A catalyst for preparing isonitric acid and a method for preparing the same

Abstract

The application discloses a catalyst for preparing isonitric acid and a preparation method thereof, and belongs to the field of chemical industry. The method uses mesoporous carbon with a large specific surface area as a carrier, and then uses manganese compounds and rare earth element compounds as a catalytic active component, so that the prepared product has high catalytic efficiency, can be applied to the preparation of isonitric acid from isonitric aldehyde, and has a highest raw material catalytic conversion rate of 99.9%, and has good stability. Meanwhile, the catalyst belongs to a heterogeneous catalyst, is very easy to separate and recycle, and has high practical value.

Description

TECHNICAL FIELD

[0001] The present application relates to the chemical technology field, and in particular to a catalyst for preparing isononyl acid and a preparation method thereof. BACKGROUND

[0002] Isononyl acid is an important organic chemical raw material, which has excellent wetting, permeability and emulsifying properties, and is widely used in lubricants, industrial detergents, cosmetics, pharmaceuticals and other fields. Direct oxidation of isononyl aldehyde to prepare isononyl acid is the main isononyl acid production process at present, which has the advantages of simple process route, mild process conditions, single raw material variety, etc.

[0003] The process for preparing isononyl acid by oxidation of isononyl aldehyde mainly uses manganese, cobalt, copper and other transition metal salts as homogeneous catalysts. Such catalysts often have the advantages of mild reaction conditions and high catalytic efficiency. However, such catalysts also have the problem of difficult recovery 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 comprehensive catalytic efficiency. SUMMARY

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

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a catalyst for preparing isononyl acid, comprising the following steps:

[0007] (1) Dissolve a surfactant and a phosphorus source in water, then add a catalyst and a silicon source, mix uniformly and react at 35-45℃ for 20-25h to obtain a mixed solution A;

[0008] (2) Crystallize the mixed solution A at 50-80℃ for 12-36h, then filter and dry to obtain a solid B;

[0009] (3) Calcine the solid B at 500-600℃ for 4-10h to obtain a solid C;

[0010] (4) the solid C is put into water, then concentrated sulfuric acid and a carbon source are added and mixed uniformly, then it is placed at 50-60℃ for 6-10h, dried, and calcined at 700-900℃ for 2-6h under a protective atmosphere, and the obtained sample is washed by hydrofluoric acid to obtain mesoporous carbon D;

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

[0012] In the technical scheme, first, a template with a specific morphology is prepared from a silicon source and other additives, 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 is obtained, then a self-assembled loading of a catalytically active component is performed by impregnation, which does not affect the original structure of the carrier, and the product prepared has a high contact area and catalytic activity during catalysis, and can be effectively recovered after 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 mixing 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 mixing reaction is 0.02-0.04:4-8:150-180:0.03-0.06:1.

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

[0015] Preferably, in the step (2), the temperature of the static crystallization is 60-65℃, and the time is 18-24h.

[0016] Preferably, in the step (3), the temperature of the calcination is 540-570℃, and the time is 6-8h.

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

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

[0019] More preferably, in the step (4), the temperature during the static placement is 54-58℃.

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

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

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

[0023] The mesoporous carbon material prepared by using the mesoporous silica molecular sieve as a hard film plate according to the method of the present application has an ideal specific surface area and pore volume, can sufficiently load catalytically active components, and provides sufficient catalytic contact area for the process of preparing isononanoic acid from isononanal, thereby improving the catalytic efficiency of the overall catalyst.

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

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

[0026] Preferably, in the step (5), the solvent of the solution 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] Under the concentration, the two catalytically active components can be effectively and uniformly loaded on the surface of the mesoporous carbon to form a composite catalyst, and no obvious agglomeration phenomenon occurs, and the catalytic effect is excellent.

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

[0029] The catalyst prepared by the method has a large specific surface area and high catalytic activity, and can achieve a raw material conversion rate of up to 99.9% when catalytically preparing isononanoic acid, and the catalyst is a heterogeneous catalyst, and thus is easy to recycle and utilize.

[0030] Still another object of the present application is to provide the application of the catalyst in the catalytic oxidation of isononanal to prepare isononanoic acid.

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

[0032] The present application has the advantages that the present application provides a preparation method of a catalyst for preparing isononyl acid, which uses mesoporous carbon with a large specific surface area as a carrier, and then uses manganese compounds and rare earth element compounds as catalytically active components, the prepared product has high catalytic efficiency, can reach a raw material catalytic conversion rate of 99.9% when applied to the preparation of isononyl acid from isononyl aldehyde, has good stability, belongs to a heterogeneous catalyst, is very easy to separate and recover, and has high practical value. DETAILED DESCRIPTION

[0033] In order to better illustrate the purposes, technical solutions and advantages of the present application, the present application will be further described below in combination with specific examples and comparative examples, and the purpose is to understand the content of the present application in detail, rather than to limit the present application. All other examples obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application. The experimental reagents and instruments involved in the implementation of the present application are all common ordinary reagents and instruments unless otherwise specified.

[0034] Example 1

[0035] An embodiment of the catalyst for preparing isononyl acid and the preparation method thereof, the preparation method comprises the following steps:

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

[0037] (2) The mixed solution A is transferred to an oven and crystallized at 60℃ for 24 h, then filtered, washed and dried to obtain a solid B;

[0038] (3) The solid B is calcined at 550℃ for 7 h in a tube furnace to obtain a white powder solid C;

[0039] (4) 1 g of the solid C is placed in 800 mL of water, then 0.2 g of concentrated sulfuric acid and 1 g of sucrose are added and mixed uniformly, then the mixture is placed at 55℃ for 8 h, dried at 130℃ for 8 h, and calcined at 800℃ for 5 h under a nitrogen atmosphere with a pressure of 1 MPa, and the obtained sample is immersed and washed in a hydrogen fluoride solution for 6 h, then washed with deionized water and dried to obtain mesoporous carbon D; the specific surface area of the mesoporous carbon D is 1100 m 2 / g, and the pore volume is 1.2 cm 3 / g.

[0040] (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 carbon D is added to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0041] Example 2

[0042] An embodiment of the catalyst for preparing isononyl acid and the method of preparing the same according to the present application is different from Example 1 only in that the step (5) is:

[0043] (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 carbon D is added to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0044] Example 3

[0045] An embodiment of the catalyst for preparing isononyl acid and the method of preparing the same according to the present application is different from Example 1 only in that the step (5) is:

[0046] (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 carbon D is added to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0047] Example 4

[0048] An embodiment of the catalyst for preparing isononyl acid and the method of preparing the same according to the present application is different from Example 1 only in that the step (5) is:

[0049] (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 carbon D is added to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0050] Comparative Example 1

[0051] An embodiment of the catalyst for preparing isononyl acid and the method of preparing the same according to the present application is different from Example 1 only in 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 to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0053] Comparative Example 2

[0054] One embodiment of a catalyst for preparing isononyl acid and a method for preparing the same, the difference from Example 1 is only that the step (5) is:

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

[0056] Comparative Example 3

[0057] One embodiment of a catalyst for preparing isononyl acid and a method for preparing the same, the method for preparing the same comprises the following steps:

[0058] 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 commercial ZSM-5 molecular sieve was added to impregnate at 80°C for 5 h, dried, tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0059] Comparative Example 4

[0060] One embodiment of a catalyst for preparing isononyl acid and a method for preparing the same, the method for preparing the same comprises the following steps:

[0061] (1) 0.2 g of surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene), 40 g of phosphoric acid was dissolved in 1500 mL of water, and then 0.5 g of tin chloride and 10 g of TEOS were added, mixed uniformly 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 crystallized at 60°C for 24 h, and then filtered, washed, and dried to obtain a solid B;

[0063] (3) The solid B was calcined at 550°C for 7 h in a tube furnace to obtain a white powder solid C;

[0064] (4) 1 g of solid C was placed in 800 mL of water, and then 0.2 g of concentrated sulfuric acid and 1 g of sucrose were added and mixed uniformly, and then placed at 55°C for 8 h, dried at 130°C for 8 h, and calcined at 800°C for 5 h under a nitrogen atmosphere at a pressure of 1 MPa, washed with deionized water and dried to obtain mesoporous silicon-carbon D;

[0065] (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 silica-carbon D was added and mixed for impregnation at 80°C for 5 h, dried, and then tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0066] Comparative Example 5

[0067] An embodiment of a catalyst for preparing isononyl acid and a method of preparing the same, the method of preparing the same, comprising the steps of:

[0068] (1) 0.2 g of a surfactant P123 (polyoxyethylene-polyoxypropylene-polyoxypropylene), 40 g of phosphoric acid, and 1500 mL of water were mixed to prepare a solution, and then 0.5 g of tin chloride and 10 g of TEOS were added and mixed to prepare a mixed solution A;

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

[0070] (3) The solid B was calcined at 550°C for 7 h in a tube furnace to obtain a white powder solid C;

[0071] (4) 1 g of the solid C was placed in 800 mL of water, and then 0.2 g of concentrated sulfuric acid and 1 g of sucrose were added and mixed to prepare a solution, and then the solution was left to stand at 55°C for 8 h, dried at 130°C for 8 h, and calcined at 600°C for 3 h under a nitrogen atmosphere at a pressure of 1 MPa, and then the obtained sample was impregnated with a solution prepared by dissolving hydrogen fluoride in water for 6 h, and then 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, and the pore volume was 0.7 cm 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 silica-carbon D was added and mixed for impregnation at 80°C for 5 h, dried, and then tableted, crushed, and sieved to 100-200 mesh to obtain the catalyst for preparing isononyl acid.

[0073] Comparative Example 6

[0074] An embodiment of a catalyst for preparing isononyl acid and a method of preparing the same, the method of preparing the same, comprising the steps of:

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

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

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

[0078] (4) 1 g of the solid C was placed into 800 mL of water, then 0.2 g of concentrated sulfuric acid and 1 g of sucrose were added and mixed uniformly, then placed at 55°C for 8 h, dried at 130°C for 8 h and calcined at 1000°C for 8 h under the nitrogen atmosphere at a pressure of 2 MPa, and the obtained sample was immersed and washed by a solution prepared from hydrofluoric acid for 6 h, then washed by deionized water and dried to obtain a mesoporous carbon D; the specific surface area of the mesoporous carbon D was 650 m 2 / g, and the pore volume was 0.6 cm 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, then 25 g of the mesoporous carbon D was added and mixed for impregnation at 80°C for 5 h, dried, and then tabletted, crushed, sieved to 100-200 meshes to obtain the catalyst for preparing isonitric acid.

[0080] Effect Example 1

[0081] In order to verify the catalytic effect of the catalyst prepared by the method of the present application, the catalysts prepared in each example and the comparative example were taken in equal amounts and added into the same amount of isonitroaldehyde, and reacted in a 1L high-pressure reaction kettle under the conditions of 50°C, 0.5 MPa and an oxygen flow rate of 500 mL / min for 4 h, after the reaction, the product composition was detected by gas chromatography, and the conversion rate of isonitroaldehyde and the selectivity of isonitric acid were calculated, and the results are shown in Table 1.

[0082] Table 1

[0083]

[0084]

[0085] From Table 1, it can be seen that the catalysts prepared according to the present application have very high raw material catalytic conversion efficiency when used to prepare isonitric acid by catalytic oxidation. The conversion rate of isonitroaldehyde can reach more than 99% and the selectivity of isonitric acid can reach more than 95% when the products of the four examples are used. In comparison, the product of Comparative Example 3, which uses a commercial molecular sieve as a carrier, has low selectivity of isonitroaldehyde and isonitric acid because the catalytically active components cannot be fully contacted. If the hard template is not removed during the preparation of the carrier, as shown in the product of Comparative Example 4, the subsequent loading of catalytically active components and the final catalytic effect are not ideal. Even if the hard template is removed, if the conditions during the calcination of the mesoporous carbon are not properly set, as shown in Comparative Examples 5 and 6, the structure of the carrier is not ideal and the catalytic effect of the product is affected. In the selection of catalytically active components, as shown in Comparative Examples 1 and 2, if only manganese catalytic components or rare earth catalytic components are selected, the best catalytic effect cannot be achieved.

[0086] Subsequently, the catalyst in Example 1 was recovered and used to prepare isonitric acid in a second batch under the same conditions. This step was repeated five times, and the catalytic results data of the catalyst after one, two and five cycles of recycling were counted. The test and counting methods were the same as above, and the results are shown in Table 2.

[0087] Table 1

[0088] Cycles of recycling Conversion of isonitroaldehyde (%) Selectivity of isonitric acid (%) 1 99.1 95.2 2 98.7 94.9 5 96.7 93.7

[0089] As can be seen, after multiple cycles of recycling, the catalyst prepared in Example 1 indeed has a decline in effect when used, but after five cycles of recycling, the conversion rate of isonitroaldehyde can still be more than 95% and the selectivity of isonitric acid can be more than 92%, and the recycling performance is still better than that of the catalyst product prepared from the commercial molecular sieve described in Comparative Example 3.

[0090] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for preparing a catalyst for isononanoic acid, characterized in that, Includes the following steps: (1) Dissolve the surfactant and phosphorus source in water, then add the catalyst and silicon source, mix evenly, and react at 35~45℃ for 20~25h to obtain mixture A; (2) Let the mixture A stand at 50~80℃ for 12~36h to crystallize, then filter and dry to obtain solid B; (3) Calcine solid B at 500~600℃ for 4~10h to obtain solid C; (4) Solid C is placed in water, then concentrated sulfuric acid and carbon source are added and mixed evenly. The mixture is then allowed to stand at 50-60℃ for 6-10 hours, dried, and calcined at 700-900℃ for 2-6 hours under a protective atmosphere. The resulting sample is washed with hydrofluoric acid to obtain mesoporous carbon D. The specific surface area of ​​mesoporous carbon D is 650-1100 m². 2 / g, pore volume ≥1cm³ 3 / g; (5) Prepare a solution by mixing manganese source and rare earth element source, then add mesoporous carbon D and mix and impregnate at 60~90℃ for 4~6h, dry, and after pressing, crushing and sieving to 100~200 mesh, the catalyst for preparing isononanoic acid is obtained; the solvent of the solution is at least one of methanol, ethanol, propanol, n-butanol, isoamyl alcohol, n-hexanol and acetone, the mass content of manganese source in the solution is 1~10%, the mass content of rare earth element source is 0.01~1%, the mass of solvent is 1000 g, and the mass of mesoporous carbon D is 25 g.

2. The method for preparing the catalyst for isononanoic acid as described in claim 1, characterized in that, In 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. The mass ratio of surfactant, phosphoric acid, water, catalyst and tetraethyl orthosilicate in the mixed reaction is 0.01~0.05:2~10:100~200:0.01~0.09:

1.

3. The method for preparing the catalyst for isononanoic acid as described in claim 1, characterized in that, The carbon source in step (4) is sucrose.

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

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

6. The catalyst for preparing isononanoic acid prepared by the preparation method according to any one of claims 1 to 5.

7. The application of the catalyst as described in claim 6 in the catalytic oxidation of isonononal as a raw material to prepare isonononic acid.

8. The application as described in claim 7, characterized in that, The catalytic oxidation was carried out at a temperature of 50-60℃, a pressure of 0.1-1MPa, and an oxygen flow rate of 400-600mL / min.

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