Anthracene hydrogenation catalyst and preparation method thereof

Abstract

The invention provides an anthracene hydrogenation catalyst and a preparation method thereof. The anthracene hydrogenation catalyst comprises a metal active component, a metal additive and a composite oxide carrier, the metal active components are Ni and Cu, the metal additive is Zn, and the composite oxide carrier is SiO2.gamma-Al2O3. The anthracene hydrogenation catalyst aNi-bCu-cZn / dSiO2.e gamma-Al2O3 disclosed by the invention has excellent activity, and under the condition that anthracene is completely converted, the required reaction temperature is 220 DEG C, the pressure is 2.5 MPa and the reaction time is 3 hours; the reaction temperature of the anthracene hydrogenation catalyst in the prior art is 275 DEG C, the pressure is up to 4 MPa, and the reaction time is 4 hours under the condition that anthracene is completely converted, that is, higher reaction temperature, higher reaction pressure and longer reaction time are required in the prior art, and the reaction conditions are harsh.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts and relates to anthracene hydrogenation, and specifically relates to an anthracene hydrogenation catalyst and a preparation method thereof. Background Art

[0002] Anthracene is a polycyclic aromatic hydrocarbon containing three benzene rings and is also an important component of coal tar. The deep hydrogenation product perhydroanthracene is prepared by catalytic hydrogenation and saturation of anthracene, which realizes the light weight conversion of heavy components of coal tar and obtains high-quality chemical raw materials or fuels. Therefore, anthracene catalytic hydrogenation technology is an important technical approach for the high-value conversion and utilization of coal tar. A large number of studies have shown that the core of anthracene hydrogenation reaction lies in the development of high-performance catalysts.

[0003] Prior art "Bai Lijun. Application of bimetallic Pd-based catalysts in anthracene hydrogenation reaction and research on their performance [D]. Taiyuan University of Technology, 2022, Taiyuan, Shanxi" discloses an anthracene hydrogenation catalyst PdLa / γ-Al 2 O 3 However, the anthracene hydrogenation catalyst PdLa / γ-Al 2 O 3 The scarce precious metal Pd is used, and the catalyst cost is high. 2 O 3 The activity of anthracene hydrogenation catalyst PdLa / γ-Al is low and requires harsh reaction conditions. 2 O 3 The reaction temperature is 275°C, the pressure is as high as 4Mpa, and the reaction time is 4 hours, so the prospects for industrial application are limited. Summary of the invention

[0004] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an anthracene hydrogenation catalyst and a preparation method thereof, so as to solve the technical problems of the anthracene hydrogenation catalyst in the prior art in that the reaction conditions are harsh and the raw material resources are scarce.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:

[0006] An anthracene hydrogenation catalyst comprises a metal active component, a metal promoter and a composite oxide carrier.

[0007] The metal active components are Ni and Cu.

[0008] The metal auxiliary agent is Zn.

[0009] The composite oxide carrier is SiO 2 γ-Al 2 O3 .

[0010] The present invention also has the following technical features:

[0011] The composition of the anthracene hydrogenation catalyst is represented by aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 ;

[0012] in:

[0013] a is the ratio of the mass of Ni to the total mass of the composite oxide support;

[0014] b is the ratio of the mass of Cu to the total mass of the composite oxide support;

[0015] c is the ratio of the mass of Zn to the total mass of the composite oxide support;

[0016] d is nano-scale SiO 2 The ratio of the mass of the composite oxide support to the total mass of the composite oxide support;

[0017] e is γ-Al 2 O 3 The ratio of the mass of the composite oxide support to the total mass of the composite oxide support.

[0018] The a is 0.01 to 0.02.

[0019] The b is 0.005 to 0.015.

[0020] The c is 0.005 to 0.02.

[0021] The d is 0.2 to 0.3.

[0022] The e is 0.7 to 0.8.

[0023] The present invention also protects a method for preparing the anthracene hydrogenation catalyst as described above, the method comprising the following steps:

[0024] Step 1: Use mechanical ball milling to grind nano-sized SiO 2 and γ-Al 2 O 3 Mechanical mixing is performed to uniformly disperse the composite oxide support SiO 2 γ-Al 2 O 3 .

[0025] Step 2: impregnate an equal volume of a mixed aqueous solution containing nickel nitrate and copper nitrate into the composite oxide support SiO2 obtained in step 1. 2 γ-Al 2 O3 After mechanical stirring, drying, roasting and H 2 Reduction to obtain anthracene hydrogenation catalyst, namely aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 .

[0026] Preferably, in step 1, the rotation speed of the mechanical ball milling method is 80 to 120 r / min.

[0027] Preferably, in step 1, the mechanical mixing time is 2 to 4 hours.

[0028] Specifically, in step 1, the nano-scale SiO 2 The particle size is 10 to 20 nm.

[0029] Preferably, in step 2, the mechanical stirring time is 2 to 3 hours.

[0030] Preferably, in step 2, the drying is performed at a temperature of 110° C. for 6 to 10 hours.

[0031] Preferably, in step 2, the calcination is carried out at a temperature of 600° C. for 3 to 5 hours.

[0032] Preferably, in step 2, the H 2 The reduction is carried out at a temperature of 600°C for 1 to 2 hours.

[0033] Compared with the prior art, the present invention has the following technical effects:

[0034] (I) Anthracene hydrogenation catalyst of the present invention aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 It has excellent activity. When anthracene is completely converted, the required reaction temperature is 220°C, the pressure is 2.5MPa and the reaction time is 3h. However, when anthracene is completely converted, the anthracene hydrogenation catalyst in the prior art requires a reaction temperature of 275°C, a pressure of up to 4MPa and a reaction time of 4h. That is, the prior art requires a higher reaction temperature, a higher reaction pressure and a longer reaction time, and the reaction conditions are harsh.

[0035] (II) Anthracene hydrogenation catalyst of the present invention aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 The metal active components are non-precious metal nickel-copper dual components, which are widely available and have lower costs.

[0036] (III) Anthracene hydrogenation catalyst of the present invention aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 Ni and Cu are used as metal active components, Zn is used as metal additive, and SiO 2 γ-Al 2 O 3 As a composite oxide carrier with a large surface area and high temperature resistance, the synergistic effect between materials is utilized to improve the comprehensive performance of the anthracene hydrogenation catalyst, thereby achieving the goal of reducing the cost and improving the activity of the anthracene hydrogenation catalyst.

[0037] The specific contents of the present invention are further explained in detail below in conjunction with embodiments. DETAILED DESCRIPTION

[0038] It should be noted that the raw materials and instruments used in the present invention, unless otherwise specified, are all raw materials and instruments known in the prior art. 2 Using known nano-scale SiO 2 ,γ-Al 2 O 3 Using the known γ-Al 2 O 3 .

[0039] The equal volume impregnation in the present invention adopts the known equal volume impregnation.

[0040] It should be noted that the performance evaluation method of the anthracene hydrogenation catalyst in the embodiment of the present invention is consistent with the catalyst performance evaluation method in the comparative document "Bai Lijun. Application of bimetallic Pd-based catalysts in anthracene hydrogenation reaction and performance research [D]. Taiyuan University of Technology, 2022, Taiyuan, Shanxi".

[0041] The anthracene hydrogenation catalyst provided by the present invention is used for the complete conversion reaction of anthracene. The reaction temperature of the complete conversion reaction of anthracene is 220° C., the pressure is 2.5 MPa and the reaction time is 3 hours.

[0042] In accordance with the above technical scheme, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of this application fall within the protection scope of the present invention.

[0043] Embodiment 1:

[0044] This embodiment provides an anthracene hydrogenation catalyst, wherein the metal active components of the anthracene hydrogenation catalyst are Ni and Cu, the metal promoter is Zn, and the composite oxide carrier is SiO 2 γ-Al 2 O 3.

[0045] The composition of anthracene hydrogenation catalyst is expressed as aNi-bCu-cZn / dSiO 2 ·eγ-Al 2 O 3 ;

[0046] in:

[0047] a is the ratio of the mass of Ni to the total mass of the composite oxide support;

[0048] b is the ratio of the mass of Cu to the total mass of the composite oxide support;

[0049] c is the ratio of the mass of Zn to the total mass of the composite oxide support;

[0050] d is nano-scale SiO 2 The ratio of the mass of the composite oxide support to the total mass of the composite oxide support;

[0051] e is γ-Al 2 O 3 The ratio of the mass of the composite oxide support to the total mass of the composite oxide support.

[0052] In this embodiment, a is 0.015; b is 0.01; c is 0.005; d is 0.3; and e is 0.7.

[0053] The preparation method of the anthracene hydrogenation catalyst of the present embodiment specifically comprises the following steps:

[0054] Step 1: Use mechanical ball milling to grind nano-scale SiO 2 and γ-Al 2 O 3 The composite oxide carrier SiO was obtained by mechanical mixing at a rotation speed of 80 r / min for 2 h to obtain uniform dispersion. 2 γ-Al 2 O 3 .

[0055] Step 2: impregnate an equal volume of a mixed aqueous solution containing nickel nitrate and copper nitrate into the composite oxide support SiO2 obtained in step 1. 2 γ-Al 2 O 3 The mixture was then dried at 110 °C for 6 h, calcined at 600 °C for 3 h, and heated at 600 °C for 3 h at a flow rate of 100 mL / min. 2 After reduction for 1 h, anthracene hydrogenation catalyst was obtained, which was 0.015Ni-0.01Cu-0.005Zn / 0.3SiO 2 0.7γ-Al 2 O3 .

[0056] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 220° C., the pressure is 2.5 MPa and the reaction time is 3 h.

[0057] Embodiment 2:

[0058] This embodiment provides an anthracene hydrogenation catalyst. The anthracene hydrogenation catalyst and its preparation method are basically the same as those in Example 1, except that: a is 0.01; b is 0.015; c is 0.01; d is 0.2; e is 0.8; in step 1, the rotation speed is 100 r / min, and the mechanical mixing time is 3 h; in step 2, the mechanical stirring time is 3 h, the drying time is 8 h, the roasting time is 4 h, and H 2 The reduction time was 2 h, and the anthracene hydrogenation catalyst was obtained, which was 0.01Ni-0.015Cu-0.01Zn / 0.2SiO 2 0.8γ-Al 2 O 3 .

[0059] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 210° C., the pressure is 2.5 MPa and the reaction time is 3 h.

[0060] Embodiment 3:

[0061] This example provides an anthracene hydrogenation catalyst. The anthracene hydrogenation catalyst and its preparation method are basically the same as those in Example 1, except that: a is 0.02; b is 0.005; c is 0.015; d is 0.2; and e is 0.8. In step 1, the rotation speed is 120 r / min, and the mechanical mixing time is 4 h; in step 2, the drying time is 10 h, and the calcination time is 4 h. The anthracene hydrogenation catalyst is obtained, namely 0.02Ni-0.005Cu-0.015Zn / 0.2SiO 2 0.8γ-Al 2 O 3 .

[0062] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 220° C., the pressure is 2.5 MPa and the reaction time is 2 h.

[0063] Embodiment 4:

[0064] This embodiment provides an anthracene hydrogenation catalyst. The anthracene hydrogenation catalyst and its preparation method are basically the same as those in Embodiment 1, except that: d is 0.25; e is 0.75; in step 1, the rotation speed is 100 r / min, and the mechanical mixing time is 3 h; in step 2, the mechanical stirring time is 3 h, the drying time is 10 h, the calcination time is 5 h, and H 2 The reduction time is 2 h, and the anthracene hydrogenation catalyst is obtained, which is 0.015Ni-0.01Cu-0.005Zn / 0.25SiO 2 0.75γ-Al 2 O 3 .

[0065] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 220° C., the pressure is 2 MPa, and the reaction time is 3 h.

[0066] Embodiment 5:

[0067] This embodiment provides an anthracene hydrogenation catalyst. The anthracene hydrogenation catalyst and its preparation method are basically the same as those in Example 1, except that: a is 0.01; b is 0.015; c is 0.02; d is 0.2; e is 0.8; in step 1, the mechanical mixing time is 4 h; in step 2, the drying time is 10 h, the roasting time is 5 h, and H 2 The reduction time is 2 h, and the anthracene hydrogenation catalyst is obtained, which is 0.01Ni-0.015Cu-0.02Zn / 0.2SiO 2 0.8γ-Al 2 O 3 .

[0068] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 210° C., the pressure is 2.5 MPa and the reaction time is 2 h.

[0069] Embodiment 6:

[0070] This embodiment provides an anthracene hydrogenation catalyst. The anthracene hydrogenation catalyst and its preparation method are basically the same as those in Example 1, except that: c is 0.01; in step 1, the rotation speed is 120 r / min, and the mechanical mixing time is 3 h; in step 2, the mechanical stirring time is 3 h, the drying time is 8 h, and the calcination time is 4 h. The anthracene hydrogenation catalyst is obtained, that is, 0.015Ni-0.01Cu-0.01Zn / 0.3SiO 2 0.7γ-Al 2 O 3 .

[0071] According to the performance evaluation method of anthracene hydrogenation catalyst, the reaction temperature for the complete conversion reaction of anthracene is 220° C., the pressure is 2.5 MPa and the reaction time is 2 h.

Claims

1. An anthracene hydrogenation catalyst, characterized in that The anthracene hydrogenation catalyst comprises a metal active component, a metal promoter and a composite oxide carrier; The metal active components are Ni and Cu; The metal additive is Zn; The composite oxide carrier is SiO2·γ-Al2O3.

2. The anthracene hydrogenation catalyst according to claim 1, characterized in that The composition of the anthracene hydrogenation catalyst is expressed as aNi-bCu-cZn / dSiO2·eγ-Al2O3; in: a is the ratio of the mass of Ni to the total mass of the composite oxide support; b is the ratio of the mass of Cu to the total mass of the composite oxide support; c is the ratio of the mass of Zn to the total mass of the composite oxide support; d is the ratio of the mass of nano-SiO2 to the total mass of the composite oxide support; e is the ratio of the mass of γ-Al2O3 to the total mass of the composite oxide support.

3. The anthracene hydrogenation catalyst according to claim 2, wherein: The a is 0.01 to 0.02; The b is 0.005 to 0.015; The c is 0.005 to 0.02; The d is 0.2 to 0.3; The e is 0.7 to 0.

8.

4. A method for preparing anthracene hydrogenation catalyst according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: Step 1: using a mechanical ball milling method, nano-sized SiO2 and γ-Al2O3 are mechanically mixed to be uniformly dispersed to obtain a composite oxide carrier SiO2·γ-Al2O3; Step 2: Impregnate an equal volume of a mixed aqueous solution containing nickel nitrate and copper nitrate onto the composite oxide support SiO2·γ-Al2O3 obtained in step 1 and mechanically stir, and obtain an anthracene hydrogenation catalyst, i.e., aNi-bCu-cZn / dSiO2·eγ-Al2O3, after drying, calcination and H2 reduction.

5. The method for preparing anthracene hydrogenation catalyst according to claim 4, wherein: In step 1, the rotation speed of the mechanical ball milling method is 80-120 r / min; In step 1, the mechanical mixing time is 2 to 4 hours; In step 1, the particle size of the nano-scale SiO2 is 10 to 20 nm.

6. The method for preparing anthracene hydrogenation catalyst according to claim 4, characterized in that: In step 2, the mechanical stirring time is 2 to 3 hours; In step 2, the drying is carried out at a temperature of 110° C. for 6 to 10 hours; In step 2, the calcination is carried out at a temperature of 600° C. for 3 to 5 hours; In step 2, the H2 reduction is carried out at a temperature of 600°C for 1 to 2 hours.