Kenone selective hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention discloses a ketene selective hydrogenation catalyst as well as a preparation method and application thereof. The catalyst is prepared by mixing and roasting a carrier and an active metal substance in a molten state, the mixing amount of the active metal substance is (0.01-0.2): 1, preferably (0.02-0.1): 1 according to the mass ratio of the metal element to the carrier; 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 resin; the active metal substance is selected from at least one metal salt or metal simple substance of metal Pd, Pt and Ru. The catalyst provided by the invention has the characteristics of uniform composition, small active component granularity, high activity, high product selectivity, good application effect and the like.

Description

Technical Field

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

[0002] Ketones can be selectively reduced to obtain fine chemicals with high utilization value. Currently, palladium catalysts are generally used in the industry to achieve selective hydrogenation of ketenes. Palladium metal is conducive to activating hydrogen, and it is recommended to regulate the activity of palladium through a series of means to prevent it from further converting the target product into other by-products. How to better regulate the activity of palladium metal, avoid the loss of active components, and improve the stability of the catalyst is an urgent problem to be solved.

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

[0004] CN105218339A discloses a method of selectively hydrogenating 6-methyl-3,5-heptadien-2-one to obtain 6-methyl-5-heptene-2-one using a homogeneous Rh / Pd and a diphosphine ligand catalyst. The catalytic selectivity of the catalyst is 90-94%, 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 selective hydrogenation catalyst for 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, thereby improving the reaction selectivity. However, the catalytic stability is poor and the service life is short. Summary of the invention

[0006] In order 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, good application effect, etc.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is 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, based on 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 metals 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 h.

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

[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 1000 to 15000 and a viscosity of 100 to 40000 mPa*s.

[0020] In some preferred examples, the active metal substance is selected from a metal salt of at least one of metal 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; the pore size is 3 to 20 nm, preferably 5 to 15 nm.

[0026] The present invention also provides a method for selective hydrogenation of ketene, specifically, the method comprises the step of selectively hydrogenating ketene to prepare ketone products 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, dienketone, and cycloketene, preferably one or more of vinyl ketone, α,γ-unsaturated dienketone, 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 invention has large specific surface area, small active component particle size, high catalytic activity, high product selectivity, good stability, 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 micrometer scale.

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

[0032] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate 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 25000mPa*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, Haizuan diamondization;

[0037] Wood activated carbon: Fujian Yuanli Activated Carbon Company

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

[0039] 1. Use gas chromatography (chromatograph: Agilent GC 8890A) to analyze the content of each component in the reaction product, and calculate the activity and selectivity of the catalyst 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 times 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 method of specific surface area and pore structure information

[0044] The specific surface area, pore volume and pore size were calculated using the low-temperature liquid nitrogen physical absorption method. The specific surface area of ​​the sample was calculated based on the BET theory, and the pore volume and pore size distribution were calculated using the t-plot BJH model. The test 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 magnified to the micrometer scale was observed using a JEOL scanning electron microscope.

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

[0050] The crystal size of the active component of the catalyst was observed and determined using a JEM2100Plus transmission electron microscope, and the average crystal size of the active component 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 subjected to a vulcanization treatment at 350° C. for 10 h to obtain a carrier;

[0054] (2) The carrier 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 20° C. warm water until there is no chloride ion in the filtrate. 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 carrier 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 there is no chloride ion in the filtrate. 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 there is no chloride ion in the filtrate. 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 subjected to a vulcanization treatment 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 35° C. warm water until there is no acetate ion 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 carrier 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 there is no nitrate ion 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 subjected to vulcanization treatment at 250° C. for 30 h to obtain a carrier;

[0079] (2) the carrier 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 there is no nitrate ion 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 subjected to vulcanization treatment at 300° C. for 18 h to obtain a carrier;

[0084] (2) melting the carrier at 400° C., adding 43.3 g of palladium nitrate and mixing for 10 h, and then calcining 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 there is no nitrate ion 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) mixing the catalyst precursor with 10 g of sodium sulfide, subjecting the mixture to a sulfidation treatment at 350° C. for 10 h, and then calcining the mixture 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 20° C. warm water until there is no chloride ion in the filtrate. 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 20° C. warm water until there is no chloride ion in the filtrate. 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 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, 2.0 g of catalyst was added, H2 was introduced into the reactor at a rate of 10 mL / min, and the introduction was continued for 10 h. The reaction temperature was controlled to be 80 ° C, the reaction pressure was 0.7 MPaG, and the stirring speed was 10 r / min. The product after the reaction was chromatographically analyzed, and the reaction conversion rate and selectivity were calculated and recorded in Table 2. After the reaction, the catalyst was filtered out, and the reaction process was repeated after cleaning and drying. The catalyst application was tested, and 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 particle size of active components and a more uniform distribution of active components than that in Comparative Example 1, and the active components can be more firmly anchored on the carrier.

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

[0110] In summary, the hydrogenation catalyst provided by the present invention has a large specific surface area, a small particle size of active components, a high catalytic activity, a high product selectivity, and good stability, and has high economic efficiency, and is suitable for selective hydrogenation of olefins 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 regarded as the scope of protection of the present invention.

Claims

1. A ketene selective hydrogenation catalyst, characterized in that The carrier is mixed with an active metal substance in a molten state and then calcined to obtain the active metal substance; the mixing amount of the active metal substance is (0.01-0.2):1, preferably (0.02-0.1):1, based on the mass ratio of the metal element to the carrier; 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 metal salts or metal elements of at least one of metals Pd, Pt and Ru.

2. The ketene selective hydrogenation catalyst according to claim 1, characterized in that The molten state temperature of the carrier is 300-400°C; Preferably, the carrier and the active metal substance are mixed for 2 to 10 hours; Preferably, the carrier and the active metal substance are mixed and calcined at 700-1200° C. for 2-10 h.

3. 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 uniformly mixed, vulcanization treatment is performed at 100-400° C., preferably 200-350° C., for 5-30 hours, preferably 10-20 hours; Preferably, the sulfiding agent is one or more of sodium sulfide, potassium sulfide, and thiourea; Preferably, the mass ratio of the vulcanizing agent to the resin precursor is (0.02-0.4):1, preferably (0.04-0.2):

1.

4. The ketene selective hydrogenation catalyst according to any one of claims 1 to 3, 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; Preferably, the furan resin has a molecular weight of 100 to 10,000 and a viscosity of 10 to 10,000 mPa*s; Preferably, the urea-formaldehyde resin has a molecular weight of 1000 to 15000 and a viscosity of 100 to 40000 mPa*s.

5. The ketene selective hydrogenation catalyst according to any one of claims 1 to 4, characterized in that The active metal substance is selected from at least one metal salt of metal Pd, Pt, and Ru, preferably one or more metal acetates, nitrates, carbonates, and chlorides.

6. The ketene selective hydrogenation catalyst according to any one of claims 1 to 5, characterized in that The hydrogenation catalyst is activated by a reducing agent, washed and dried to obtain an active hydrogenation catalyst; Preferably, the activation reaction conditions are: treatment at 10-50°C, preferably 20-30°C, for 5-40h, preferably 10-20h; Preferably, the reducing agent is selected from at least one of hydrogen, hydrazine hydrate, sodium formate and formaldehyde; 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.

7. The ketene selective hydrogenation catalyst according to any one of claims 1 to 6, characterized in that 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; the pore size is 3 to 20 nm, preferably 5 to 15 nm.

8. A method for selective hydrogenation of ketene, characterized in that: Under the action of the activated ketene selective hydrogenation catalyst as claimed in any one of claims 1 to 7, ketene is selectively hydrogenated to prepare ketone products.

9. The method for selective hydrogenation of ketene according to claim 8, characterized in that: The ketene is one or more of monoketene, dienketene and cycloketene; Preferably, the amount of the catalyst used is 0.5-5% of the mass of the ketene.

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