A selective hydrogenation catalyst for ketene and its preparation method and application

Abstract

The present invention discloses a ketene selective hydrogenation catalyst, its preparation method, and application. The catalyst is prepared by mixing a carrier in a molten state with an active metal substance and calcining the mixture. The active metal substance is mixed in a mass ratio of the metal element to the carrier of (0.01-0.2):1, preferably (0.02-0.1):1. The carrier is obtained by vulcanizing a resin precursor. The resin precursor is selected from at least one of phenolic resin, furan resin, and urea-formaldehyde resin. The active metal substance is selected from a metal salt or a metal element of at least one of Pd, Pt, and Ru. The catalyst provided by the present invention has the characteristics of uniform composition, small active component particle size, high activity, high product selectivity, and good application effect.

Description

Technical Field

[0001] The present invention relates to a hydrogenation catalyst, in particular to a ketene selective hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Selective reduction of carbon-carbon double bonds in enones can yield highly valuable fine chemicals. Currently, palladium-based catalysts are commonly used in the industry for selective hydrogenation of enones. Palladium metal facilitates hydrogen activation, and a range of methods are recommended to control palladium activity to prevent it from converting the target product into other byproducts. Optimizing palladium activity, preventing the loss of active components, and improving catalyst stability are currently pressing challenges.

[0003] CN118184499A discloses a method for preparing plant ketone by hydrogenating C18 enone using a palladium-carbon catalyst. The method can achieve continuous production, but the molar yield of the target product plant ketone is relatively low, ranging from 91.0% to 97.0%.

[0004] CN105218339A discloses a method for selectively hydrogenating 6-methyl-3,5-heptadien-2-one to obtain 6-methyl-5-heptene-2-one using a homogeneous Rh / Pd and bisphosphine ligand catalyst. The catalyst has a catalytic selectivity of 90 to 94%, but the initial dosage of the catalyst is large, and after the catalyst is used 12 times, the selectivity of the reaction is less than 90%, and the catalytic stability is poor.

[0005] CN113786862B discloses a catalyst for the selective hydrogenation of ketene, which uses an alumina carrier as a carrier, Pd as an active component, and is doped with manganese nitride and hydrides of terbium, cerium, yttrium, and lutetium as auxiliary active components. This improves the reaction selectivity, but also has poor catalytic stability and a short service life. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides a ketene selective hydrogenation catalyst and its preparation method and application. The catalyst has the characteristics of uniform composition, small active component particle size, high activity, high product selectivity, and good application effect.

[0007] To achieve the above object, the technical solutions adopted by the present invention are as follows:

[0008] A ketene selective hydrogenation catalyst is prepared by mixing a carrier in a molten state with an active metal substance and calcining the mixture; the mixing amount of the active metal substance is (0.01-0.2):1, preferably (0.02-0.1):1, calculated as the mass ratio of the metal element to the carrier;

[0009] The carrier is obtained by vulcanizing a resin precursor; the resin precursor is selected from at least one of phenolic resin, furan resin, and urea-formaldehyde resin;

[0010] The active metal substance is selected from metal salts or metal elements of at least one of Pd, Pt, and Ru.

[0011] In some preferred examples, the molten temperature of the carrier is 300-400° C.;

[0012] Preferably, the carrier and the active metal substance are mixed for 2 to 10 hours;

[0013] Preferably, the carrier and the active metal substance are mixed and calcined at 700-1200° C. for 2-10 hours.

[0014] In some preferred examples, the vulcanization process is: after uniformly mixing the resin precursor and the vulcanizing agent, vulcanizing at 100-400° C., preferably 200-350° C., for 5-30 hours, preferably 10-20 hours;

[0015] Preferably, the sulfiding agent is one or more of sodium sulfide, potassium sulfide, and thiourea;

[0016] Preferably, the mass ratio of the vulcanizing agent to the resin precursor is (0.02-0.4):1, preferably (0.04-0.2):1.

[0017] In some preferred examples, the molecular weight of the phenolic resin is 150 to 20,000, and the viscosity is 100 to 40,000 mPa*s;

[0018] Preferably, the furan resin has a molecular weight of 100 to 10,000 and a viscosity of 10 to 10,000 mPa*s;

[0019] Preferably, the urea-formaldehyde resin has a molecular weight of 1,000 to 15,000 and a viscosity of 100 to 40,000 mPa*s.

[0020] In some preferred examples, the active metal substance is selected from a metal salt of at least one of metals Pd, Pt, and Ru, preferably one or more of metal acetates, nitrates, carbonates, and chlorides.

[0021] In some preferred examples, the hydrogenation catalyst is activated by a reducing agent, washed, and dried to obtain an active hydrogenation catalyst;

[0022] Preferably, the activation reaction conditions are: treatment at 10-50°C, preferably 20-30°C, for 5-40h, preferably 10-20h;

[0023] Preferably, the reducing agent is selected from at least one of hydrogen, hydrazine hydrate, sodium formate, and formaldehyde;

[0024] Preferably, the amount of the reducing agent added is 1 to 20 times, preferably 2 to 10 times, the molar amount of the metal in the hydrogenation catalyst.

[0025] In some preferred examples, the particle size of the active hydrogenation catalyst is 10 to 100 μm, preferably 20 to 80 μm; the specific surface area is 500 to 2000 m 2 / g, preferably 800-1500m 2 / g; pore volume is 0.1~1.0cm 3 / g, preferably 0.2 to 0.8 cm 3 / g; pore diameter is 3 to 20 nm, preferably 5 to 15 nm.

[0026] The present invention also provides a method for selective hydrogenation of ketene, specifically, preparing ketone products by selective hydrogenation of ketene under the action of an activated ketene selective hydrogenation catalyst as claimed in any one of claims 1 to 7.

[0027] In some preferred method examples, the ketene is one or more of monoketene, dienketene, and cycloketene, preferably one or more of ketene, α,γ-unsaturated dienketene, and cyclohexenone;

[0028] Preferably, the amount of the catalyst used is 0.5-5% of the mass of the ketene.

[0029] The hydrogenation catalyst provided by the present invention has a large specific surface area, a small active component particle size, high catalytic activity, high product selectivity, good stability, and high economic efficiency, and is suitable for selective hydrogenation of ketene to prepare corresponding ketone products. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of the distribution of active components of the catalyst when the JEOL scanning electron microscope is magnified to the micron scale.

[0031] Figure 2 Schematic diagram of the crystallite size of the active components of the catalyst tested by JEM2100Plus transmission electron microscope. DETAILED DESCRIPTION

[0032] The present invention will be further described below through specific examples. The examples of the present invention are only for illustration of the present invention and do not limit the scope of the present invention.

[0033] The main raw materials used in the examples and comparative examples of the present invention are as follows. Unless otherwise specified, other reagents and raw materials are common commercially available products:

[0034] Phenolic resin (DN439): weight-average molecular weight 4000, viscosity 25000 mPa*s, Dow Chemical;

[0035] Furan resin (Furan type I): weight average molecular weight 6000, viscosity 30mPa*s, Zibo Shuangde;

[0036] Urea-formaldehyde resin (Haizuan 028): weight average molecular weight 6000, viscosity 6000mPa*s, Haizuanized;

[0037] Wood activated carbon: Fujian Yuanli Activated Carbon Co., Ltd.

[0038] The calculation methods and test methods used in the examples or comparative examples of the present invention are as follows:

[0039] 1. The content of each component in the reaction product was analyzed by gas chromatography (chromatograph: Agilent GC 8890A), and the activity and selectivity of the catalyst were calculated according to the following formula:

[0040] Conversion rate = (total amount of raw materials - unconverted raw materials) / total amount of raw materials × 100%;

[0041] Selectivity = (target product amount / total product amount) × 100%;

[0042] Regarding the service life of the catalyst, the maximum number of applications when both the reaction conversion rate and selectivity are maintained at 99.5% or above is recorded as the effective service life of the catalyst.

[0043] 2. Determination of specific surface area and pore structure information

[0044] The specific surface area, pore volume and pore size were determined by low-temperature liquid nitrogen physical absorption method. The specific surface area of ​​the sample was calculated based on BET theory, and the pore volume and pore size distribution were calculated using the t-plot BJH model. The testing instrument model was Micromeritics ASAP 2460.

[0045] 3. Method for determining catalyst particle size

[0046] The catalyst particle size test was carried out using a laser particle size analyzer, and the testing instrument model was Bettersize-2000LD.

[0047] 4. Distribution of active components of catalyst

[0048] The distribution of active components was determined by SEM-EDS, and the distribution was observed with a JEOL scanning electron microscope magnified to the micrometer scale.

[0049] 5. Average crystal size of active components of catalyst

[0050] The crystallite size of the active components of the catalyst was observed and determined using a JEM2100Plus transmission electron microscope, and the average crystallite size of the active components was calculated using a statistical method.

[0051] [Example 1]

[0052] Catalyst A was prepared as follows:

[0053] (1) 100 g of phenolic resin was mixed with 10 g of sodium sulfide and vulcanized at 350° C. for 10 h to obtain a carrier;

[0054] (2) The support was melted at 300°C, 16.7 g of palladium chloride was added and mixed for 2 h, and then calcined at 700°C for 2 h to obtain a hydrogenation catalyst;

[0055] (3) Add 50 g of hydrazine hydrate to the hydrogenation catalyst, mix well, and reduce at 20°C for 10 h. Wash with warm water at 20°C until the filtrate is free of chloride ions. After washing, dry at 50°C for 1 h to obtain Catalyst A.

[0056] [Example 2]

[0057] Catalyst B was prepared as follows:

[0058] (1) 100 g of furan resin was mixed with 20 g of potassium sulfide and subjected to a sulfurization treatment at 200° C. for 20 h to obtain a carrier;

[0059] (2) The support was melted at 320°C, 13.8 g of platinum chloride was added and mixed for 4 h, and then calcined at 750°C for 4 h to obtain a hydrogenation catalyst;

[0060] (3) Add 80 g of sodium formate to the hydrogenation catalyst, mix well, and reduce at 30°C for 15 h. Wash with warm water at 25°C until the filtrate is free of chloride ions. After washing, dry at 55°C for 2 h to obtain Catalyst B.

[0061] [Example 3]

[0062] Catalyst C was prepared as follows:

[0063] (1) 100 g of urea-formaldehyde resin was mixed with 30 g of thiourea and vulcanized at 280°C for 15 h to obtain a carrier;

[0064] (2) The support was melted at 340°C, 10.3 g of ruthenium chloride was added and mixed for 5 h, and then calcined at 800°C for 5 h to obtain a hydrogenation catalyst;

[0065] (3) Add 40 g of formaldehyde to the hydrogenation catalyst, mix well, and reduce at 10°C for 20 h. Wash with 30°C warm water until the filtrate is free of chloride ions. After washing, dry at 60°C for 2.5 h to obtain Catalyst C.

[0066] [Example 4]

[0067] Catalyst D was prepared as follows:

[0068] (1) 100 g of phenolic resin was mixed with 40 g of potassium sulfide and vulcanized at 100° C. for 5 h to obtain a carrier;

[0069] (2) The support was melted at 350°C, 4.2 g of palladium acetate was added and mixed for 6 h, and then calcined at 900°C for 6 h to obtain a hydrogenation catalyst;

[0070] (3) Add 30 g of hydrogen to the hydrogenation catalyst, mix well, and reduce at 50°C for 5 h. Wash with warm water at 35°C until no acetate ions are left in the filtrate. After washing, dry at 65°C for 3 h to obtain Catalyst D.

[0071] [Example 5]

[0072] Catalyst E was prepared as follows:

[0073] (1) 100 g of phenolic resin was mixed with 2 g of thiourea and vulcanized at 400 °C for 25 h to obtain a carrier;

[0074] (2) The support was melted at 360°C, 1.6 g of platinum nitrate was added and mixed for 7 h, and then calcined at 1000°C for 7 h to obtain a hydrogenation catalyst;

[0075] (3) Add 10 g of hydrazine hydrate to the hydrogenation catalyst, mix well, and reduce at 40°C for 30 h. Wash with 40°C warm water until no nitrate ions are left in the filtrate. After washing, dry at 70°C for 3.5 h to obtain Catalyst E.

[0076] [Example 6]

[0077] Catalyst F was prepared as follows:

[0078] (1) 100 g of furan resin was mixed with 4 g of thiourea and vulcanized at 250°C for 30 h to obtain a carrier;

[0079] (2) The support was melted at 380°C, 47.1 g of ruthenium nitrate was added and mixed for 8 h, and then calcined at 1100°C for 8 h to obtain a hydrogenation catalyst;

[0080] (3) Add 30 g of sodium formate to the hydrogenation catalyst, mix well, and reduce at 25°C for 40 h. Wash with 45°C warm water until no nitrate ions are left in the filtrate. After washing, dry at 75°C for 4 h to obtain Catalyst F.

[0081] [Example 7]

[0082] Catalyst G was prepared as follows:

[0083] (1) 100 g of phenolic resin was mixed with 8 g of sodium sulfide and vulcanized at 300° C. for 18 h to obtain a carrier;

[0084] (2) The support was melted at 400°C, 43.3 g of palladium nitrate was added and mixed for 10 h, and then calcined at 1200°C for 10 h to obtain a hydrogenation catalyst;

[0085] (3) Add 20 g of hydrazine hydrate to the hydrogenation catalyst, mix well, and reduce at 15°C for 18 h. Wash with 50°C warm water until no nitrate ions are left in the filtrate. After washing, dry at 80°C for 5 h to obtain Catalyst G.

[0086] [Comparative Example 1]

[0087] Catalyst A1 was prepared as follows:

[0088] (1) 100 g of phenolic resin was melted at 300° C., 16.7 g of palladium chloride was added and mixed for 2 h to obtain a catalyst precursor;

[0089] (2) The catalyst precursor was mixed with 10 g of sodium sulfide, subjected to sulfidation treatment at 350°C for 10 h, and then calcined at 700°C for 2 h to obtain a hydrogenation catalyst;

[0090] (3) Add 50 g of hydrazine hydrate to the hydrogenation catalyst, mix well, and reduce at 20°C for 10 h. Wash with warm water at 20°C until the filtrate is free of chloride ions. After washing, dry at 50°C for 1 h to obtain Catalyst A1.

[0091] [Comparative Example 2]

[0092] Catalyst A2 was prepared as follows:

[0093] (1) 100 g of phenolic resin was melted at 300° C., 16.7 g of palladium chloride was added and mixed for 2 h, and then calcined at 700° C. for 2 h to obtain a hydrogenation catalyst;

[0094] (2) Add 50 g of hydrazine hydrate to the hydrogenation catalyst, mix well, and reduce at 20°C for 10 h. Wash with warm water at 20°C until the filtrate is free of chloride ions. After washing, dry at 50°C for 1 h to obtain catalyst A2.

[0095] [Comparative Example 3]

[0096] Catalyst A3 was prepared in substantially the same manner as in Example 1, except that the sodium sulfide in step (1) was replaced by the same mass of carbon disulfide.

[0097] [Comparative Example 4]

[0098] Catalyst A4 was prepared in substantially the same manner as in Example 1, except that the phenolic resin in step (1) was replaced with wood activated carbon of the same mass.

[0099] The catalysts prepared in each embodiment and comparative example were tested for the parameters listed in Table 1, and the results are as follows:

[0100] Table 1. Catalyst indicators

[0101]

[0102]

[0103] Catalyst performance evaluation:

[0104] 100 mL of α,γ-unsaturated diene ketone was added to a 500 mL reactor, along with 2.0 g of catalyst. H₂ was introduced into the reactor at a rate of 10 mL / min for 10 hours. The reaction temperature was maintained at 80°C, the pressure at 0.7 MPaG, and the stirring rate at 10 rpm. The reaction product was chromatographically analyzed, and the conversion and selectivity were calculated and recorded in Table 2. After the reaction, the catalyst was filtered, cleaned, and dried, and the reaction process was repeated to test the catalyst's suitability. The results are shown in Table 2.

[0105] Table 2. Catalyst performance evaluation results

[0106]

[0107]

[0108] In addition, by Figure 1 It can be seen that the catalyst prepared by the method in Example 1 has a smaller active component particle size and a more uniform distribution of active components than that in Comparative Example 1, and can anchor the active components more firmly on the carrier.

[0109] Depend on Figure 2 It can be seen that the catalyst prepared by the method in Example 1 has smaller and more uniform active component grains than that in Comparative Example 1.

[0110] In summary, the hydrogenation catalyst provided by the present invention has a large specific surface area, a small active component particle size, high catalytic activity, high product selectivity, good stability, and high economic efficiency, and is suitable for the selective hydrogenation of ketene to prepare corresponding ketone products.

[0111] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be considered within the scope of protection of the present invention.

Claims

1. A ketene selective hydrogenation catalyst, characterized in that The intermediate A is prepared by mixing a carrier in a molten state with an active metal substance and calcining the mixture; the intermediate A is activated by a reducing agent to obtain the selective hydrogenation catalyst; the mixing amount of the active metal substance is (0.01-0.2):1 based on the mass ratio of the metal element to the carrier; the carrier and the active metal substance are calcined at 700-1200° C. for 2-10 hours; The carrier is obtained by vulcanizing a resin precursor with a vulcanizing agent; the resin precursor is selected from at least one of phenolic resin, furan resin, and urea-formaldehyde resin; the vulcanizing agent is one or more of sodium sulfide, potassium sulfide, and thiourea; The active metal substance is selected from metal salts of at least one of metals Pd, Pt, and Ru.

2. The ketene selective hydrogenation catalyst according to claim 1, characterized in that The mixing amount of the active metal material is calculated as a mass ratio of the metal element to the carrier, which is (0.02-0.1):

1.

3. The ketene selective hydrogenation catalyst according to claim 1, characterized in that The molten temperature of the carrier is 300-400°C.

4. The ketene selective hydrogenation catalyst according to claim 3, characterized in that The carrier and the active metal substance are mixed for 2 to 10 hours.

5. The ketene selective hydrogenation catalyst according to claim 1, characterized in that The vulcanization process is as follows: after the resin precursor and the vulcanizing agent are evenly mixed, the vulcanization treatment is performed at 100-400° C. for 5-30 hours.

6. The ketene selective hydrogenation catalyst according to claim 5, characterized in that The vulcanization process is as follows: after the resin precursor and the vulcanizing agent are evenly mixed, the vulcanization treatment is performed at 200-350° C. for 10-20 hours.

7. The ketene selective hydrogenation catalyst according to claim 5, characterized in that The mass ratio of the vulcanizing agent to the resin precursor is (0.02-0.4):

1.

8. The ketene selective hydrogenation catalyst according to claim 7, characterized in that The mass ratio of the vulcanizing agent to the resin precursor is (0.04-0.2):

1.

9. The ketene selective hydrogenation catalyst according to any one of claims 1 to 8, characterized in that The molecular weight of the phenolic resin is 150 to 20,000, and the viscosity is 100 to 40,000 mPa*s.

10. The ketene selective hydrogenation catalyst according to claim 9, characterized in that The furan resin has a molecular weight of 100 to 10,000 and a viscosity of 10 to 10,000 mPa*s.

11. The ketene selective hydrogenation catalyst according to claim 9, characterized in that The molecular weight of the urea-formaldehyde resin is 1000-15000, and the viscosity is 100-40000 mPa*s.

12. The ketene selective hydrogenation catalyst according to any one of claims 1 to 8, characterized in that The active metal substance is selected from metal salts of at least one of metals Pd, Pt, and Ru.

13. The ketene selective hydrogenation catalyst according to claim 12, characterized in that The active metal substance is selected from one or more of metal acetates, nitrates, carbonates and chlorides.

14. The ketene selective hydrogenation catalyst according to any one of claims 1 to 8, characterized in that The activation reaction conditions are: treatment at 10-50°C for 5-40 hours.

15. The ketene selective hydrogenation catalyst according to claim 14, characterized in that The activation reaction conditions are: treatment at 20-30°C for 10-20 hours.

16. The ketene selective hydrogenation catalyst according to claim 14, characterized in that The reducing agent is selected from at least one of hydrogen, hydrazine hydrate, sodium formate and formaldehyde.

17. The ketene selective hydrogenation catalyst according to claim 14, characterized in that The amount of the reducing agent added is 1 to 20 times the molar amount of the metal in the hydrogenation catalyst.

18. The ketene selective hydrogenation catalyst according to claim 17, characterized in that The amount of the reducing agent added is 2 to 10 times the molar amount of the metal in the hydrogenation catalyst.

19. The ketene selective hydrogenation catalyst according to any one of claims 1 to 8, characterized in that The particle size of the active hydrogenation catalyst is 10 to 100 μm; the specific surface area is 500 to 2000 m 2 / g; pore volume is 0.1~1.0cm 3 / g; pore diameter is 3 to 20 nm.

20. The ketene selective hydrogenation catalyst according to claim 19, characterized in that The particle size of the active hydrogenation catalyst is 20 to 80 μm; the specific surface area is 800 to 1500 m 2 / g; pore volume is 0.2~0.8cm 3 / g; pore diameter is 5~15nm.

21. A method for selective hydrogenation of ketene, characterized in that: Under the action of the activated ketene selective hydrogenation catalyst according to any one of claims 1 to 20, ketene is selectively hydrogenated to prepare ketone products.

22. The method for selective hydrogenation of ketene according to claim 21, wherein: The ketene is one or more of monoketene, dienketene and cycloketene.

23. The method for selective hydrogenation of ketene according to claim 22, wherein: The amount of the catalyst used is 0.5-5% of the mass of the ketene.

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