A phenylacetylene semi-hydrogenation catalyst, a preparation method and application thereof

Abstract

The present application belongs to the field of catalysis, and particularly relates to a phenylacetylene semi-hydrogenation catalyst, a preparation method and application thereof. The present application is dedicated to solving the problems of complicated process and environmental unfriendliness caused by the need of sulfuration of transition metal catalysts for phenylacetylene semi-hydrogenation. The present application synthesizes a high-efficiency nickel-based alumina catalyst with double enhancement of auxiliary metal and carbon-based hydrogen buffer by using a grinding method, the catalyst does not need sulfuration, has high stability, in the phenylacetylene semi-hydrogenation reaction, the conversion rate can reach 100%, and the selectivity is as high as 99.9%. The method solves the complicated process of sulfuration of transition metal catalysts in the traditional industrial semi-hydrogenation catalytic process, is environmental friendly, and can be used in the production of environment-friendly high-efficiency phenylacetylene semi-hydrogenation catalysts.

Description

Technical Field

[0001] This invention relates to a phenylacetylene semi-hydrogenation catalyst, its preparation method, and its application, belonging to the field of catalysis technology. Background Technology

[0002] Styrene (ST) is a crucial monomer in the production of polystyrene, ABS resin, and styrene-butadiene rubber, and is also an important raw material for the production of coatings and synthetic pharmaceuticals. The largest source of styrene production is the catalytic hydrogenation of phenylacetylene (PA). However, the extracted styrene product contains trace amounts of phenylacetylene. The presence of even small amounts of phenylacetylene in the styrene feedstock can easily poison the catalyst during styrene polymerization, thereby reducing its activity. Furthermore, phenylacetylene can also degrade polystyrene, causing changes in taste, color, and degradation, thus affecting its properties. Therefore, to meet the market demand for high-quality styrene products, it is essential to develop catalysts that can completely remove phenylacetylene without compromising the high selectivity of styrene.

[0003] With the breakthrough in the technological bottleneck of phenylacetylene semi-hydrogenation to styrene, a number of industrial catalysts for phenylacetylene semi-hydrogenation have been applied. The widely used Pd / C catalysts for phenylacetylene hydrogenation suffer from high activity but low stability and extremely high cost due to the precious metals involved. Therefore, using non-precious metal catalysts to achieve selective hydrogenation of phenylacetylene has become a new direction.

[0004] Currently, some researchers are dedicated to studying non-precious metal catalysts for the semi-hydrogenation of phenylacetylene. Asahi Kasei has disclosed a high-temperature, high-space-velocity hydrogenation catalyst composed of tungsten, zinc, or more elements. However, if the reaction temperature is too high, the vinyl compounds will undergo hydrogenation, while if the temperature is too low, the desired reaction proceeds slowly. CN107952440A discloses a copper catalyst for the selective hydrogenation of phenylacetylene in C8 fractions, but it has poor thermal stability, is easily poisoned by sulfur and chlorine, and has a short service life. DSM Corporation (CN1298376A) discloses a method for hydrogenating phenylacetylene in styrene-containing media using a nickel-based catalyst. It uses a nickel catalyst with a nickel content of 10-25 wt% supported on an oxide support and a bubble bed reactor to hydrogenate phenylacetylene in styrene-containing media, but its stability is poor and it cannot achieve long-term high efficiency. The highest selectivity achieved by the nickel-based catalyst without precious metals prepared by Chen Yudi (Preparation of nickel-based intermetallic compounds and their catalytic selective hydrogenation performance of phenylacetylene [D]. Beijing University of Chemical Technology, 2017.) is only 88.2%.

[0005] In summary, existing catalysts for the semi-hydrogenation catalytic conversion of phenylacetylene either have excessively high precious metal content, are complex to prepare and require sulfidation, or require harsh reaction conditions. Furthermore, existing nickel-based catalysts without precious metals typically exhibit selectivity of no more than 90% even with 100% conversion. Therefore, this invention is proposed. Summary of the Invention

[0006] To address the aforementioned issues, the present invention provides a simple and efficient method for preparing a phenylacetylene semi-hydrogenation catalyst. Furthermore, the resulting catalyst does not require sulfidation, making it environmentally friendly. The presence of a carbon-based hydrogen buffer lowers the hydrogen pressure of the reaction, resulting in milder conditions and higher reactant conversion. The obtained catalyst effectively avoids the problem of high precious metal content found in traditional phenylacetylene semi-hydrogenation catalysts and eliminates the need for any template agents or polymerization inhibitors, significantly reducing the complexity and cost of the reaction.

[0007] The first objective of this invention is to provide a method for preparing a phenylacetylene semi-hydrogenation catalyst, comprising the following steps:

[0008] S1. Preparation of porous catalyst support containing auxiliary metal M;

[0009] Dissolve the salts of Ni(NO3)2, Ni(CH3COO)2, and auxiliary metal M in water in a certain proportion to obtain an impregnation solution;

[0010] Among them, the auxiliary metal M is a non-precious metal and M is not nickel;

[0011] S2. The porous catalyst support of S1 is brought into contact with the impregnation solution, so that the active material in the impregnation solution is loaded onto the porous catalyst support to obtain Ni(M) catalyst.

[0012] S3. The Ni(M) catalyst is reduced in a hydrogen atmosphere. After the reduction is completed, it is mixed with carbon material containing double bonds under oxygen-free conditions and ground to obtain the phenylacetylene semi-hydrogenation catalyst.

[0013] Further, in step S1, the auxiliary metal M is selected from one or more of Ti, Cu, Zn, La, and Zr.

[0014] Further, in step S1, the molar ratio of Ni(NO3)2, Ni(CH3COO)2, and the salt of auxiliary metal M is 1:1:1-100.

[0015] Further, in step S1, the porous catalyst support containing the auxiliary metal M is obtained by mixing the support body, the colloidal solvent, the salt containing the auxiliary agent and water, molding, drying and calcining. The salt is in the form of the auxiliary metal M, and the salt decomposes during calcination to form pores in the catalyst support.

[0016] Furthermore, the molding time is 5-500 min, the drying time is 5-500 min, the calcination temperature is 100-1000℃, the calcination time is 5-500 min, and the calcination equipment is a muffle furnace.

[0017] Furthermore, the carrier body includes, but is not limited to, metal oxides (such as alumina), silicon dioxide, molecular sieves, etc.

[0018] Furthermore, the adhesive solvent is selected from one or more of epoxy resin, polyurethane, silicone ester, polyimide, polyacrylate, polymethacrylate, and methanol.

[0019] Furthermore, the additives are selected from one or more of phenolic resin, polyurethane, urea-formaldehyde resin, melamine-formaldehyde resin, furfural resin, unsaturated polyester resin, chloroprene rubber, nitrile rubber, grafted chloroprene rubber, SBS, SIS, SEBS, α-cyanoacrylate, anaerobic adhesive, modified acrylate fast-curing adhesive, acrylate pressure-sensitive adhesive, polyvinyl acetate emulsion, and acrylate emulsion, to promote the hydrogen overflow effect on the catalyst surface and improve the selectivity of the reaction.

[0020] Furthermore, the salt is selected from MCl hydrochloride. x (x is taken from 1 to 5), sulfate M(SO4) y (y is taken from 1 to 5), nitrate M(NO3) z (z is taken from one or more of 1 to 5).

[0021] Furthermore, the molar ratio of the carrier body, the adhesive solvent, the salt containing the additives, and water is 10:1:1-100.

[0022] Furthermore, in the salt and water containing the additive, the molar ratio of the additive, salt and water is 1:1:1-100.

[0023] Further, in step S1, the concentration of the impregnation solution is 1-100 g / L.

[0024] Further, in step S2, the catalyst porous support is immersed in the impregnation solution for a period of time, and then aged, dried and calcined to obtain the Ni(M) catalyst.

[0025] Furthermore, the impregnation time is 1-96 hours, the aging time is 5-500 minutes, the drying time is 5-500 minutes, the calcination temperature is 100-1000℃, the calcination time is 5-500 minutes, and the calcination equipment is specifically a muffle furnace.

[0026] Furthermore, in step S3, the carbon material containing double bonds is selected from one or more of carbon nanotubes, carbon fibers, graphene, and graphyne.

[0027] Furthermore, in step S3, the reduction temperature is 400-800℃ and the reduction time is 2-10h.

[0028] Furthermore, in step S3, the carbon material accounts for 0.1%-50% of the phenylacetylene semi-hydrogenation catalyst.

[0029] Furthermore, in step S3, the particle size after grinding is 10-100 mesh.

[0030] Furthermore, in step S3, the grinding time is 5-240 min, and the mortar material is selected from agate, stainless steel, and zirconium oxide.

[0031] The second objective of this invention is to provide a phenylacetylene semi-hydrogenation catalyst prepared by the above-described method.

[0032] In this invention, the Ni(M)-C / Al2O3 catalyst is prepared in a glove box using an oxygen-free grinding method. During grinding, the carbon material containing closed double bonds comes into full contact with the precursor catalyst. After grinding, the carbon material, Ni, and the second metal M form a stable and uniformly distributed structure on the alumina support surface. Due to the small particle size of the carbon material, the interaction between the carbon material and the alumina support is greatly increased, which is beneficial to the adsorption of hydrogen and the desorption of styrene in the hydrogenation reaction. This results in the obtained Ni(M)-C / Al2O3 catalyst having a selectivity of over 95%, far exceeding the 88% selectivity of nickel-based catalysts without precious metals prepared by conventional methods. In addition, this method is environmentally friendly because it does not require a sulfidation process. The presence of a carbon-based hydrogen buffer reduces the hydrogen pressure of the reaction, making the conditions milder and achieving better technical results.

[0033] A third objective of this invention is to provide the application of the above-mentioned phenylacetylene semi-hydrogenation catalyst in the catalytic semi-hydrogenation of phenylacetylene.

[0034] The beneficial effects of this invention are:

[0035] This invention aims to solve the problems of complex processes and environmentally unfriendly conditions caused by the need for sulfidation in existing phenylacetylene semi-hydrogenation catalysts. It provides a method for preparing a phenylacetylene semi-hydrogenation catalyst that is simple, efficient, and free of precious metals, thus greatly reducing costs. The preparation process does not require sulfidation, making it environmentally friendly. Due to the presence of a carbon-based hydrogen buffer, the hydrogen pressure of the reaction is reduced, resulting in milder conditions, high catalytic efficiency, and a reactant conversion rate of up to 100% and 99.9%. Attached Figure Description

[0036] Figure 1 The Ni-Zr-C obtained in Example 1 60STEM HAADF images of the Al2O3 catalyst.

[0037] Figure 2 The Ni-Zr-C obtained in Example 1 60 STEM BF images of the Al2O3 catalyst.

[0038] Figure 3 The Ni-Zr-C obtained in Example 1 60 EDS-mapping diagram of Al2O3 catalyst. Detailed Implementation

[0039] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0040] The materials involved in the following embodiments are as follows:

[0041] The materials involved in this invention, such as polyurethane and acrylate emulsions, were all purchased from Basf Company.

[0042] Example 1

[0043] (1) Weigh a certain amount of Al2O3 powder, polyurethane, and Zr(NO3)4 solution containing acrylate emulsion according to a molar ratio of 10:1:2 and add them to a kneader. Stir and knead to form a plastic material, then shape for 120 min, dry for 60 min, and calcine for 400 min to obtain a catalyst support. The molar ratio of acrylate emulsion, Zr(NO3)4 and water is 1:1:10.

[0044] (2) Weigh a certain amount of catalyst support, and dissolve Ni(NO3)2, Ni(CH3COO)2 and Zr(NO3)4, which provide catalyst active components, in a certain amount of water at a molar ratio of 1:1:12 to prepare an impregnation solution of 10 g / L. Impregnate the support for 48 h, then age for 120 min, dry for 200 min, and calcine for 180 min to obtain the catalyst Ni-Zr / Al2O3.

[0045] (3) A certain amount of the catalyst synthesized in step (2) was reduced at 500℃ for 2 hours under a hydrogen atmosphere. After being sealed with a sealing film to isolate it from air, it was transferred to a glove box. 5% graphyne was added and the mixture was ground for 20 minutes to obtain the phenylacetylene semi-hydrogenation catalyst Ni-Zr-C. 60 / Al2O3.

[0046] Example 2

[0047] Following the method of Example 1, Ti(NO3)4 was used instead of Zr(NO3)4 in steps (1) to (2) to synthesize the phenylacetylene semi-hydrogenation catalyst Ni-Ti-C. 60 / Al2O3.

[0048] Example 3

[0049] Following the method of Example 1, Cu(NO3)2 was used instead of Zr(NO3)4 in steps (1) to (2) to synthesize the phenylacetylene semi-hydrogenation catalyst Ni-Cu. 60 -C / Al2O3.

[0050] Example 4

[0051] Following the method of Example 1, Zn(NO3)2 was used instead of Zr(NO3)4 in steps (1) to (2) to synthesize the phenylacetylene semi-hydrogenation catalyst Ni-Zn. 60 -C / Al2O3.

[0052] Example 5

[0053] Following the method of Example 1, using La(NO3)2 instead of Zr(NO3)4 in steps (1) to (2), the phenylacetylene semi-hydrogenation catalyst Ni-La was synthesized. 60 -C / Al2O3.

[0054] Comparative Example 1

[0055] A certain amount of Al2O3 powder, polyurethane, and acrylate emulsion were weighed and added to a kneader according to a molar ratio of 10:1:2. The mixture was stirred and kneaded into a plastic material, then shaped for 120 minutes, dried for 60 minutes, and calcined for 400 minutes to obtain a catalyst support. The molar ratio of acrylate emulsion to water was 1:10.

[0056] A certain amount of catalyst support was weighed, and Ni(NO3)2 and Ni(CH3COO)2, which provide the active components of the catalyst, were dissolved in a certain amount of water at a molar ratio of 1:1 to prepare an impregnation solution of 10 g / L. The support was impregnated for 48 h, and then aged for 120 min, dried for 200 min, and calcined for 180 min to obtain the catalyst Ni / Al2O3.

[0057] Comparative Example 2

[0058] A certain amount of Al2O3 powder, polyurethane, and acrylate emulsion were weighed and added to a kneader according to a molar ratio of 10:1:2. The mixture was stirred and kneaded into a plastic material, then shaped for 120 minutes, dried for 60 minutes, and calcined for 400 minutes to obtain a catalyst support. The molar ratio of acrylate emulsion to water was 1:10.

[0059] A certain amount of catalyst support was weighed, and Ni(NO3)2, Ni(CH3COO)2, and Zr(NO3)4, which provide the active components of the catalyst, were dissolved in a certain amount of water at a molar ratio of 1:1:12 to prepare an impregnation solution of 10 g / L. The support was impregnated for 48 h, then aged for 120 min, dried for 200 min, and calcined for 180 min to obtain the catalyst Ni-Zr / Al2O3.

[0060] Comparative Example 3

[0061] According to the method in the literature [Bao Zhichang. Preparation of SiO2-supported Ni-based catalyst and its application in the selective hydrogenation reaction of phenylacetylene [D]. East China University of Science and Technology, 2021. DOI:10.27148 / d.cnki.ghagu.2021.000102.], a series of NiM catalysts with different M (M = Zn, Co) / Ni molar ratios were prepared by glucose pyrolysis. x The structural properties and selective hydrogenation performance of NiZn / SiO2 bimetallic catalysts for phenylacetylene were investigated. The results showed that when the phenylacetylene conversion was >99%, the styrene selectivity of NiZn / SiO2 and NiCo0.1 / SiO2 was only 86.3% and 88%, respectively.

[0062] Comparative Example 4

[0063] Following the method described in the literature [MD Navalikhina; NE Kavalerskaya; ESLokteva, et al. Selective hydrogenation of phenylacetylene on Ni and Ni-Pd catalysts modified with heteropoly compounds of the keggin type[J]. Russian Journal of Physical Chemistry A, 2012, 86(12): 1800-1807.], unmodified nickel catalysts and nickel catalysts modified with molybdenum and tungsten heteropoly compounds (6%) were investigated. 6% K4SiW 12 O 40 The activity of three catalysts for the hydrogenation of phenylacetylene was evaluated using an Al₂O₃ catalyst. Results showed that, in the presence of 6% Ni-0.015% Pd / Al₂O₃, the activity of the catalyst was significantly higher using HPC-modified K₄SiMo₆W₆O₃. 40 With the modified nickel catalyst, the conversion rate of PA at 100℃ was only 87% when the mass ratio of styrene to ethylbenzene was 1:1.

[0064] Test Example 1

[0065] Ni-Zr-C obtained in Example 1 60 Using Al2O3 as a catalyst, a semi-hydrogenation reaction of phenylacetylene was carried out in a high-pressure reactor.

[0066] Reaction conditions: 1.0 MPa, 85 °C, hydrogen mass ratio of 1.2.

[0067] Experimental procedure: Air was replaced with nitrogen three times, and the temperature was raised to 70°C under a nitrogen atmosphere of 1.0 MPa. Then, nitrogen was replaced with hydrogen three times, and the temperature was raised to 85°C under a hydrogen atmosphere of 1.0 MPa (heating rate 2°C / min). The reaction was carried out at 85°C for 40 min, producing styrene and a very small amount of ethylbenzene. The following examples were conducted under the same catalytic conditions.

[0068] Test Example 2

[0069] Using the Ni-Ti-C obtained in Example 2 60 Using Al2O3 as a catalyst, a phenylacetylene semi-hydrogenation reaction was carried out under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2, producing styrene and a very small amount of ethylbenzene.

[0070] Test Example 3

[0071] Using the Ni-Cu-C obtained in Example 3 60 Using Al2O3 as a catalyst, a phenylacetylene semi-hydrogenation reaction was carried out under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2, producing styrene and a very small amount of ethylbenzene.

[0072] Test Example 4

[0073] Ni-Zn-C obtained in Example 4 60 Using Al2O3 as a catalyst, a phenylacetylene semi-hydrogenation reaction was carried out under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2, producing styrene and a very small amount of ethylbenzene.

[0074] Test Example 5

[0075] Using the Ni-La-C obtained in Example 5 60 Using Al2O3 as a catalyst, a phenylacetylene semi-hydrogenation reaction was carried out under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2, producing styrene and a very small amount of ethylbenzene.

[0076] Test Example 6

[0077] The phenylacetylene semi-hydrogenation reaction was carried out using the Ni-Zr / Al2O3 catalyst obtained in Example 1 under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2.

[0078] Test Example 7

[0079] The phenylacetylene semi-hydrogenation reaction was carried out using the Ni / Al2O3 catalyst obtained in Comparative Example 1 under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2.

[0080] Test Example 8

[0081] The phenylacetylene semi-hydrogenation reaction was carried out using the Ni-Zr / Al2O3 catalyst obtained in Comparative Example 2 under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2.

[0082] Test Example 9

[0083] NiM obtained using Comparative Example 3 x The phenylacetylene semi-hydrogenation reaction was carried out using a SiO2 bimetallic catalyst under reaction conditions of 1.0 MPa, 85 °C, and a hydrogen-to-mass ratio of 1.2.

[0084] Test Case 10

[0085] Using the results obtained from Comparative Example 4, in the presence of 6% Ni-0.015% Pd / Al₂O₃, via HPC K₄SiMo₆W₆O 40 The modified nickel catalyst was used to carry out the phenylacetylene semi-hydrogenation reaction under the reaction conditions of 1.0 MPa, 85 °C and hydrogen mass ratio of 1.2.

[0086] The results are as follows:

[0087] Table 1. Parameters and conversion rates of Examples 1-5 and Comparative Examples 1-4

[0088]

[0089] Table 2 Catalytic performance evaluation of Examples 1-5 and Comparative Examples 1-4

[0090]

[0091] According to the experimental data of Test Examples 1-5, the selectivity of the obtained catalysts in the phenylacetylene semi-hydrogenation reaction is greater than 95%, which is much higher than the 88% and 87% of the prior art. Among Examples 1-5, the catalyst obtained in Example 1 has the best catalytic effect.

[0092] The catalysts obtained in Examples 1-5 and Comparative Examples 1-4 were used to carry out the phenylacetylene semi-hydrogenation reaction under reaction conditions of 1.0 MPa, 85 °C and hydrogen mass ratio of 1.2. Compared with the reaction of the catalysts obtained in the comparative examples, the catalysts prepared by this method can achieve a reaction conversion rate of 100% for the phenylacetylene semi-hydrogenation reaction, and the selectivity can reach up to 99.9% under the premise of 100% conversion rate.

[0093] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing a phenylacetylene semi-hydrogenation catalyst, characterized in that, Includes the following steps: S1. Preparation of porous catalyst support containing auxiliary metal M; Dissolve Ni(NO3)2, Ni(CH3COO)2, and salt of auxiliary metal M in water in a certain proportion to obtain an impregnation solution; the molar ratio of Ni(NO3)2, Ni(CH3COO)2, and salt of auxiliary metal M is 1:1:1-100. Wherein, the auxiliary metal M is a non-precious metal and M is not nickel; the porous catalyst support containing the auxiliary metal M is obtained by mixing the support body, the colloidal solvent, the salt containing the auxiliary agent and water, molding, drying and calcining, wherein the salt is in the form of the auxiliary metal M. S2. The porous catalyst support of S1 is brought into contact with the impregnation solution, so that the active material in the impregnation solution is loaded onto the porous catalyst support to obtain Ni(M) catalyst. S3. The Ni(M) catalyst is reduced in a hydrogen atmosphere. After the reduction is completed, it is mixed with carbon material containing double bonds under oxygen-free conditions and ground to obtain the phenylacetylene semi-hydrogenation catalyst. The proportion of carbon material containing double bonds in the phenylacetylene semi-hydrogenation catalyst is 0.1%-50%.

2. The preparation method according to claim 1, characterized in that, In step S1, the auxiliary metal M is selected from one or more of Ti, Cu, Zn, La, and Zr.

3. The preparation method according to claim 1, characterized in that, The carrier body is selected from one or more of metal oxides, silica, and molecular sieves; the additives are selected from one or more of phenolic resin, polyurethane, urea-formaldehyde resin, melamine-formaldehyde resin, furfural resin, unsaturated polyester resin, chloroprene rubber, nitrile rubber, grafted chloroprene rubber, SBS, SIS, SEBS, α-cyanoacrylate, anaerobic adhesive, modified acrylate fast-curing adhesive, acrylate pressure-sensitive adhesive, polyvinyl acetate emulsion, and acrylate emulsion.

4. The preparation method according to claim 1, characterized in that, The molar ratio of the carrier body, the adhesive solvent, the salt containing the additives, and water is 10:1:1-100.

5. The preparation method according to claim 1, characterized in that, Salts of the auxiliary metal M are selected from one or more of the following: hydrochloride, sulfate, and nitrate.

6. The preparation method according to claim 1, characterized in that, In step S3, the carbon material containing double bonds is selected from one or more of carbon nanotubes, carbon fibers, graphene, and graphyne.

7. The phenylacetylene semi-hydrogenation catalyst prepared by the preparation method according to any one of claims 1-6.

8. The application of the phenylacetylene semi-hydrogenation catalyst according to claim 7 in the catalytic semi-hydrogenation of phenylacetylene.

Images