Binary non-metallic element co-doped nickel-based catalyst as well as preparation method and application thereof

Abstract

The invention provides a binary non-metallic element co-doped nickel-based catalyst as well as a preparation method and application thereof. The nickel-based catalyst comprises a carrier and an active component loaded on the carrier, the active component comprises nickel oxide, a first auxiliary agent and a second auxiliary agent; the first auxiliary agent is C; and the second auxiliary agent comprises any one or a combination of at least two of B, P or S. The nickel-based catalyst has high catalytic activity and catalytic stability at a low reaction temperature, and when the nickel-based catalyst is used for a methyl acrylate hydrogenation reaction, the content of by-products can be reduced, and the hydrogenation reaction can be stably and continuously carried out.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogenation catalysts and their preparation, and in particular relates to a binary non-metallic element co-doped nickel-based catalyst and its preparation method and application. Background Art

[0002] As an important monomer in the world market, methyl methacrylate (MMA) is mainly used in the production of plastics, paints, adhesives, coatings, etc. Its most important application is the production of organic glass, namely polymethyl methacrylate (PMMA). This material has good mechanical strength, high transparency, and strong anti-aging properties. It has great application prospects in deep-sea exploration, aerospace and other fields.

[0003] Currently, existing MMA production facilities primarily utilize the ACH and isobutylene processes, with nearly 70% utilizing the ACH process. However, the ACH process consumes large amounts of sulfuric acid, placing high demands on equipment materials, and produces large amounts of ammonium bisulfate as a by-product. This process is lengthy and places significant environmental pressures. Therefore, adopting a green MMA process as an alternative production route is imperative.

[0004] Given the current environment's rich coal, low oil, and limited gas, the production of MMA using methyl acetate and formaldehyde as raw materials is a green, economical, and sustainable coal-based process, not only efficiently utilizing coal resources but also alleviating environmental pollution. However, this process involves the hydrogenation of methyl acrylate, which, due to the easy polymerization of methyl acrylate and the difficulty in separating it from the product methyl propionate, requires a high catalyst activity under mild reaction conditions.

[0005] CN102125864A discloses a supported Ni-B-molecular sieve hydrogenation catalyst for α-pinene hydrogenation. The catalyst has high low-temperature hydrogenation activity, and the conversion rate of α-pinene reaches 99.28%. However, the catalyst preparation requires a two-step process: first, preparing the Ni-molecular sieve hydrogenation catalyst by an impregnation method, and then reducing the prepared catalyst with potassium borohydride to obtain the Ni-B-molecular sieve hydrogenation catalyst. The preparation process is complex, and a large amount of potassium borohydride is used as a reducing agent, making it difficult to industrialize large-scale production.

[0006] CN101549284B discloses a NiB amorphous alloy catalyst for the hydrogenation of 4-nitrophenol. The catalyst has high activity, with a 4-nitrophenol conversion rate of up to 99.8% and a 4-aminophenol selectivity of up to 99.6%. However, the catalyst uses aluminum sol as a carrier and is prepared by a chemical reduction method. A large amount of wastewater is generated during the reduction process, and the preparation process is complex, resulting in high production costs and unsuitable for industrial production.

[0007] In summary, providing a new catalyst for the hydrogenation reaction of methyl acrylate and a preparation method thereof to further simplify the production process and at the same time increase the yield is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0008] The present invention aims to provide a binary non-metallic element co-doped nickel-based catalyst, a preparation method, and an application thereof. The nickel-based catalyst has high catalytic activity and catalytic stability at a relatively low reaction temperature. When the nickel-based catalyst is used in the hydrogenation reaction of methyl acrylate, it can not only reduce the content of by-products but also ensure that the hydrogenation reaction can be carried out stably and continuously.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a binary non-metallic element co-doped nickel-based catalyst, the nickel-based catalyst comprising a carrier and an active component supported on the carrier;

[0011] The active components include nickel oxide, a first auxiliary agent and a second auxiliary agent;

[0012] The first auxiliary agent is C;

[0013] The second auxiliary agent includes any one of B, P or S or a combination of at least two of them.

[0014] The present invention provides a binary non-metallic element co-doped nickel-based catalyst using nickel oxide as the primary active component. The addition of a first carbon additive regulates the interaction between the nickel and the support during catalyst preparation, particularly suppressing the formation of the NiAl2O4 phase, which is detrimental to the hydrogenation process, thereby facilitating the generation of more active sites. The addition of a second additive element not only promotes the dispersion of the active component nickel but also facilitates the hydrogenation reaction. The present invention utilizes the synergistic effects between the first and second additive elements and the primary active component to enhance the activity and stability of the catalyst.

[0015] As a preferred technical solution of the present invention, the loading amount of the nickel oxide accounts for 8-12% of the total mass of the nickel-based catalyst, for example, it can be 8.2%, 8.5%, 8.7%, 9%, 9.2%, 9.5%, 9.7%, 10%, 10.5%, 11% or 11.5%, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0016] Preferably, the loading amount of the first auxiliary agent accounts for 0.2-1% of the total mass of the nickel-based catalyst, for example, it can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0017] Preferably, the loading amount of the second auxiliary agent is 0-4% of the total mass of the nickel-based catalyst, for example, it can be 0.2%, 0.5%, 0.7%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.5%, 3% or 3.5%, etc., but is not limited to the listed values. Other values ​​not listed in the numerical range are also applicable, and 0 is not included.

[0018] As a preferred technical solution of the present invention, the carrier includes any one of α-Al2O3, β-Al2O3 or γ-Al2O3 or a combination of at least two of them, preferably γ-Al2O3.

[0019] In a second aspect, the present invention provides a method for preparing the nickel-based catalyst as described in the first aspect, the preparation method comprising the following steps:

[0020] (1) dissolving a nickel source, a first auxiliary agent source, and a second auxiliary agent source in an aqueous solution, then immersing the pretreated support in the solution, and after standing and drying, obtaining a nickel-based catalyst precursor;

[0021] (2) The nickel-based catalyst precursor of step (1) is cracked and calcined to obtain the nickel-based catalyst.

[0022] The preparation method provided by the present invention can prepare a binary non-metallic element co-doped nickel-based catalyst through processes such as impregnation-cracking-roasting. The preparation method is simple, easy to operate, and suitable for large-scale production.

[0023] As a preferred technical solution of the present invention, the nickel source in step (1) includes nickel nitrate.

[0024] Preferably, the first auxiliary agent source in step (1) includes any one of sucrose, glucose or maltose, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of sucrose and glucose, a combination of glucose and maltose, a combination of sucrose, glucose and maltose, etc.

[0025] Preferably, the second auxiliary agent source in step (1) includes any one of a B source, a P source or an S source, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of a B source and a P source, a combination of a P source and an S source, a combination of a B source, a P source and an S source, etc., preferably a B source.

[0026] Preferably, the B source comprises boric acid.

[0027] Preferably, the P source comprises phosphoric acid.

[0028] Preferably, the S source comprises thiourea.

[0029] Preferably, in step (1), the molar ratio of the first auxiliary agent source to the nickel source is (0.2-1.2):1, for example, it can be 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1 or 1.1:1, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, the pretreatment in step (1) comprises: calcining the carrier at a temperature of 550-650° C. for 3-6 hours.

[0031] In the present invention, the calcination temperature is 550-650°C, for example, it can be 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C or 640°C, and the calcination time is 3-6h, for example, it can be 3.2h, 3.5h, 3.7h, 4h, 4.2h, 4.5h, 4.7h, 5h, 5.2h, 5.5h, 5.7h or 5.9h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0032] As a preferred technical solution of the present invention, the standing time in step (1) is 10-14 hours, for example, it can be 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours or 13.8 hours, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0033] In the present invention, the impregnation in step (1) is an equal volume impregnation method.

[0034] Preferably, the drying temperature in step (1) is 100-140°C, for example, it can be 105°C, 110°C, 115°C, 120°C, 125°C, 130°C or 135°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0035] Preferably, the drying time in step (1) is 8-12 h, for example, 8.2 h, 8.5 h, 8.7 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h or 11.5 h, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0036] As a preferred technical solution of the present invention, the cracking in step (2) is carried out in an inert gas.

[0037] In the present invention, the cracking in step (2) is carried out in a tubular furnace.

[0038] Preferably, the heating rate of the cracking in step (2) is 5-10°C / min, for example, it can be 5.5°C / min, 6°C / min, 6.5°C / min, 7°C / min, 7.5°C / min, 8°C / min, 8.5°C / min, 9°C / min or 9.5°C / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] Preferably, the heating end point of the cracking in step (2) is 400-600°C, for example, it can be 420°C, 450°C, 470°C, 500°C, 520°C, 550°C, 560°C, 570°C, 580°C or 590°C, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 550-600°C.

[0040] Preferably, the lysis time in step (2) is 2-4 h, for example, 2.2 h, 2.5 h, 2.7 h, 3 h, 3.2 h, 3.5 h, 3.7 h or 3.9 h, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] Preferably, the calcination temperature in step (2) is 400-600°C, for example, it can be 420°C, 450°C, 470°C, 500°C, 520°C, 550°C, 560°C, 570°C or 590°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] In the present invention, the calcination in step (2) is carried out in a muffle furnace.

[0043] Preferably, the calcination time in step (2) is 3-5 h, for example, 3.2 h, 3.5 h, 3.7 h, 4 h, 4.2 h, 4.5 h, 4.7 h or 4.9 h, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0044] In a third aspect, the present invention provides a use of the nickel-based catalyst according to the first aspect, characterized in that the nickel-based catalyst is used for the hydrogenation reaction of methyl acrylate, specifically comprising the following steps:

[0045] (a) loading the nickel-based catalyst into a fixed bed apparatus and performing hydrogen reduction;

[0046] (b) introducing the mixed reaction raw materials and hydrogen into a fixed bed apparatus, reacting at a reaction temperature and reaction pressure to obtain a hydrogenated product.

[0047] When the nickel-based catalyst provided by the present invention is used in the hydrogenation reaction of methyl acrylate, nickel oxide is converted into zero-valent nickel after in-situ reduction with hydrogen. The catalyst has the advantages of stable catalytic performance, recyclability, low consumption, good hydrogenation effect, and low hydrogen consumption. At the same time, the problem of easy polymerization of methyl acrylate when heated and the temperature rise of the hydrogenation reaction are solved, so that the hydrogenation reaction of methyl acrylate can be carried out stably and continuously, and has good engineering application prospects.

[0048] As a preferred technical solution of the present invention, before the hydrogen reduction in step (a), the process further includes: purging the fixed bed device with nitrogen.

[0049] Preferably, the temperature of the hydrogen reduction in step (a) is 400-500°C, for example, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C or 490°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0050] Preferably, the time for hydrogen reduction in step (a) is 4-6 h, for example, 4.2 h, 4.5 h, 4.7 h, 5 h, 5.2 h, 5.5 h, 5.7 h or 5.9 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] As a preferred technical solution of the present invention, the reaction raw material in step (b) is a mixture of methyl acrylate and methyl propionate.

[0052] In the present invention, since the hydrogenation reaction is exothermic, a mixture of methyl acrylate and methyl propionate is selected as the reaction raw material.

[0053] Preferably, the molar ratio of methyl acrylate to methyl propionate is (0.5-1):1, for example, it can be 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1 or 0.95:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0054] Preferably, the molar ratio of the reaction raw materials and hydrogen in step (b) is 1:(4-8), for example, it can be 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5 or 1:7.8, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0055] Preferably, in the fixed bed apparatus, the liquid hourly space velocity is 1-3h -1 , for example, it can be 1.2h -1 , 1.5h -1 , 1.7h -1, 2h -1 , 2.2h -1 , 2.5h -1 , 2.7h -1 or 2.9 hours -1 The present invention is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0056] Preferably, the reaction temperature in step (b) is 70-100°C, for example, 75°C, 80°C, 85°C, 90°C, 95°C or 98°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0057] Preferably, the reaction pressure in step (b) is 0.8-1.2 MPa, for example, 0.85 MPa, 0.9 MPa, 0.95 MPa, 1 MPa, 1.05 MPa, 1.1 MPa or 1.15 MPa, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0058] Preferably, after the reaction in step (b) is completed, the method further comprises: cooling and depressurizing the fixed bed device, and unloading the nickel-based catalyst after purging with nitrogen.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] (1) The binary non-metallic element co-doped nickel-based catalyst provided by the present invention has high catalytic activity and catalytic stability at a relatively low reaction temperature. At the same time, the preparation method provided by the present invention can prepare the nickel-based catalyst through a process such as impregnation-cracking-roasting. The preparation method is simple, easy to operate, and suitable for large-scale production.

[0061] (2) When the binary non-metallic element co-doped nickel-based catalyst provided by the present invention is used for the hydrogenation reaction of methyl acrylate, the nickel-based catalyst has the advantages of stable catalytic performance, recyclability, low consumption, good hydrogenation effect, and low hydrogen consumption. At the same time, it solves the problem of easy polymerization of methyl acrylate when heated and the temperature rise of the hydrogenation reaction, so that the hydrogenation reaction of methyl acrylate can be carried out stably and continuously, and the product yield can be as high as 99%, which has a good engineering application prospect. DETAILED DESCRIPTION

[0062] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0063] Example 1

[0064] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, wherein the nickel-based catalyst comprises a carrier and an active component supported on the carrier;

[0065] The active component includes nickel oxide, a first auxiliary agent and a second auxiliary agent; the first auxiliary agent is element C; the second auxiliary agent is element B;

[0066] The loading amount of the nickel oxide accounts for 10% of the total mass of the nickel-based catalyst; the loading amount of the C element accounts for 0.5% of the total mass of the nickel-based catalyst; the loading amount of the B element accounts for 1% of the total mass of the nickel-based catalyst; the general formula of the nickel-based catalyst is 10% Ni-1% B-0.5% C / γ-Al2O3;

[0067] The preparation method comprises the following steps:

[0068] (1) 4.4 g of nickel nitrate, 3.12 g of sucrose, 0.2 g of boric acid, and 8.32 g of distilled water were mixed to obtain a solution, and then 10 g of γ-Al2O3 was calcined at 600°C for 4 h and then immersed in the solution. After standing at room temperature for 14 h and drying at 120°C for 12 h, a nickel-based catalyst precursor was obtained;

[0069] (2) The nickel-based catalyst precursor of step (1) is placed in a tubular furnace in a nitrogen atmosphere, heated to 570°C at a heating rate of 5°C / min and kept warm for 2 hours, and then placed in a muffle furnace and calcined at 450°C for 4 hours to obtain the nickel-based catalyst.

[0070] Example 2

[0071] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof. The composition of the nickel-based catalyst is the same as that of Example 1;

[0072] The preparation method comprises the following steps:

[0073] (1) 4.4 g of nickel nitrate, 3.12 g of sucrose, 0.2 g of boric acid, and 8.32 g of distilled water were mixed to obtain a solution, and then 10 g of γ-Al2O3 was calcined at 600°C for 3 h and then immersed in the solution. After standing at room temperature for 10 h and drying at 120°C for 12 h, a nickel-based catalyst precursor was obtained;

[0074] (2) The nickel-based catalyst precursor of step (1) is placed in a tubular furnace in a nitrogen atmosphere, heated to 600°C at a heating rate of 10°C / min and kept warm for 3 hours, and then placed in a muffle furnace and calcined at 500°C for 3 hours to obtain the nickel-based catalyst.

[0075] Example 3

[0076] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the general formula of the nickel-based catalyst is 10% Ni-1% B-0.2% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0077] Example 4

[0078] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the general formula of the nickel-based catalyst is 10% Ni-1% B-1% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0079] Example 5

[0080] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the second auxiliary agent is S element and the general formula of the nickel-based catalyst is 10% Ni-1% S-0.5% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0081] Example 6

[0082] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the general formula of the nickel-based catalyst is 10% Ni-1% B-0.1% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0083] Example 7

[0084] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the general formula of the nickel-based catalyst is 10% Ni-1% B-1.5% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0085] Example 8

[0086] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof, except that the general formula of the nickel-based catalyst is 10% Ni-5% B-0.5% C / γ-Al2O3; other conditions are the same as those in Example 1.

[0087] Example 9

[0088] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof. Except that the cracking in step (2) is carried out in an air atmosphere, other conditions are the same as those in Example 1.

[0089] Example 10

[0090] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof. Except that the heating end point of the cracking in step (2) is 400°C, other conditions are the same as those in Example 1.

[0091] Example 11

[0092] This embodiment provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof. Except that the heating end point of the cracking in step (2) is 700°C, other conditions are the same as those in Example 1.

[0093] Comparative Example 1

[0094] This comparative example provides a non-metallic element doped nickel-based catalyst and a preparation method thereof. Except that the general formula of the nickel-based catalyst is 10% Ni-1% P / γ-Al2O3, other conditions are the same as those in Example 1.

[0095] Comparative Example 2

[0096] This comparative example provides a non-metallic element doped nickel-based catalyst and a preparation method thereof. Except that the general formula of the nickel-based catalyst is 10% Ni-1% S / γ-Al2O3, other conditions are the same as those in Example 1.

[0097] Comparative Example 3

[0098] This comparative example provides a non-metallic element doped nickel-based catalyst and a preparation method thereof. Except that the general formula of the nickel-based catalyst is 10% Ni-1% B / γ-Al2O3, other conditions are the same as those in Example 1.

[0099] Comparative Example 4

[0100] This comparative example provides a binary non-metallic element co-doped nickel-based catalyst and a preparation method thereof. Except that no cracking is performed during the preparation process, other conditions are the same as those in Example 1.

[0101] Application Example 1

[0102] This application example provides a nickel-based catalyst prepared in Example 1 for use in the hydrogenation reaction of methyl acrylate, which specifically includes the following steps:

[0103] (a) 10 g of nickel-based catalyst was loaded into a fixed bed apparatus, purged with nitrogen, and then reduced with hydrogen at 450° C. for 5 h;

[0104] (b) The reaction raw materials and hydrogen were introduced into a fixed bed apparatus at a molar ratio of 1:8, and the temperature was 70°C, the pressure was 1 MPa, and the liquid hourly space velocity was 1 h -1 The reaction is carried out under the following conditions to obtain a hydrogenation product;

[0105] The reaction raw materials are methyl acrylate and methyl propionate in a molar ratio of 1:1;

[0106] (c) Cooling and depressurizing the fixed bed device, and then discharging the nickel-based catalyst after purging with nitrogen.

[0107] Application Example 2-11

[0108] Application Example 2-11 provides a nickel-based catalyst prepared in Example 2-11 for the hydrogenation reaction of methyl acrylate, and other conditions are the same as those in Application Example 1.

[0109] Application Example 12

[0110] This application example provides a nickel-based catalyst prepared in Example 1 for the hydrogenation reaction of methyl acrylate, except that in step (b), the reaction raw materials and hydrogen are introduced into a fixed bed device at a molar ratio of 1:5, and the temperature is 70°C, the pressure is 0.5 MPa, and the liquid hourly space velocity is 2h -1 Except that the reaction was carried out under the following conditions, other conditions were the same as those in Application Example 1.

[0111] Application Example 13

[0112] This application example provides a nickel-based catalyst prepared in Example 1 for the hydrogenation reaction of methyl acrylate, except that in step (b), the reaction raw materials and hydrogen are introduced into a fixed bed device at a molar ratio of 1:8, and the temperature is 40°C, the pressure is 1 MPa, and the liquid hourly space velocity is 1 h -1 Except that the reaction was carried out under the following conditions, other conditions were the same as those in Application Example 1.

[0113] Comparative Application Examples 1-4

[0114] Comparative Application Example 1-4 provides a nickel-based catalyst prepared in Comparative Example 1-4 for use in the hydrogenation reaction of methyl acrylate, with other conditions being the same as those in Application Example 1.

[0115] The methyl propionate products obtained in the above application examples and comparative application examples were detected by chromatography, and the results are shown in Table 1.

[0116] Table 1

[0117] Catalyst used Yield Application Example 1 Example 1 99％ Application Example 2 Example 2 97％ Application Example 3 Example 3 93％ Application Example 4 Example 4 92％ Application Example 5 Example 5 93％ Application Example 6 Example 6 91％ Application Example 7 Example 7 83％ Application Example 8 Example 8 89％ Application Example 9 Example 9 80％ Application Example 10 Example 10 91％ Application Example 11 Example 11 84％ Application Example 12 Example 1 82％ Application Example 13 Example 1 62％ Comparative Application Example 1 Comparative Example 1 73％ Comparative Application Example 2 Comparative Example 2 68％ Comparative Application Example 3 Comparative Example 3 86％ Comparative Application Example 4 Comparative Example 4 87％

[0118] From Table 1 we can see that:

[0119] (1) The nickel-based catalyst provided by the present invention and its preparation method have excellent catalytic activity and catalytic stability. When used in the hydrogenation reaction of methyl acrylate, it has an excellent product yield of up to 99%;

[0120] (2) A comparison between Application Example 1 and Application Examples 6-7 shows that when the content of the first promoter element is low, the catalyst performance is reduced due to the formation of NiAl2O4 in the catalyst; when the content of the first promoter element is high, the catalyst performance is reduced due to the generation of carbon deposits; a comparison between Application Example 1 and Application Example 8 shows that when the content of the second promoter element is high, the dispersion of the active components is not conducive, resulting in reduced catalyst performance;

[0121] (3) A comparison of Application Example 1 and Application Examples 9-11 shows that when the cracking is carried out in an air atmosphere, the catalyst generates a large amount of NiAl2O4, which is not conducive to reduction, resulting in a decrease in catalyst performance; when the temperature rise end point of the cracking is too low, the carbon precursor is not completely cracked, resulting in a decrease in catalyst performance; when the temperature rise end point of the cracking is too high, it is not conducive to the dispersion of the active components, resulting in a decrease in catalyst performance;

[0122] (4) A comparison of Application Example 1 and Application Examples 12-13 shows that when the pressure of the hydrogenation reaction is too low, the low pressure is not conducive to the progress of the hydrogenation reaction, resulting in a decrease in product yield; when the temperature of the hydrogenation reaction is too low, the catalyst activity is low, resulting in a decrease in product yield;

[0123] (5) From the comparison between Application Example 1 and Comparative Application Examples 1-3, it can be seen that when the first promoter element is not contained, the formation of the NiAl2O4 phase cannot be suppressed, resulting in a decrease in catalyst activity and stability;

[0124] (6) From the comparison between Application Example 1 and Comparative Application Example 4, it can be seen that when the cracking process is not carried out, a large amount of NiAl2O4 phase is formed in the catalyst, resulting in a decrease in catalyst activity.

[0125] The applicant declares that the present invention is intended to illustrate the detailed structural features of the present invention through the above-described embodiments, but the present invention is not limited to the above-described detailed structural features. This does not mean that the present invention must rely on the above-described detailed structural features in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for selected components, additions of auxiliary components, and selection of specific embodiments, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A binary non-metallic element co-doped nickel-based catalyst, characterized in that: The nickel-based catalyst comprises a carrier and an active component supported on the carrier; The active components include nickel oxide, a first auxiliary agent and a second auxiliary agent; The first auxiliary agent is C; The second auxiliary agent includes any one of B, P or S or a combination of at least two of them.

2. The nickel-based catalyst according to claim 1, characterized in that The nickel oxide loading accounts for 8-12% of the total mass of the nickel-based catalyst; Preferably, the loading amount of the first auxiliary agent accounts for 0.2-1% of the total mass of the nickel-based catalyst; Preferably, the loading amount of the second auxiliary agent accounts for 0-4% of the total mass of the nickel-based catalyst, excluding 0.

3. The nickel-based catalyst according to claim 1 or 2, characterized in that The carrier includes any one of α-Al2O3, β-Al2O3 or γ-Al2O3 or a combination of at least two of them, preferably γ-Al2O3.

4. A method for preparing a nickel-based catalyst according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (1) dissolving a nickel source, a first auxiliary agent source, and a second auxiliary agent source in an aqueous solution, then immersing the pretreated support in the solution, and after standing and drying, obtaining a nickel-based catalyst precursor; (2) The nickel-based catalyst precursor of step (1) is cracked and calcined to obtain the nickel-based catalyst.

5. The preparation method according to claim 4, characterized in that The nickel source in step (1) comprises nickel nitrate; Preferably, the first auxiliary agent source in step (1) includes any one of sucrose, glucose or maltose, or a combination of at least two thereof; Preferably, the second auxiliary agent source in step (1) includes any one of a B source, a P source or an S source, or a combination of at least two thereof, preferably a B source; Preferably, the B source comprises boric acid; Preferably, the P source comprises phosphoric acid; Preferably, the S source comprises thiourea; Preferably, in step (1), the molar ratio of the first auxiliary agent source to the nickel source is (0.2-1.2):1; Preferably, the pretreatment in step (1) comprises: calcining the carrier at a temperature of 550-650° C. for 3-6 hours.

6. The preparation method according to claim 4 or 5, characterized in that The standing time in step (1) is 10-14 hours; Preferably, the drying temperature in step (1) is 100-140°C; Preferably, the drying time in step (1) is 8-12 hours.

7. The preparation method according to any one of claims 4 to 6, characterized in that The cracking in step (2) is carried out in an inert gas; Preferably, the heating rate of the pyrolysis in step (2) is 5-10°C / min; Preferably, the temperature rise end point of the cracking in step (2) is 400-600°C, preferably 550-600°C; Preferably, the lysis time in step (2) is 2-4 hours; Preferably, the calcination temperature in step (2) is 400-600°C; Preferably, the calcination time in step (2) is 3-5 hours.

8. Use of the nickel-based catalyst according to any one of claims 1 to 3, characterized in that: The nickel-based catalyst is used for the hydrogenation reaction of methyl acrylate, which specifically comprises the following steps: (a) loading the nickel-based catalyst into a fixed bed apparatus and performing hydrogen reduction; (b) introducing the mixed reaction raw materials and hydrogen into a fixed bed apparatus, reacting at a reaction temperature and reaction pressure to obtain a hydrogenated product.

9. The use according to claim 8, characterized in that Before the hydrogen reduction in step (a), the method further comprises: purging the fixed bed device with nitrogen; Preferably, the temperature of the hydrogen reduction in step (a) is 400-500°C; Preferably, the time for hydrogen reduction in step (a) is 4-6 hours.

10. The use according to claim 8 or 9, characterized in that: The reaction raw material of step (b) is a mixture of methyl acrylate and methyl propionate; Preferably, the molar ratio of methyl acrylate to methyl propionate is (0.5-1):1; Preferably, the molar ratio of the reaction raw materials to hydrogen in step (b) is 1:(4-8); Preferably, in the fixed bed apparatus, the liquid hourly space velocity is 1-3h -1 ; Preferably, the reaction temperature in step (b) is 70-100°C; Preferably, the reaction pressure in step (b) is 0.8-1.2 MPa; Preferably, after the reaction in step (b) is completed, the method further comprises: cooling and depressurizing the fixed bed device, and unloading the nickel-based catalyst after purging with nitrogen.