Catalyst for preparing isononanoic acid and preparation method thereof

Abstract

The invention discloses a catalyst for preparing isononanoic acid and a preparation method of the catalyst, and belongs to the field of chemical engineering. According to the method, mesoporous carbon with a large specific surface area serves as a carrier, then a manganese compound and a rare earth element compound are compounded to serve as a catalytic active component, the prepared product is high in catalytic efficiency, the highest raw material catalytic conversion rate can reach 99.9% when the product is applied to preparation of isononanoic acid with isononanal as a raw material, stability is good, meanwhile, the product belongs to a heterogeneous catalyst, and the catalyst is suitable for industrial production. The method is very easy to separate and recycle, and has high practical value.

Description

Technical Field

[0001] The invention relates to the technical field of chemical industry, and in particular to a catalyst for preparing isononanoic acid and a preparation method thereof. Background Art

[0002] Isononanoic acid is an important organic chemical raw material. It has excellent wettability, permeability and emulsification, so it is widely used in lubricants, industrial detergents, cosmetics, medicine and other fields. The direct oxidation of isononanal to prepare isononanoic acid is the main isononanoic acid production process at present. This process has the advantages of simple process route, mild process conditions and single raw material variety.

[0003] The process of preparing isononanoic acid by oxidation of isononanal mainly uses transition metal salts such as manganese, cobalt, and copper as homogeneous catalysts. Such catalysts often have advantages such as mild reaction conditions and high catalytic efficiency; however, such catalysts also have problems such as difficulty in recycling and reuse. On the other hand, some heterogeneous catalysts have also been developed and applied, such as products prepared by loading transition metal compounds on metal organic frameworks; however, the preparation process of such heterogeneous catalysts is too complicated, and the specific surface area of ​​the carrier is generally small, resulting in low overall catalytic efficiency. Summary of the invention

[0004] Based on the defects of the prior art, the purpose of the present invention is to provide a method for preparing a catalyst for preparing isononanoic acid, which uses mesoporous carbon with a large specific surface area as a carrier, and then uses a manganese compound and a rare earth element compound as a catalytically active component. The prepared product not only has high catalytic efficiency and good stability, but is also very easy to separate and recover, and has high practical value.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing a catalyst for preparing isononanoic acid comprises the following steps:

[0007] (1) dissolving a surfactant and a phosphorus source in water, then adding a catalyst and a silicon source, mixing them evenly, and reacting them at 35 to 45° C. for 20 to 25 hours to obtain a mixed solution A;

[0008] (2) allowing the mixed solution A to stand for crystallization at 50-80° C. for 12-36 hours, followed by filtering and drying to obtain a solid B;

[0009] (3) calcining solid B at 500-600°C for 4-10 hours to obtain solid C;

[0010] (4) placing solid C in water, then adding concentrated sulfuric acid and a carbon source and mixing evenly, then standing at 50-60° C. for 6-10 h, drying, and calcining at 700-900° C. for 2-6 h under a protective atmosphere. The obtained sample is washed with hydrofluoric acid to obtain mesoporous carbon D;

[0011] (5) A manganese source and a rare earth element source are prepared into a solution, and then the mesoporous carbon D is added and mixed and impregnated at 60 to 90° C. for 4 to 6 hours, dried, tableted, crushed, and sieved to 100 to 200 meshes to obtain the catalyst for preparing isononanoic acid.

[0012] In the technical solution of the present invention, a template with a specific morphology is first prepared with a silicon source and other additives, and then a carbon source is introduced to prepare a mesoporous carbon precursor. After calcination and template removal, a mesoporous carbon carrier with a high specific surface area can be obtained. Subsequently, the catalytically active components are self-assembled and loaded by impregnation, which will not affect the original structure of the carrier. The prepared product has a high contact area and catalytic activity during catalysis, and can be effectively recovered after the catalysis is completed.

[0013] Preferably, in the step (1), the surfactant is polyoxyethylene-polyoxypropylene-polyoxypropylene, the phosphorus source is phosphoric acid, the catalyst is tin chloride, the silicon source is tetraethyl orthosilicate, and the mass ratio of the surfactant, phosphoric acid, water, catalyst and tetraethyl orthosilicate during the mixed reaction is 0.01-0.05: 2-10: 100-200: 0.01-0.09: 1. More preferably, the mass ratio of the surfactant, phosphoric acid, water, catalyst and tetraethyl orthosilicate during the mixed reaction is 0.02-0.04: 4-8: 150-180: 0.03-0.06: 1.

[0014] Preferably, the temperature of the mixing reaction in step (1) is 38-42°C.

[0015] Preferably, the temperature for standing crystallization in step (2) is 60-65° C. and the time is 18-24 hours.

[0016] Preferably, the calcination temperature in step (3) is 540-570° C. and the calcination time is 6-8 hours.

[0017] Under the process conditions, the raw materials can effectively react and form a mesoporous molecular sieve material with an ideal morphology, and then serve as a hard template to generate a mesoporous carbon with a pore structure in a subsequent process.

[0018] Preferably, the carbon source in step (4) is sucrose.

[0019] More preferably, the temperature during standing in step (4) is 54-58°C.

[0020] Preferably, the drying temperature in step (4) is 120-160° C. and the drying time is 5-10 hours.

[0021] Preferably, the protective atmosphere in step (4) is nitrogen, and the pressure is 0.1 to 5 MPa; more preferably 0.5 to 2 MPa.

[0022] Preferably, the specific surface area of ​​the mesoporous carbon D in step (4) is 650-1100 m 2 / g, pore volume ≥1cm 3 / g.

[0023] The mesoporous carbon material prepared by using mesoporous silica molecular sieve as the hard film plate according to the method steps of the present invention has an ideal specific surface area and pore volume, can fully load the catalytic active components, provide sufficient catalytic contact area for the process of catalyzing isononanaldehyde to prepare isononanoic acid, and improve the catalytic efficiency of the overall catalyst.

[0024] Preferably, in step (5), the manganese source is at least one of manganese acetate, manganese sulfate, manganese nitrate, manganese bromide and manganese chloride.

[0025] Preferably, in step (5), the rare earth element source is at least one of cerium chloride, yttrium chloride, cerium sulfate, yttrium sulfate and cerium nitrate.

[0026] Preferably, the solvent of the solution in step (5) is at least one of methanol, ethanol, propanol, n-butanol, isoamyl alcohol, n-hexanol and acetone, the mass content of the manganese source in the solution is 1-10%, and the mass content of the rare earth element source is 0.01-1%; more preferably, the mass content of the manganese source in the solution is 2-5%, and the mass content of the rare earth element source is 0.02-0.1%.

[0027] At the concentration, the two catalytically active components can be effectively and evenly loaded on the surface of the mesoporous carbon to form a composite catalyst without obvious agglomeration, and the catalytic effect is excellent.

[0028] Another object of the present invention is to provide a catalyst for preparing isononanoic acid prepared by the preparation method.

[0029] The catalyst prepared by the method of the present invention has a large specific surface area and high catalytic activity. When catalytically preparing isononanoic acid, a raw material conversion rate of up to 99.9% can be achieved. Since the catalyst is a heterogeneous catalyst, it is also easy to recycle and reuse.

[0030] Another object of the present invention is to provide an application of the catalyst in the preparation of isononanoic acid by catalytic oxidation using isononanal as a raw material.

[0031] Preferably, the temperature during the catalytic oxidation is 50-60° C., the pressure is 0.1-1 MPa, and the oxygen flow rate is 400-600 mL / min.

[0032] The beneficial effect of the present invention is that the present invention provides a preparation method of a catalyst for preparing isononanoic acid. The method uses mesoporous carbon with a large specific surface area as a carrier, and then uses a manganese compound and a rare earth element compound as a catalytic active component. The prepared product has not only high catalytic efficiency, but also can achieve a raw material catalytic conversion rate of up to 99.9% when used in preparing isononanoic acid from isononaldehyde as a raw material, and has good stability. At the same time, it is a heterogeneous catalyst, which is very easy to separate and recover and has high practical value. DETAILED DESCRIPTION

[0033] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention, unless otherwise specified, are all commonly used common reagents and instruments.

[0034] Example 1

[0035] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof according to the present invention, wherein the preparation method comprises the following steps:

[0036] (1) 0.2 g of surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene) and 40 g of phosphoric acid were dissolved in 1500 mL of water, and then 0.5 g of tin chloride and 10 g of TEOS were added, mixed evenly and reacted at 40° C. for 24 h to obtain a mixed solution A;

[0037] (2) The mixed solution A was transferred to an oven and allowed to stand at 60° C. for crystallization for 24 h, and then filtered, washed, and dried to obtain solid B;

[0038] (3) calcining solid B at 550°C in a tube furnace for 7 h to obtain solid C in the form of a white powder;

[0039] (4) 1 g of solid C was placed in 800 mL of water, followed by adding 0.2 g of concentrated sulfuric acid and 1 g of sucrose and mixing evenly, followed by standing at 55 ° C for 8 h, drying at 130 ° C for 8 h, and calcining at 800 ° C for 5 h in a nitrogen atmosphere at a pressure of 1 MPa. The obtained sample was immersed in a solution prepared with hydrofluoric acid for 6 h, washed with deionized water and dried to obtain mesoporous carbon D; the specific surface area of ​​the mesoporous carbon D was 1100 m 2 / g, pore volume is 1.2cm 3 / g;

[0040] (5) 30 g of manganese acetate and 2 g of cerium chloride were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0041] Example 2

[0042] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof according to the present invention is different from Embodiment 1 only in that the step (5) is:

[0043] (5) 30 g of manganese sulfate and 2 g of cerium chloride were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0044] Example 3

[0045] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof according to the present invention is different from Embodiment 1 only in that the step (5) is:

[0046] (5) 30 g of manganese nitrate and 2 g of cerium chloride were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0047] Example 4

[0048] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof according to the present invention is different from Embodiment 1 only in that the step (5) is:

[0049] (5) 30 g of manganese acetate and 2 g of cerium sulfate were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0050] Comparative Example 1

[0051] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof, the difference from embodiment 1 is only that the step (5) is:

[0052] (5) 30 g of manganese sulfate was dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0053] Comparative Example 2

[0054] An embodiment of a catalyst for preparing isononanoic acid and a preparation method thereof, the difference from embodiment 1 is only that the step (5) is:

[0055] (5) 2 g of cerium chloride is dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D is added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononanoic acid.

[0056] Comparative Example 3

[0057] A catalyst for preparing isononanoic acid and an embodiment of a preparation method thereof, the preparation method comprising:

[0058] 30 g of manganese sulfate and 2 g of cerium chloride are dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of commercial ZSM-5 molecular sieve is added, mixed and impregnated at 80° C. for 5 h, dried, tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0059] Comparative Example 4

[0060] A catalyst for preparing isononanoic acid and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:

[0061] (1) 0.2 g of surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene) and 40 g of phosphoric acid were dissolved in 1500 mL of water, and then 0.5 g of tin chloride and 10 g of TEOS were added, mixed evenly and reacted at 40° C. for 24 h to obtain a mixed solution A;

[0062] (2) The mixed solution A was transferred to an oven and allowed to stand at 60° C. for crystallization for 24 h, and then filtered, washed, and dried to obtain solid B;

[0063] (3) calcining solid B at 550°C in a tube furnace for 7 h to obtain solid C in the form of a white powder;

[0064] (4) 1 g of solid C was placed in 800 mL of water, followed by adding 0.2 g of concentrated sulfuric acid and 1 g of sucrose and mixing well, followed by standing at 55 ° C for 8 h, drying at 130 ° C for 8 h, and calcining at 800 ° C for 5 h in a nitrogen atmosphere at a pressure of 1 MPa, washing with deionized water and drying to obtain mesoporous silicon-carbon D;

[0065] (5) 30 g of manganese acetate and 2 g of cerium chloride are dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous silicon-carbon D is added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0066] Comparative Example 5

[0067] A catalyst for preparing isononanoic acid and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:

[0068] (1) 0.2 g of surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene) and 40 g of phosphoric acid were dissolved in 1500 mL of water, and then 0.5 g of tin chloride and 10 g of TEOS were added, mixed evenly and reacted at 40° C. for 24 h to obtain a mixed solution A;

[0069] (2) The mixed solution A was transferred to an oven and allowed to stand at 60° C. for crystallization for 24 h, and then filtered, washed, and dried to obtain solid B;

[0070] (3) calcining solid B at 550°C in a tube furnace for 7 h to obtain solid C in the form of a white powder;

[0071] (4) 1 g of solid C was placed in 800 mL of water, followed by adding 0.2 g of concentrated sulfuric acid and 1 g of sucrose and mixing evenly, followed by standing at 55 ° C for 8 h, drying at 130 ° C for 8 h, and calcining at 600 ° C for 3 h in a nitrogen atmosphere at a pressure of 1 MPa. The obtained sample was immersed in a solution prepared with hydrofluoric acid for 6 h, washed with deionized water and dried to obtain mesoporous carbon D; the specific surface area of ​​the mesoporous carbon D was 700 m 2 / g, pore volume is 0.7cm 3 / g;

[0072] (5) 30 g of manganese acetate and 2 g of cerium chloride were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0073] Comparative Example 6

[0074] A catalyst for preparing isononanoic acid and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:

[0075] (1) 0.2 g of surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene) and 40 g of phosphoric acid were dissolved in 1500 mL of water, and then 0.5 g of tin chloride and 10 g of TEOS were added, mixed evenly and reacted at 40° C. for 24 h to obtain a mixed solution A;

[0076] (2) The mixed solution A was transferred to an oven and allowed to stand at 60° C. for crystallization for 24 h, and then filtered, washed, and dried to obtain solid B;

[0077] (3) calcining solid B at 550°C in a tube furnace for 7 h to obtain solid C in the form of a white powder;

[0078] (4) 1 g of solid C was placed in 800 mL of water, followed by adding 0.2 g of concentrated sulfuric acid and 1 g of sucrose and mixing evenly, followed by standing at 55 ° C for 8 h, drying at 130 ° C for 8 h, and calcining at 1000 ° C for 8 h in a nitrogen atmosphere at a pressure of 2 MPa. The obtained sample was immersed in a solution prepared with hydrofluoric acid for 6 h, washed with deionized water and dried to obtain mesoporous carbon D; the specific surface area of ​​the mesoporous carbon D was 650 m 2 / g, pore volume is 0.6cm 3 / g;

[0079] (5) 30 g of manganese acetate and 2 g of cerium chloride were dissolved in 1000 g of ethanol to prepare a solution, and then 25 g of mesoporous carbon D was added and mixed and impregnated at 80° C. for 5 h, dried, and tableted, crushed, and sieved to 100-200 meshes to obtain the catalyst for preparing isononanoic acid.

[0080] Effect Example 1

[0081] In order to verify the catalytic effect of the catalyst prepared by the method of the present invention, equal amounts of the catalysts prepared in the embodiments and comparative examples were added with the same amount of isononanal, and the reaction was carried out in a 1L high-pressure reactor at 50°C, 0.5MPa and an oxygen flow rate of 500mL / min for 4h. After the reaction, the product composition was detected by gas chromatography, and the conversion rate of isononanal and the selectivity of isononanoic acid were statistically calculated. The results are shown in Table 1.

[0082] Table 1

[0083]

[0084]

[0085] As can be seen from Table 1, the catalyst of the present invention has an extremely high catalytic conversion efficiency of raw materials when catalytic oxidation is performed to prepare isononanoic acid. When the products of the four embodiments are used, the conversion rate of isononanal can reach more than 99%, and the selectivity of isononanoic acid can reach nearly 95% or more. In contrast, the product of Comparative Example 3 using commercial molecular sieves as carriers has low selectivities of isononanal and isononanoic acid because it cannot fully achieve comprehensive contact of catalytically active components. In the process of carrier preparation, if the hard template is not removed, as shown in the product of Comparative Example 4, the subsequent loading of catalytically active components and the final catalytic effect are not ideal; and even if the hard template is removed later, if the conditions are not properly set during the process of calcining to generate mesoporous carbon, as shown in Comparative Examples 5 and 6, the constructed carrier structure is not ideal, and the catalytic effect of the product will also be affected. In the selection of catalytically active components, it can be seen from Comparative Examples 1 and 2 that if only manganese catalytic components or rare earth element catalytic components are selected, the best catalytic effect cannot be achieved.

[0086] Subsequently, the catalyst in Example 1 was recovered and used to prepare a second batch of isononanoic acid under the same conditions. This step was repeated 5 times, and the catalytic result data of the catalyst when it was recycled and used 1 time, 2 times and 5 times were statistically analyzed. The test and statistical methods were the same as above, and the results are shown in Table 2.

[0087] Table 1

[0088] Recycling times Isononanal conversion rate (%) Isononanoic acid selectivity (%) 1 99.1 95.2 2 98.7 94.9 5 96.7 93.7

[0089] It can be seen that after multiple cycles of recovery, the effect of the catalyst prepared in Example 1 is indeed reduced during use, but after 5 cycles of recovery, it can still ensure that the conversion rate of isononanal reaches more than 95%, and the selectivity of isononanoic acid reaches more than 92%. The cycle performance is still better than the catalyst product prepared by the commercial molecular sieve described in Comparative Example 3.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a catalyst for preparing isononanoic acid, characterized in that: The following steps are involved: (1) dissolving a surfactant and a phosphorus source in water, then adding a catalyst and a silicon source, mixing them evenly, and reacting them at 35 to 45° C. for 20 to 25 hours to obtain a mixed solution A; (2) allowing the mixed solution A to stand for crystallization at 50-80° C. for 12-36 hours, followed by filtering and drying to obtain a solid B; (3) calcining solid B at 500-600°C for 4-10 hours to obtain solid C; (4) placing solid C in water, then adding concentrated sulfuric acid and a carbon source and mixing evenly, then standing at 50-60° C. for 6-10 h, drying, and calcining at 700-900° C. for 2-6 h under a protective atmosphere. The obtained sample is washed with hydrofluoric acid to obtain mesoporous carbon D; (5) A manganese source and a rare earth element source are prepared into a solution, and then the mesoporous carbon D is added and mixed and impregnated at 60 to 90° C. for 4 to 6 hours, dried, tableted, crushed, and sieved to 100 to 200 meshes to obtain the catalyst for preparing isononanoic acid.

2. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: In the step (1), the surfactant is polyoxyethylene-polyoxypropylene-polyoxypropylene, the phosphorus source is phosphoric acid, the catalyst is tin chloride, and the silicon source is tetraethyl orthosilicate. During the mixing reaction, the mass ratio of the surfactant, phosphoric acid, water, catalyst and tetraethyl orthosilicate is 0.01-0.05:2-10:100-200:0.01-0.09:

1.

3. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: In the step (4), the carbon source is sucrose.

4. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: The specific surface area of ​​the mesoporous carbon D in step (4) is 650 to 1100 m 2 / g, pore volume ≥1cm 3 / g.

5. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: In the step (5), the manganese source is at least one of manganese acetate, manganese sulfate, manganese nitrate, manganese bromide and manganese chloride.

6. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: In the step (5), the rare earth element source is at least one of cerium chloride, yttrium chloride, cerium sulfate, yttrium sulfate, and cerium nitrate.

7. The method for preparing a catalyst for preparing isononanoic acid according to claim 1, characterized in that: The solvent of the solution in step (5) is at least one of methanol, ethanol, propanol, n-butanol, isopentanol, n-hexanol and acetone, the mass content of manganese source in the solution is 1-10%, and the mass content of rare earth element source is 0.01-1%.

8. A catalyst for preparing isononanoic acid obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the catalyst as claimed in claim 8 in the preparation of isononanoic acid by catalytic oxidation using isononanal as a raw material.

10. The use according to claim 9, characterized in that The temperature during the catalytic oxidation is 50-60° C., the pressure is 0.1-1 MPa, and the oxygen flow rate is 400-600 mL / min.

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