A nickel-based catalyst, its preparation method and application

Abstract

The present application relates to the field of hydrogenation catalysis technology, and particularly relates to a nickel-based catalyst, a preparation method and application thereof. The nickel-based catalyst comprises: 10.0wt%-40.0wt% of metal nickel; 1.0wt%-10.0wt% of metal copper; 0.5wt%-5.0wt% of at least one metal of lanthanum and cerium; 1.0wt%-10.0wt% of at least one element of silicon, phosphorus and fluorine; and the balance of alumina. The nickel-based catalyst provided by the present application can be used as a catalyst for selective hydrogenation of butadiene in carbon four fraction. When used for selective hydrogenation of butadiene in carbon four fraction with a butadiene content of 0.1%-2.0%, the catalyst has good low-temperature activity, selectivity and stability, and has a high butadiene hydrogenation rate and an extremely low monolefin loss rate.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrogenation catalysis, in particular to a nickel-based catalyst, its preparation method and application. BACKGROUND

[0002] C4 fraction produced by catalytic cracking, thermal cracking, MTO and other processes contains a small amount of butadiene, which is a harmful impurity and needs to be removed in time. Butadiene has a negative impact on some deep processing processes and products of C4 fraction. For example, butadiene can generate heavy condensates during alkylation, which increases the dry point of alkylation oil, reduces the octane number, and increases the acid consumption; a small amount of butadiene makes the quality of 1-butene not meet the requirements of a comonomer during oligomerization, and easily causes the catalyst to be deactivated due to coking; butadiene is easy to oligomerize on the etherification resin during etherification, generating gum that blocks the pores of the catalyst, thereby reducing the service life of the catalyst. Industrially, the impurity butadiene is mainly removed by extractive distillation or selective hydrogenation, but extractive distillation has high energy consumption, large material loss and poor economic benefits. The selective hydrogenation technology has been continuously improved and has incomparable advantages over extractive distillation. Not only can butadiene be removed, but also the yield of mono-olefins can be increased. It is currently the most economical method that is widely accepted.

[0003] In recent years, with the continuous development of the ethylene industry and the oil refining industry, C4 mono-olefins can be converted into propylene and ethylene by catalytic cracking or olefin disproportionation, which can effectively expand the source of C2 and C3 low-carbon olefins. Currently, many companies have realized industrial application, and the successful application of this technology provides technical support for the effective utilization of low-value C4 olefins and the expansion of the source of low-carbon olefins. With the continuous construction and production of olefin cracking technology and olefin disproportionation technology for increasing the production of ethylene and propylene, a large amount of carbon four mono-olefins are needed as raw materials. Therefore, the research on the selective hydrogenation catalyst and process technology of trace butadiene in carbon four fraction has a very broad market prospect.

[0004] Chinese patent 200810239462.3 discloses a selective hydrogenation method of highly unsaturated hydrocarbons in carbon four fraction. The residual material rich in alkyne obtained after butadiene extraction is used as raw material, a fixed bed reactor is used, and butadiene is obtained by selective hydrogenation in the presence of a catalyst. The reaction product is sent back to the extraction device to achieve the purpose of increasing the production of butadiene. The hydrogenation process conditions are as follows: reaction temperature 30-90℃, reaction pressure 1.0-4.0 MPa, liquid space velocity 7-20 h -1 . The catalyst is palladium / alumina, the specific surface area is 50-150 m 2 / g, and the specific pore volume is 0.25-1.0 mL / g. In this method, a noble metal catalyst is used, which has high cost and affects the overall benefit of the device.

[0005] Chinese patent CN109096032A discloses a cracking C4 selective hydrogenation catalyst and a method for increasing butene-1 production by cracking C4 hydrogenation treatment. The method uses a composite catalyst of a first stage Ni catalyst and a second stage Pd catalyst and its hydrogenation process for butadiene-containing C4 material hydrogenation to increase butene-1 production. In this method, a noble metal catalyst is used, which has high cost and affects the overall benefit of the device. Secondly, the yield of mono-olefin is not high.

[0006] USP3531545 passivates active metal Pd by actively adding sulfide to the catalytic material to reduce its hydrogenation activity, which achieves good reaction selectivity. However, since Pd is passivated, the reaction must be promoted by increasing the reaction temperature (above 160°C). USP3485887 selects an Al2O3 carrier containing spinel lithium aluminate, which produces a supported Pd selective hydrogenation catalyst with excellent stability, but its selectivity for butadiene is low, resulting in large raw material loss.

[0007] In the prior art, the cracking C4 selective hydrogenation process uses two reactors in series, which are filled with different catalysts and are matched with corresponding reaction processes. The butadiene content in the product is often higher than 10 ppm, which cannot meet the requirements for preparing high-purity butene-1, and there is an urgent need to develop an efficient and energy-saving butene-1 catalyst and process.

[0008] The most widely used butadiene hydrogenation catalyst in industrial application at present is Pd-based catalyst. Early Pd catalysts have a single composition, which generally loads a single component Pd on an alumina carrier. However, due to its high activity, over-hydrogenation reaction occurs, which not only makes butadiene hydrogenate to form 1-butene, but also makes part of the mono-olefins continue to hydrogenate to form alkanes, resulting in more by-products and loss of reaction raw materials. On the other hand, a small amount of alkyne and butadiene contained in the raw material will form a complex with metal Pd, resulting in loss of Pd in the catalyst, which seriously affects the reaction activity, stability and service life of the catalyst.

[0009] In summary, there are still many problems in the development of butadiene selective hydrogenation catalysts at present, and there are few industrial implementation schemes. There are many types and uses of modified additives, but there are still few catalysts that can comprehensively improve the reaction activity, selectivity, especially the stability of the catalyst. Therefore, it is of great significance to find a non-noble catalyst with high butadiene selective hydrogenation activity, high selectivity and good stability for the upgrading and utilization of C4 fraction. SUMMARY

[0010] Therefore, the present application aims to provide a nickel-based catalyst, a preparation method and application thereof, the nickel-based catalyst provided by the present application can be used as a catalyst for selective hydrogenation of butadiene in carbon four fraction, and has high butadiene hydrogenation rate and extremely low mono-olefin loss rate.

[0011] The present application provides a nickel-based catalyst, comprising:

[0012]

[0013] Preferably, the pore volume of the nickel-based catalyst is 0.5-1.2 cm 3 / g, and the average pore size is 10-20 nm.

[0014] Preferably, in the nickel-based catalyst, the content of metallic nickel is 15.0wt%-30.0wt%, the content of metallic copper is 3.0wt%-8.0wt%, the content of at least one metal of lanthanum and cerium is 1.0wt%-3.0wt%, and the content of at least one element of silicon, phosphorus and fluorine is 3.0wt%-6.0wt%.

[0015] The present application further provides a preparation method of the nickel-based catalyst, comprising the following steps:

[0016] A1) mixing a nickel salt solution and a carrier to perform impregnation;

[0017] The preparation method of the carrier comprises the following steps:

[0018] Alumina, sesbania powder, copper carbonate, an acid solution, a nitrate solution and component a are mixed to form a green body after molding; the acid solution comprises a phosphoric acid solution and / or a nitric acid solution; the nitrate solution comprises a lanthanum nitrate solution and / or a cerium nitrate solution; the component a comprises an amino silicon sol and / or an ammonium fluoride solution;

[0019] The green body is dried and then calcined to obtain the carrier;

[0020] A2) drying the impregnated carrier, and then calcining the dried carrier in air at 400-600 DEG C to obtain the nickel-based catalyst.

[0021] Preferably, the alumina is theta-alumina;

[0022] The acid solution is a phosphoric acid solution containing nitric acid, the mass concentration of the phosphoric acid in the phosphoric acid solution containing nitric acid is 10%-50%, and the mass concentration of the nitric acid is 0.5%-2.0%; or the acid solution is a nitric acid solution, and the mass concentration of the nitric acid solution is 2.0%-5.0%;

[0023] The mass concentration of the nitrate solution is 15%-50%;

[0024] The mass concentration of silicon oxide in the amino-silica sol is 20% to 40%.

[0025] Preferably, the drying temperature in the preparation of the carrier is 100 to 120℃, and the time is 12 to 20h.

[0026] The calcination temperature is 400 to 600℃, and the time is 6 to 10h.

[0027] Preferably, the nickel salt solution comprises a nickel nitrate solution; the mass concentration of the nickel salt solution is 10% to 50%;

[0028] The volume of the nickel salt solution is not less than the water absorption of the carrier.

[0029] The impregnation is carried out at room temperature, and the impregnation time is 0.5 to 5.0h.

[0030] Preferably, in step A2), the drying temperature is 100 to 140℃, and the time is 6 to 10h.

[0031] The calcination time is 2 to 6h.

[0032] The application further provides an application of the nickel-based catalyst described above or the nickel-based catalyst prepared by the preparation method described above as a catalyst for selective hydrogenation.

[0033] The application further provides a method for selectively hydrogenating butadiene in a carbon four fraction, comprising the following steps:

[0034] B1) reducing the catalyst with hydrogen;

[0035] The catalyst is the nickel-based catalyst described above or the nickel-based catalyst prepared by the preparation method described above;

[0036] B2) sulfidizing the catalyst reduced with hydrogen with dimethyl disulfide;

[0037] B3) using the sulfidized catalyst for selective hydrogenation of butadiene in a carbon four fraction.

[0038] The application provides a nickel-based catalyst, comprising: 10.0wt%-40.0wt% of metal nickel; 1.0wt%-10.0wt% of metal copper; 0.5wt%-5.0wt% of at least one metal of lanthanum and cerium; 1.0wt%-10.0wt% of at least one element of silicon, phosphorus and fluorine; and the balance of alumina. The nickel-based catalyst provided by the application can be used as a catalyst for selectively hydrogenating butadiene in carbon four fraction. When used for selectively hydrogenating butadiene in carbon four fraction with a butadiene content of 0.1%-2.0%, the catalyst has good low-temperature activity, selectivity and stability, and has a high butadiene hydrogenation rate and an extremely low monolefin loss rate. DETAILED DESCRIPTION

[0039] The technical solutions of the application will be described clearly and completely below in combination with the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0040] The application provides a nickel-based catalyst, comprising:

[0041]

[0042]

[0043] The nickel-based catalyst is a macroporous nickel-based catalyst, the pore volume is 0.5-1.2cm 3 / g, and the average pore size is 10-20nm.

[0044] In some embodiments of the application, the content of metal nickel in the nickel-based catalyst is 15.0wt%-30.0wt%. In some embodiments of the application, the content of metal nickel in the nickel-based catalyst is 10.0wt%, 20.0wt%, 25.0wt%, 30.0wt% or 40.0wt%.

[0045] In some embodiments of the application, the content of metal copper in the nickel-based catalyst is 3.0wt%-8.0wt%. In some embodiments of the application, the content of metal copper in the nickel-based catalyst is 1.0wt%, 3.0wt%, 5.0wt%, 8.0wt% or 10.0wt%.

[0046] In some embodiments of the present application, the content of at least one metal of lanthanum and cerium in the nickel-based catalyst is 1.0wt% to 3.0wt%. In some embodiments of the present application, the content of at least one metal of lanthanum and cerium in the nickel-based catalyst is 0.5wt%, 1.5wt%, 3wt%, 4wt% or 5wt%. In some embodiments of the present application, the nickel-based catalyst comprises lanthanum and cerium in a mass ratio of 1:1.

[0047] In some embodiments of the present application, the content of at least one element of silicon, phosphorus and fluorine in the nickel-based catalyst is 3.0wt% to 6.0wt%. In some embodiments of the present application, the content of at least one element of silicon, phosphorus and fluorine in the nickel-based catalyst is 5.0wt%, 8.0wt% or 10.0wt%. In some embodiments of the present application, the nickel-based catalyst comprises silicon and phosphorus in a mass ratio of 4.5:0.5. In some embodiments of the present application, the nickel-based catalyst comprises phosphorus and fluorine in a mass ratio of 5.0:5.0. In some embodiments of the present application, the nickel-based catalyst comprises silicon and fluorine in a mass ratio of 5.5:2.5.

[0048] In some embodiments of the present application, the pore volume of the nickel-based catalyst is 0.5 to 1.2cm 3 / g, and the average pore size is 10 to 20nm. In some embodiments, the pore volume of the nickel-based catalyst is 0.6 to 1.1cm 3 / g; and the average pore size is 12 to 18nm. In some embodiments, the pore volume of the nickel-based catalyst is 1.12cm 3 / g, 0.68cm 3 / g, 0.86cm 3 / g, 0.95cm 3 / g or 0.88cm 3 / g; and the average pore size is 10nm, 12nm, 15nm, 16nm or 18nm.

[0049] The present application also provides a preparation method of the nickel-based catalyst described above, comprising the following steps:

[0050] A1) mixing a nickel salt solution and a carrier to perform impregnation;

[0051] The preparation method of the carrier comprises the following steps:

[0052] mixing alumina, sesbania powder, copper carbonate, an acid solution, a nitrate solution and component a, and forming a green body after shaping; the acid solution comprises a phosphoric acid solution and / or a nitric acid solution; the nitrate solution comprises a lanthanum nitrate solution and / or a cerium nitrate solution; the component a comprises an amino silicon sol and / or an ammonium fluoride solution;

[0053] After drying the green body, calcining to obtain the carrier;

[0054] A2) after drying the impregnated carrier, calcining in air at 400-600℃ to obtain the nickel-based catalyst.

[0055] In step A1):

[0056] Mixing the nickel salt solution and the carrier to impregnate.

[0057] The preparation method of the carrier comprises the following steps:

[0058] Mixing the alumina, the sesbania powder, the copper carbonate, the acid solution, the nitrate solution and component a, and after shaping, obtaining the green body; the acid solution comprises a phosphoric acid solution and / or a nitric acid solution; the nitrate solution comprises a lanthanum nitrate solution and / or a cerium nitrate solution; the component a comprises an amino silicon sol and / or an ammonium fluoride solution;

[0059] After drying the green body, calcining to obtain the carrier.

[0060] In some embodiments of the present application, the alumina is preferably θ-alumina.

[0061] In some embodiments of the present application, the acid solution is a phosphoric acid solution containing nitric acid; in the phosphoric acid solution containing nitric acid, the mass concentration of the phosphoric acid is 10%-50%, specifically 10%-20%, such as 10%, and the mass concentration of the nitric acid is 0.5%-2.0%, such as 1.0%; or the acid solution is a nitric acid solution, and the mass concentration of the nitric acid solution is 2.0%-5.0%.

[0062] In some embodiments of the present application, the mass concentration of the nitrate solution is 15%-50%, such as 15%, and the solvent is water.

[0063] In some embodiments of the present application, the mass concentration of the silicon oxide in the amino silicon sol is 20%-40%, such as 40%. The present application does not have special limitations on the source of the amino silicon sol, which can be generally commercially available or self-made.

[0064] In some embodiments of the present application, the mass concentration of the ammonium fluoride solution is 30%-60%, and the solvent is water.

[0065] In some embodiments of the present application, the shaping method is extrusion molding; the shaped green body is one of clover-shaped, cylindrical, Raschig ring-shaped or four-leaf clover-shaped; in some embodiments, the length of the green body is 2-15 mm, and the diameter is 1.0-3.0 mm; specifically, the diameter is 2.0 mm.

[0066] In some embodiments of the present application, the drying temperature is 100-120℃, and the drying time is 12-20h.

[0067] In some embodiments of the present application, the calcination temperature is 400-600℃, such as 400℃, 600℃, 500℃, 550℃; and the calcination time is 6-10h, such as 6h, 10h, 8h.

[0068] After calcination, the sesbania powder is converted into carbon dioxide and water. After calcination, the amino silicon sol is converted into silicon dioxide; and after calcination, the ammonium in ammonium fluoride is converted into ammonia, and fluorine interacts with aluminum oxide and remains in the catalyst.

[0069] After obtaining the carrier, the nickel salt solution and the carrier are mixed to perform impregnation.

[0070] In some embodiments of the present application, the nickel salt solution comprises a nickel nitrate solution. The mass concentration of the nickel salt solution is 10%-50%, such as 10%, 50%, 40%, 35%, or 30%.

[0071] The volume of the nickel salt solution is not less than the water absorption of the carrier.

[0072] The impregnation is performed at room temperature, and the impregnation time is 0.5-5.0h; such as 1h.

[0073] In step A2):

[0074] After drying the impregnated carrier, the carrier is calcined in air at 400-600℃ to obtain a nickel-based catalyst.

[0075] In some embodiments of the present application, the drying temperature is 100-140℃, and the drying time is 6-10h.

[0076] In some embodiments of the present application, the calcination temperature is 450℃, 500℃, or 600℃; and the calcination time is 2-6h, such as 4h.

[0077] The present application also provides a use of the nickel-based catalyst described above or the nickel-based catalyst prepared by the preparation method described above as a catalyst for selective hydrogenation. Specifically, a use of the catalyst for selective hydrogenation of butadiene in a carbon four fraction. In some embodiments of the present application, the mass content of butadiene in the carbon four fraction is 0.1%-2.0%, specifically 0.1%-0.5%.

[0078] The present application also provides a method for selective hydrogenation of butadiene in a carbon four fraction, comprising the following steps:

[0079] B1) reducing the catalyst with hydrogen;

[0080] The catalyst is a nickel-based catalyst as described above or a nickel-based catalyst prepared by the preparation method as described above.

[0081] B2) sulfidizing the hydrogen-reduced catalyst with dimethyl disulfide;

[0082] B3) using the sulfidized catalyst for selective hydrogenation of butadiene in a C4 fraction.

[0083] In step B1):

[0084] reducing the catalyst with hydrogen;

[0085] The catalyst is a nickel-based catalyst as described above or a nickel-based catalyst prepared by the preparation method as described above.

[0086] In some embodiments of the present application, the temperature of the reduction is 400-600°C, such as 450°C; and the time is 10-30h, such as 16h.

[0087] The hydrogen pressure of the reduction is 0.1-1.0MPa, such as 0.5MPa; and the hydrogen flow rate is 500-2000mL / min, such as 1000mL / min.

[0088] In some embodiments of the present application, after the reduction, the method further comprises: cooling. The temperature after the cooling is 40-60°C, such as 50°C.

[0089] In step B2):

[0090] sulfidizing the hydrogen-reduced catalyst with dimethyl disulfide.

[0091] Specifically, the method comprises: mixing the hydrogen-reduced catalyst with a cyclohexane solution of dimethyl disulfide to perform sulfidization.

[0092] In some embodiments of the present application, the cyclohexane solution of dimethyl disulfide has a sulfur content of 100-400ppm, such as 300ppm. The mass concentration of the cyclohexane solution of dimethyl disulfide is 0.014%-0.060%.

[0093] The temperature of the sulfidization is 40-60°C, such as 50°C; and the time is 5-15h, such as 9h.

[0094] The hydrogen pressure of the sulfidization is 0.1-1.0MPa, such as 0.5MPa; and the hydrogen flow rate is 500-2000mL / min, such as 1000mL / min.

[0095] In step B3):

[0096] The sulfided catalyst is used in selective hydrogenation of butadiene in carbon four fraction.

[0097] In some embodiments of the present application, the mass content of butadiene in the carbon four fraction is 0.1% to 2.0%, specifically 0.1% to 0.5%.

[0098] In some embodiments of the present application, the temperature of the selective hydrogenation is 35 to 70°C, such as 50°C; the pressure is 1.0 to 3.0 MPa, such as 2.0 MPa; the fresh oil volume space velocity is 4.0 to 8.0 h -1 , such as 6 h -1 .

[0099] In the selective hydrogenation, the molar ratio of hydrogen to butadiene is 2 to 4:1, such as 3:1.

[0100] The catalyst prepared in the present application has good low-temperature activity, selectivity and stability when used in selective hydrogenation of butadiene in carbon four fraction with butadiene content of 0.1% to 2.0%.

[0101] The raw material used in the present application is not particularly limited and can be generally commercially available.

[0102] In order to further illustrate the present application, a nickel-based catalyst, its preparation method and application provided by the present application are described in detail below with examples, but it should not be understood as limiting the scope of protection of the present application.

[0103] Example 1

[0104] 1) Preparation of the carrier:

[0105] 76.5g of γ-alumina, 2.5g of sesbania powder, 15.2g of copper carbonate, 32g of phosphoric acid solution containing nitric acid (mass concentration of phosphoric acid is 10%, mass concentration of nitric acid is 1.0%), 7.7g of lanthanum nitrate solution with mass concentration of 15%, and 18.8g of amino silicon sol (mass concentration of silicon oxide is 40%) are mixed, extruded into clover-shaped with size length of 2 to 15mm, to obtain a green body;

[0106] The green body is dried at 120°C for 12h and calcined at 400°C for 6h to obtain the carrier Z1.

[0107] 2) Preparation of the nickel-based catalyst:

[0108] The carrier Z1 is mixed with 488g of nickel nitrate solution with mass concentration of 10% in multiple times and impregnated at room temperature for 1h; the volume of the nickel nitrate solution is not less than the water absorption of the carrier;

[0109] After drying the impregnated carrier at 120°C for 8h, calcining at 450°C in air for 4h, a nickel-based catalyst C1 was obtained.

[0110] The composition, pore volume and average pore diameter of the nickel-based catalyst C1 are shown in Table 1.

[0111] Example 2

[0112] 1) Preparation of carrier:

[0113] 44g of θ-alumina, 3.0g of sesbania powder, 1.9g of copper carbonate, 32g of a phosphoric acid solution containing nitric acid (mass concentration of phosphoric acid is 50%, mass concentration of nitric acid is 1.0%), 11.6g of a lanthanum nitrate solution with a mass concentration of 50%, 11.6g of a cerium nitrate solution with a mass concentration of 50%, and 17g of an ammonium fluoride solution with a mass concentration of 60% were mixed, and extruded into a clover shape with a size of 2-15mm in length to obtain a green body; After drying the green body at 120°C for 12h, calcining at 600°C for 10h, a carrier Z2 was obtained.

[0114]

[0115] 2) Preparation of nickel-based catalyst:

[0116] The carrier Z2 was mixed with 390g of a nickel nitrate solution with a mass concentration of 50% in multiple times, and impregnated at room temperature for 2h; the volume of the nickel nitrate solution was not less than the water absorption of the carrier;

[0117] After drying the impregnated carrier at 120°C for 8h, calcining at 600°C in air for 4h, a nickel-based catalyst C2 was obtained.

[0118] The composition, pore volume and average pore diameter of the nickel-based catalyst C2 are shown in Table 1.

[0119] Example 3

[0120] 1) Preparation of carrier:

[0121] 60.5g of θ-alumina, 5g of sesbania powder, 19g of copper carbonate, 25g of a nitric acid solution with a mass concentration of 4.0%, 17.4g of a cerium nitrate solution with a mass concentration of 20%, 22.9g of a silicic acid amino sol (wherein the mass concentration of silicon oxide is 40%), and 16.7g of an ammonium fluoride solution with a mass concentration of 30% were mixed, and extruded into a clover shape with a size of 2-15mm in length to obtain a green body; After drying the green body at 120°C for 15h, calcining at 500°C for 8h, a carrier Z3 was obtained.

[0122]

[0123] 2) Preparation of nickel-based catalyst: ​​

[0124] The carrier Z3 is mixed with 244 g of a nickel nitrate solution with a mass concentration of 40% in multiple times, and is impregnated at normal temperature for 3 h; the volume of the nickel nitrate solution is not less than the water absorption of the carrier;

[0125] After the impregnated carrier is dried at 120 ℃ for 8 h, it is calcined in air at 450 ℃ for 10 h to obtain the nickel-based catalyst C3.

[0126] The composition, pore volume and average pore diameter of the nickel-based catalyst C3 are shown in Table 1.

[0127] Example 4

[0128] 1) Preparation of the carrier:

[0129] 55 g of θ-alumina, 1.5 g of sesbania powder, 5.7 g of copper carbonate, 10 g of a nitric acid solution with a mass concentration of 3%, 11.6 g of a lanthanum nitrate solution with a mass concentration of 40%, 15.5 g of a cerium nitrate solution with a mass concentration of 30%, and 32 g of an ammonium fluoride solution with a mass concentration of 50% are mixed, and are extruded into a trilobe shape with a size of 2-15 mm to obtain a green body;

[0130] After the green body is dried at 120 ℃ for 16 h and calcined at 600 ℃ for 10 h, the carrier Z4 is obtained.

[0131] 2) Preparation of the nickel-based catalyst:

[0132] The carrier Z4 is mixed with 419 g of a nickel nitrate solution with a mass concentration of 35% in multiple times, and is impregnated at normal temperature for 5 h; the volume of the nickel nitrate solution is not less than the water absorption of the carrier;

[0133] After the impregnated carrier is dried at 120 ℃ for 8 h, it is calcined in air at 600 ℃ for 4 h to obtain the nickel-based catalyst C4.

[0134] The composition, pore volume and average pore diameter of the nickel-based catalyst C4 are shown in Table 1.

[0135] Example 5

[0136] 1) Preparation of the carrier:

[0137] 57 g of θ-alumina, 2.5 g of sesbania powder, 9.5 g of copper carbonate, 15 g of a nitric acid solution with a mass concentration of 2%, 23 g of a cerium nitrate solution with a mass concentration of 30%, and 42 g of an amino silicon sol (wherein the mass concentration of silicon oxide is 40%) are mixed, and are extruded into a trilobe shape with a size of 2-15 mm to obtain a green body;

[0138] After the green body is dried at 120 ℃ for 18 h and calcined at 550 ℃ for 10 h, the carrier Z5 is obtained.​​

[0139] 2) Preparation of the nickel-based catalyst:

[0140] The carrier Z5 was mixed with 407 g of a nickel nitrate solution with a mass concentration of 30% in multiple times and impregnated at normal temperature for 4 h; the volume of the nickel nitrate solution was not less than the water absorption amount of the carrier;

[0141] After the impregnated carrier was dried at 120°C for 8 h and calcined at 500°C in air for 4 h, a nickel-based catalyst C5 was obtained.

[0142] The composition, pore volume and average pore diameter of the nickel-based catalyst C5 are shown in Table 1.

[0143] Comparative Example 1

[0144] 1) Preparation of the carrier:

[0145] 75 g of θ-alumina, 3.3 g of sesbania powder and 19.6 g of a nitric acid solution with a mass concentration of 2% were mixed and extruded into a trilobe shape with a size of 2-15 mm in length to obtain a green body.

[0146] After the green body was dried at 120°C for 18 h and calcined at 550°C for 10 h, a carrier D1 was obtained.

[0147] 2) Preparation of the nickel-based catalyst:

[0148] The carrier D1 was mixed with 533 g of a nickel nitrate solution with a mass concentration of 30% in multiple times and impregnated at normal temperature for 4 h; the volume of the nickel nitrate solution was not less than the water absorption amount of the carrier;

[0149] After the impregnated carrier was dried at 120°C for 8 h and calcined at 500°C in air for 4 h, a nickel-based catalyst CD1 was obtained.

[0150] The composition, pore volume and average pore diameter of the nickel-based catalyst CD1 are shown in Table 1.

[0151] Comparative Example 2

[0152] 1) Preparation of the carrier:

[0153] 67 g of θ-alumina, 2.9 g of sesbania powder, 11.1 g of copper carbonate, 17.5 g of a nitric acid solution with a mass concentration of 2%, 26.9 g of a cerium nitrate solution with a mass concentration of 30% were mixed and extruded into a trilobe shape with a size of 2-15 mm in length to obtain a green body.

[0154] After the green body was dried at 120°C for 18 h and calcined at 550°C for 10 h, a carrier D2 was obtained.

[0155] ​​2) Preparation of the nickel-based catalyst:

[0156] The support D2 was mixed with 476 g of a nickel nitrate solution with a mass concentration of 30% in multiple times and impregnated at normal temperature for 4 h; the volume of the nickel nitrate solution was not less than the water absorption of the support;

[0157] After the impregnated support was dried at 120°C for 8 h, it was calcined in air at 500°C for 4 h to obtain the nickel-based catalyst CD2.

[0158] The composition, pore volume and average pore diameter of the nickel-based catalyst CD2 are shown in Table 1.

[0159] Comparative Example 3

[0160] 1) Preparation of the support:

[0161] 60 g of θ-alumina, 2.6 g of sesbania powder, 10 g of copper carbonate, 15.7 g of a nitric acid solution with a mass concentration of 2%, and 44 g of an amino silicon sol (in which the mass concentration of silicon oxide is 40%) were mixed and extruded into a trilobe shape with a size of 2-15 mm in length to obtain a green body. After the green body was dried at 120°C for 18 h and calcined at 550°C for 10 h, the support D3 was obtained.

[0162] After the impregnated support was dried at 120°C for 8 h, it was calcined in air at 500°C for 4 h to obtain the nickel-based catalyst CD2.

[0163] 2) Preparation of the nickel-based catalyst:

[0164] The support D3 was mixed with 427 g of a nickel nitrate solution with a mass concentration of 30% in multiple times and impregnated at normal temperature for 4 h; the volume of the nickel nitrate solution was not less than the water absorption of the support;

[0165] After the impregnated support was dried at 120°C for 8 h, it was calcined in air at 500°C for 4 h to obtain the nickel-based catalyst CD2.

[0166] The composition, pore volume and average pore diameter of the nickel-based catalyst CD2 are shown in Table 1.

[0167] Comparative Example 4

[0168] The difference from Example 5 is that:

[0169] The θ-alumina was changed to α-alumina; the obtained support is denoted as D4; and the obtained nickel-based catalyst is denoted as CD4.

[0170] The composition, pore volume and average pore diameter of the nickel-based catalyst CD4 are shown in Table 1.

[0171] Table 1 Composition, pore volume and average pore diameter of the nickel-based catalysts of Examples 1-5 and Comparative Examples 1-3

[0172]

[0173]

[0174] Example 1

[0175] The catalysts obtained in Examples 1-5 and Comparative Examples 1-3 were used in selective hydrogenation of butadiene in carbon four fraction (butadiene mass content 0.1%-0.5%).

[0176] Each 100 mL of the catalysts obtained in Examples 1-5 and Comparative Examples 1-3 was reduced under the conditions of hydrogen pressure 0.5 MPa, temperature 450°C and hydrogen flow rate 1000 mL / min for 16 h; then cooled to 50°C, and under the conditions of maintaining hydrogen flow rate and pressure, a dimethyl disulfide cyclohexane solution (mass concentration 0.044%, sulfur content 300 ppm) was introduced for vulcanization for 9 h; under the conditions of temperature 50°C, reaction pressure 2.0 MPa, hydrogen to butadiene molar ratio 3:1, fresh oil volume space velocity 6 h -1 The carbon four fraction raw material mass percentage composition is shown in Table 2. The hydrogenation results are shown in Table 3.

[0177] Table 2 Carbon four fraction raw material mass percentage composition

[0178] Component Content, % Butane 10.85 C4 mono-olefins 88.83 1,3-Butadiene 0.236 C4 cut 0.015

[0179] Table 3 Selective hydrogenation reaction results

[0180]

[0181]

[0182] As shown in Tables 1-3, the catalysts of the present application have high butadiene hydrogenation rate and very low mono-olefin loss rate, the outlet butadiene content is less than 10 ppm, and the mono-olefin loss rate is less than 1.0%, which can be used in industrial production of selective hydrogenation of trace butadiene in carbon four fraction.

[0183] The above description of disclosed examples enables one skilled in the art to make or use the application. Numerous modifications to these examples will be apparent to those skilled in the art, and the general principles defined herein can be applied to other examples without departing from the spirit or scope of the application. Therefore, the present application is not to be limited to the examples presented herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A nickel-based catalyst, comprising: Nickel metal 10.0 wt%~40.0 wt%; Metallic copper 1.0 wt%~10.0 wt%; At least one metal selected from lanthanum and cerium, 0.5 wt% to 5.0 wt%; At least one of silicon, phosphorus, and fluorine, in amounts of 1.0 wt% to 10.0 wt%; The remainder is aluminum oxide; The nickel-based catalyst has a pore volume of 0.5–1.2 cm³. 3 / g, with an average pore size of 10~20 nm; The preparation method of the nickel-based catalyst includes the following steps: A1) Mix the nickel salt solution and the carrier, and then impregnate the carrier; The method for preparing the carrier includes the following steps: Alumina, guar gum powder, copper carbonate, acid solution, nitrate solution, and component a are mixed and shaped to obtain a green body; the acid solution includes phosphoric acid solution and / or nitric acid solution; the alumina is θ-alumina; the nitrate solution includes lanthanum nitrate solution and / or cerium nitrate solution; component a includes aminosilica sol and / or ammonium fluoride solution. After drying the blank, it is calcined to obtain the carrier; A2) After drying the impregnated support, it is calcined in air at 400~600℃ to obtain a nickel-based catalyst.

2. The nickel-based catalyst according to claim 1, characterized in that, The nickel-based catalyst contains 15.0 wt% to 30.0 wt% of metallic nickel; 3.0 wt% to 8.0 wt% of metallic copper; 1.0 wt% to 3.0 wt% of at least one metal selected from lanthanum and cerium; and 3.0 wt% to 6.0 wt% of at least one element selected from silicon, phosphorus, and fluorine.

3. A method for preparing the nickel-based catalyst according to any one of claims 1 to 2, comprising the following steps: A1) Mix the nickel salt solution and the carrier, and then impregnate the carrier; The method for preparing the carrier includes the following steps: Alumina, guar gum powder, copper carbonate, acid solution, nitrate solution, and component a are mixed and shaped to obtain a green body; the acid solution includes phosphoric acid solution and / or nitric acid solution; the nitrate solution includes lanthanum nitrate solution and / or cerium nitrate solution; component a includes amino silica sol and / or ammonium fluoride solution. After drying the blank, it is calcined to obtain the carrier; A2) After drying the impregnated support, it is calcined in air at 400~600℃ to obtain a nickel-based catalyst.

4. The preparation method according to claim 3, characterized in that, The acid solution is a phosphoric acid solution containing nitric acid; in the phosphoric acid solution containing nitric acid, the mass concentration of phosphoric acid is 10%~50% and the mass concentration of nitric acid is 0.5%~2.0%; or the acid solution is a nitric acid solution, and the mass concentration of the nitric acid solution is 2.0%~5.0%. The mass concentration of the nitrate solution is 15%~50%; The mass concentration of silicon dioxide in the aminosilicone sol is 20% to 40%.

5. The preparation method according to claim 3, characterized in that, In the preparation of the carrier, the drying temperature is 100~120℃ and the time is 12~20 h; The roasting temperature is 400~600℃ and the time is 6~10 h.

6. The preparation method according to claim 3, characterized in that, The nickel salt solution includes a nickel nitrate solution; the mass concentration of the nickel salt solution is 10%~50%. The volume of the nickel salt solution is not less than the water absorption capacity of the carrier; The impregnation is carried out at room temperature for 0.5 to 5.0 hours.

7. The preparation method according to claim 3, characterized in that, In step A2), the drying temperature is 100~140℃ and the time is 6~10 h; The roasting time is 2-6 hours.

8. The application of the nickel-based catalyst according to any one of claims 1 to 2 or the nickel-based catalyst prepared by the preparation method according to any one of claims 3 to 7 as a catalyst for selective hydrogenation.

9. A method for selective hydrogenation of butadiene in a C4 fraction, comprising the following steps: B1) Reduce the catalyst with hydrogen; The catalyst is the nickel-based catalyst according to any one of claims 1 to 2 or the nickel-based catalyst prepared by the preparation method according to any one of claims 3 to 7; B2) The catalyst after hydrogen reduction is sulfided with dimethyl disulfide; B3) The sulfidated catalyst was used for the selective hydrogenation of butadiene in the C4 fraction.

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