and age for 12 h, then filter by suction. Wash the filter cake with deionized water until it is neutral, dry at 120 °C for 12 h, calcine at 400 °C for 4 h, and press into tablets to obtain the initial catalyst powder.

[0031] The specific process of step (2) is as follows: Put the catalyst powder into deionized water, prepare salt solutions of Co, Pt, and Pd in proportion, select at least one or more of them and mix evenly. Use a peristaltic pump to gradually drop this solution into the stirred aqueous solution of the catalyst powder and stir and impregnate for 2 hours. Then switch to the alkali solution and use a peristaltic pump to drop it drop by drop into the stirred reaction solution at room temperature, adjust the pH value to 8.5, stop dropping, continue aging and stirring and impregnating for 5 h, filter, and repeat washing with pure water until the pH is neutral, filter, and dry the filter cake layer at 120 °C for 5 hours to obtain the catalyst powder. After pressing into tablets, a fixed-bed granular catalyst with a particle size of 1-2 mm is obtained.

[0032] The present invention also provides a method for preparing 2-propylheptanol, including:

[0033] Under the action of the hydrogenation catalyst, 2-propyl-2-heptenal undergoes a hydrogenation reaction in a hydrogen atmosphere to obtain the 2-propylheptanol.

[0034] Preferably, first pass hydrogen to reduce the hydrogenation catalyst at normal pressure, and the reduction temperature is 220-240 °C; then carry out the hydrogenation reaction, the reaction pressure is 2-4 MPa, and the reaction temperature is 140 °C-170 °C.

[0035] Preferably, the hydrogen-oil ratio is 2-4:1 (molar ratio), and the olefin aldehyde space velocity is 1.0-1.5 h -1 .

[0036] Preferably, the hydrogenation catalyst is loaded in a fixed-bed reactor, and the 2-propyl-2-heptenal and hydrogen are introduced into the fixed-bed reactor for hydrogenation reaction.

[0037] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0038] The present invention improves the existing CuO-ZnO-Al 2 O 3 catalyst by adding specific non-noble metal promoters and noble metal promoters, effectively improving the catalytic activity of the catalyst, increasing the selectivity of the product, reducing the generation of by-product over-hydrogen, and having higher stability of the catalyst. Description of the Drawings

[0039] Figure 1 It is the evaluation result of the catalyst stability test in Test Example 37. Detailed Description of the Invention

[0040] Example 1

[0041] Select metals such as Cu, Zn, and Al, with a metal ratio of 1:1:0.16. Weigh 152.1 g of Cu(NO 3 ) 2 ·3H 2 O, 182.0 g of Zn(NO 3 ) 2 ·6H 2 O and 24.2 g of pseudo-boehmite, add 1500 ml of pure water and stir to dissolve. Weigh 150 g of sodium carbonate, add 1500 ml of water and stir to dissolve completely. At room temperature, pump the above-prepared metal salt solution and sodium carbonate aqueous solution into 300 ml of pure aqueous solution under stirring state by a peristaltic pump at the same time, control the pH value of the solution to 8 until the feeding is completed, heat up to 65 °C, stir and age slowly for 12 h, then filter by suction, wash the filter cake with pure water until neutral, dry at 120 °C for 12 h, and calcine at 400 °C for 4 h to obtain the initial catalyst powder. Then, through tabletting and sieving treatment, a granular catalyst with a particle size of 1-2 mm is obtained.

[0042] Example 2

[0043] Select metals such as Cu, Zn, Al, and Mg, with a metal ratio of 1:1:0.16:0.06. Weigh 152.1 g of Cu(NO 3 ) 2 ·3H 2 O, 182.0 g of Zn(NO 3 ) 2 ·6H 2 O, 182.0 g of Mg(NO 3 ) 2 ·6H 2Dissolve 24.2 g of O and pseudoboehmite in 1500 ml of pure water with stirring. Weigh 155 g of sodium carbonate, add 1500 ml of water and stir until completely dissolved. At room temperature, simultaneously pump the above-prepared metal salt solution and sodium carbonate aqueous solution into 300 ml of pure water under stirring using a peristaltic pump, control the pH value of the solution to 8 until the feeding is completed, raise the temperature to 65 °C, stir slowly for aging for 12 h, then filter by suction, wash the filter cake with pure water until neutral, dry at 120 °C for 12 h, and calcine at 400 °C for 4 h to obtain the as-prepared catalyst powder. Then, through tabletting and sieving, a granular catalyst with a particle size of 1 - 2 mm is obtained.

[0044] Example 3

[0045] Select metals such as Cu, Zn, Al, Mg, and Ca, with a metal ratio of 1:1:0.16:0.06:0.03. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 ) 2 ·4H 2 O 11.66 g and 24.2 g of pseudoboehmite, dissolve them in 1500 ml of pure water with stirring. Weigh 160 g of sodium carbonate, add 1600 ml of water and stir until completely dissolved. At room temperature, simultaneously pump the above-prepared metal salt solution and sodium carbonate aqueous solution into 300 ml of pure water under stirring using a peristaltic pump, control the pH value of the solution to 8 until the feeding is completed, raise the temperature to 65 °C, stir slowly for aging for 12 h, then filter by suction, wash the filter cake with pure water until neutral, dry at 120 °C for 12 h, and calcine at 400 °C for 4 h to obtain the as-prepared catalyst powder. Then, through tabletting and sieving, a granular catalyst with a particle size of 1 - 2 mm is obtained.

[0046] Example 4

[0047] Select metals such as Cu, Zn, Al, Mg, Ca, and Cr, with a metal ratio of 1:1:0.16:0.06:0.03:0.06. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H2 O, Ca(NO 3 )2·4H 2 O 11.66g, Cr(NO 3 ) 3 ·9H 2 O

[0048] 11.66 g of O, Ca(NO

[0049] Example 5

[0050] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, and Mo, with a metal ratio of 1:1:0.16:0.06:0.03:0.06:0.03. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 )2·4H 2 O 11.66 g, Cr(NO 3 ) 3 ·9H 2 O 18.47 g, H 8 MoN 2 O 4 2.45 g and 24.2 g of pseudo-boehmite are added to 1500 ml of pure water and stirred until dissolved. Weigh 165 g of sodium carbonate, add 1650 ml of water, and stir until completely dissolved. At room temperature, the above-prepared metal salt solution and sodium carbonate aqueous solution are simultaneously pumped into 300 ml of pure aqueous solution under stirring using a peristaltic pump. The pH value of the solution is controlled at 8 until the feeding is completed. Then, the temperature is raised to 65°C, and it is slowly stirred and aged for 12 h. Then, it is filtered by suction, and the filter cake is washed with pure water until neutral. It is dried at 120°C for 12 h and calcined at 400°C for 4 h to obtain the as-prepared catalyst powder. Then, it is subjected to tabletting and sieving to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0051] Example 6

[0052] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, Mo, Pd, etc., with a metal ratio of 1:1:0.16:0.06:0.03:0.06:0.03:0.0033. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 )2·4H2O 11.66 g, Cr(NO 3 ) 3 ·9H 2 O 18.47 g, H 8 MoN 2 O 4 2.45 g and pseudoboehmite 24.2 g, add 1500 ml of pure water and stir to dissolve. Weigh 165 g of sodium carbonate, add 1650 ml of water and stir until completely dissolved. At room temperature, simultaneously pump the above-prepared metal salt solution and sodium carbonate aqueous solution into 300 ml of pure aqueous solution under stirring using a peristaltic pump. Control the pH value of the solution at 8 until the feeding is completed. Heat up to 65 °C and slowly stir and age for 12 h. Then, perform suction filtration. Wash the filter cake with pure water until it is neutral. Dry it at 120 °C for 12 h and calcine it at 400 °C for 4 h to obtain the as-prepared catalyst powder. Put the catalyst powder into 500 ml of pure water. Weigh Pd(NO 3 ) 2 0.286 g, add 20 ml of pure water to dissolve it. Gradually drop this solution into the aqueous solution of the catalyst powder under stirring using a peristaltic pump and stir for impregnation for 2 hours. Then, continue to switch to the alkali solution and gradually drop it into the reaction solution under stirring at room temperature using a peristaltic pump. Adjust the pH value to 8.5, stop dropping, continue aging and stirring for impregnation for 5 h, filter, repeatedly wash with pure water until the pH is neutral, filter, and dry the filter cake layer at 120 °C for 5 hours to obtain the catalyst powder. Then, perform tableting and sieving to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0053] Example 7

[0054] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, Mo, Pt, etc., with a metal ratio of 1:1:0.16:0.06:0.03:0.06:0.03:0.0033. Weigh Cu(NO 3 ) 2 ·3H2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 ) 2 ·4H2O 11.66 g, Cr(NO 3 ) 3 ·9H 2 O 18.47 g, H 8 MoN 2 O 4 2.45 g and pseudo-boehmite 24.2 g are added to 1500 ml of pure water and stirred until dissolved. 165 g of sodium carbonate is weighed and added to 1650 ml of water and stirred until completely dissolved. At room temperature, the above-prepared metal salt solution and sodium carbonate aqueous solution are simultaneously pumped into 300 ml of pure aqueous solution in a stirred state using a peristaltic pump. The pH value of the solution is controlled at 8 until the feeding is completed. Then, it is heated to 65 °C and slowly stirred and aged for 12 h. Then, it is filtered by suction, and the filter cake is washed with pure water until neutral, dried at 120 °C for 12 h, and calcined at 400 °C for 4 h to obtain the as-prepared catalyst powder. The catalyst powder is put into 500 ml of pure water, and 0.216 g of Pt(NO 3 ) 2 is weighed according to the proportion and dissolved in 20 ml of pure water. This solution is gradually added dropwise to the aqueous solution of the catalyst powder in a stirred state using a peristaltic pump and stirred for impregnation for 2 hours. Then, the alkali solution is continued to be added dropwise to the reaction solution in a stirred state at room temperature using a peristaltic pump, the pH value is adjusted to 8.5, the dropping is stopped, and the aging and stirring impregnation are continued for 5 h. Then, it is filtered, and the pure water is repeatedly washed until the pH is neutral. After filtration, the filter cake layer is dried at 120 °C for 5 hours to obtain the catalyst powder, and then it is processed by tableting and sieving to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0055] Example 8

[0056] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, Mo, Co, etc., and the metal ratio is 1:1:0.16:0.06:0.03:0.06:0.03:0.0033. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3) 2 ·4H 2 O 11.66 g, Cr(NO 3 ) 3 ·9H 2 O 18.47 g, H 8 MoN 2 O 4 2.45 g and pseudoboehmite 24.2 g are added to 1500 ml of pure water and stirred until dissolved. 165 g of sodium carbonate is weighed and added to 1650 ml of water and stirred until completely dissolved. At room temperature, the above-prepared metal salt solution and sodium carbonate aqueous solution are simultaneously pumped into 300 ml of pure aqueous solution in a stirred state using a peristaltic pump. The pH value of the solution is controlled at 8 until the feeding is completed. Then, the temperature is raised to 65 °C and slowly stirred and aged for 12 h. Then, it is filtered by suction, and the filter cake is washed with pure water until neutral, dried at 120 °C for 12 h, and calcined at 400 °C for 4 h to obtain the as-prepared catalyst powder. The catalyst powder is put into 500 ml of pure water, and Co(NO 3 ) 2 ·6H 2 O 0.652 g is weighed and dissolved in 20 ml of pure water. This solution is gradually added dropwise to the aqueous solution of the catalyst powder in a stirred state using a peristaltic pump and stirred for impregnation for 2 h. Then, the alkali solution is switched and gradually added dropwise to the reaction solution in a stirred state at room temperature using a peristaltic pump. The pH value is adjusted to 8.5, and the dropping is stopped. The aging and stirring impregnation are continued for 5 h, filtered, and repeatedly washed with pure water until the pH is neutral, filtered, and the filter cake layer is dried at 120 °C for 5 h to obtain the catalyst powder, which is then processed by tableting and sieving to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0057] Example 9

[0058] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, Mo, Pd, Co, etc. The metal ratio is 1:1:0.16:0.06:0.03:0.06:0.03:0.0033:0.0033. Weigh Cu(NO 3 ) 2 ·3H 2 O 152.1 g, Zn(NO 3 ) 2 ·6H 2 O 182.0 g, Mg(NO 3 ) 2 ·6H 2 O, Ca(NO 3 )2·4H 2 O 11.66 g, Cr(NO 3 ) 3 ·9H 2 O 18.47 g, H 8 MoN2 O 4 Dissolve 2.45 g of O and 24.2 g of pseudo-boehmite in 1500 ml of pure water with stirring. Weigh 165 g of sodium carbonate and dissolve it completely in 1650 ml of water with stirring. At room temperature, simultaneously pump the above-prepared metal salt solution and sodium carbonate aqueous solution into 300 ml of pure water under stirring using a peristaltic pump. Control the pH value of the solution at 8 until the feeding is completed. Then, raise the temperature to 65 °C and stir slowly for aging for 12 h. Then, perform suction filtration, wash the filter cake with pure water until it is neutral, dry it at 120 °C for 12 h, and calcine it at 400 °C for 4 h to obtain the as-prepared catalyst powder. Put the catalyst powder into 500 ml of pure water. Weigh 0.286 g of Pd(NO 3 ) 2 and 0.652 g of Co(NO 3 ) 2 ·6H 2 O, dissolve them in 20 ml of pure water. Gradually drip this solution into the stirred aqueous solution of the catalyst powder using a peristaltic pump and stir for impregnation for 2 h. Then, continue to switch to the alkali solution and gradually drip it into the stirred reaction solution at room temperature using a peristaltic pump. Adjust the pH value to 8.5, stop dripping, continue aging and stirring for impregnation for 5 h, filter, repeatedly wash with pure water until the pH is neutral, filter, and dry the filter cake layer at 120 °C for 5 h to obtain the catalyst powder. Then, perform tabletting and sieving treatment to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0059] Example 10

[0060] Select metals such as Cu, Zn, Al, Mg, Ca, Cr, Mo, Pt, Co, etc., with a metal ratio of 1:1:0.16:0.06:0.03:0.06:0.03:0.0033:0.0033. Weigh 152.1 g of Cu(NO 3 ) 2 ·3H 2 O, 182.0 g of Zn(NO 3 ) 2 ·6H 2 O, Mg(NO 3 ) 2 ·6H 2 O, 11.66 g of Ca(NO 3 )2·4H 2 O, 18.47 g of Cr(NO 3 ) 3 ·9H 2 O, H 8 MoN 2 O 42.45 g of pseudo-boehmite and 24.2 g are added to 1500 ml of pure water and stirred until dissolved. 165 g of sodium carbonate is weighed and added to 1650 ml of water and stirred until completely dissolved. At room temperature, the above-prepared metal salt solution and sodium carbonate aqueous solution are simultaneously pumped into 300 ml of pure water under stirring by a peristaltic pump. The pH value of the solution is controlled at 8 until the feeding is completed. Then, the temperature is raised to 65 °C and slowly stirred and aged for 12 h. Then, filtration is carried out, and the filter cake is washed with pure water until neutral, dried at 120 °C for 12 h, and calcined at 400 °C for 4 h to obtain the as-prepared catalyst powder. The catalyst powder is put into 500 ml of pure water. According to the proportion, 0.216 g of Pt(NO 3 ) 2 and 0.652 g of Co(NO 3 ) 2 ·6H 2 O are weighed and dissolved in 20 ml of pure water. This solution is gradually added dropwise to the stirred aqueous solution of the catalyst powder by a peristaltic pump and stirred for impregnation for 2 h. Then, the alkali solution is switched and gradually added dropwise to the stirred reaction solution at room temperature by a peristaltic pump. The pH value is adjusted to 8.5, the dropping is stopped, and the aging and stirring impregnation are continued for 5 h. Filtration is carried out, and the washing with pure water is repeated until the pH is neutral. Filtration is carried out again, and the filter cake layer is dried at 120 °C for 5 h to obtain the catalyst powder. Then, it is processed by tabletting and sieving to obtain a granular catalyst with a particle size of 1 - 2 mm.

[0061] Test Examples 1 - 36:

[0062] Catalyst performance evaluation: 80 g of the catalyst is loaded into a fixed bed with an inner diameter of 12 mm. Hydrogen is passed at 50 ml / min and reduced at 230 °C under atmospheric pressure for 5 h. Then, the temperature is lowered to the reaction temperature in Table 1, the reaction pressure is 3 MPa, and other conditions are shown in Table 1. The raw material has a 2-propyl-2-heptenal content of 97.58%.

[0063] Table 1

[0064]

[0065]

[0066] a The product of full hydrogenation is the hydrogenated product.

[0067] The results of the above test examples show that compared with ordinary CuO-ZnO-Al 2 O 3Compared with the catalyst, after only adding the Mg promoter, the catalytic effect of hydrogen over - reduction is reduced and the selectivity is improved; when further adding non - noble metal promoters such as Mg, Ca, Cr, Mo, etc., the content of by - product hydrogen over - reduction is significantly reduced and the product yield is increased; when further adding noble metal promoters such as Pt, Pd, Co, etc., the content of hydrogen over - reduction is further significantly reduced, and at the same time, the product content is also increased.

[0068] Test Example 37 Catalyst Stability Test

[0069] Select the catalyst of Example 10 and conduct a long - term catalyst life test under the conditions of Test Example 35. The evaluation results are shown in Figure 1 .

[0070] It can be seen from Figure 1 that for the composite high - selectivity, high - activity, and high - stability catalyst developed in the present invention, in Example 10, after 28 weeks of testing, the catalyst activity and selectivity do not decrease, and the product content basically remains unchanged. In Example 1 with the ordinary scheme, the conversion rate and product content significantly decrease after about 10 weeks.

[0071] The embodiments of the present invention have been described above. The above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A hydrogenation catalyst for 2-propyl-2-heptenal, characterized in that It includes active ingredients and auxiliary ingredients; The active components are Cu, Zn and Al, with a Cu content of 20-50%, a Zn content of 20-50%, and an Al content of 4-10% by mass; The auxiliary agent component comprises a non-precious metal auxiliary agent; The non-precious metal additive is a combination of one or more of Ca, Cr, Mo and Mg; By mass, the Mg content is 1-3%, the Ca content is 0.5-1%, the Cr content is 1-5%, and the Mo content is 0.1-1.5%.

2. The hydrogenation catalyst for 2-propyl-2-heptenal according to claim 1, characterized in that The non-precious metal additives are four components: Mg, Ca, Cr and Mo.

3. The hydrogenation catalyst for 2-propyl-2-heptenal according to claim 1 or 2, characterized in that The auxiliary agent component further comprises a precious metal auxiliary agent; The noble metal additive is one or more of Pt, Pd and Co, and the content of the noble metal additive is 0.1% to 0.5%.

4. The hydrogenation catalyst for 2-propyl-2-heptenal according to claim 3, characterized in that The noble metal additives are Pt, Pd and Co.

5. A method for preparing a hydrogenation catalyst according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) dissolving a salt or oxide containing an active combination and a salt containing a non-precious metal additive in water to obtain a metal salt solution, then adding the metal salt solution and an alkali solution simultaneously to water in a stirring state, heating and aging after the addition is completed, and then filtering, washing, drying and calcining to obtain a primary catalyst powder; (2) The primary catalyst powder is directly tableted and sieved, or stirred and impregnated with a salt containing a precious metal additive, then aged with an alkaline solution, washed with water, dried, and then tableted and sieved to obtain the hydrogenation catalyst.

6. The method for preparing a hydrogenation catalyst according to claim 5, characterized in that: The salt containing the active combination is Cu(NO3)2·3H2O, Zn(NO3)2·6H2O and pseudo-boehmite; The salt of the non-precious metal additive is one or more of Mg(NO3)2·6H2O, Ca(NO3)2·4H2O, Cr(NO3)3·9H2O, and H8MoN2O4; The salt of the noble metal catalyst is one or more of Pt(NO3)2, Pd(NO3)2 or Co(NO3)2·6H2O.

7. The method for preparing a hydrogenation catalyst according to claim 5, characterized in that: In step (1), the pH value during the addition of the material is 7.5 to 8.5; The heating aging temperature is 60-70°C, and the stirring aging time is 10-15h; The drying temperature is 110-130°C and the drying time is 10-15h; The calcination temperature is 350-450°C and the calcination time is 3-5h; In step (2), an alkaline solution is added to control the pH value to 8-9.

8. A method for preparing 2-propylheptanol, characterized in that: include: Under the action of the hydrogenation catalyst described in any one of claims 1 to 4, 2-propyl-2-heptenal is hydrogenated in a hydrogen atmosphere to obtain the 2-propylheptanol.

9. The method for preparing 2-propylheptanol according to claim 8, characterized in that: First, the hydrogenation catalyst is reduced at normal pressure by passing hydrogen gas at a reduction temperature of 220-240° C.; then the hydrogenation reaction is carried out at a reaction pressure of 2-4 MPa and a reaction temperature of 140-170° C.

10. The method for preparing 2-propylheptanol according to claim 8 or 9, characterized in that: The hydrogenation catalyst is loaded in a fixed bed reactor, and the 2-propyl-2-heptenal and hydrogen are introduced into the fixed bed reactor for hydrogenation reaction.

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