阅读说明：本技术 汽油加氢脱硫催化剂的制备方法和汽油加氢脱硫催化剂及其应用 (Preparation method of gasoline hydrodesulfurization catalyst, gasoline hydrodesulfurization catalyst and application thereof ) 是由 任亮 邵志才 刘涛 施瑢 邓中活 聂鑫鹏 于 2018-09-11 设计创作，主要内容包括：本公开涉及一种汽油加氢脱硫催化剂的制备方法和汽油加氢脱硫催化剂及其应用,该方法包括以下步骤：a、将含有第一金属组分、第二金属组分和催化油浆的混合物料填充到具有空腔的石墨棒中,然后封闭所述石墨棒,得到阳极石墨棒；b、将步骤a得到的所述阳极石墨棒与阴极石墨棒置于电弧放电装置中,在含有氢气和氦气的混合气氛下,使所述阳极石墨棒与阴极石墨棒发生电弧放电,待所述阳极石墨棒消耗完毕后收集所述电弧放电装置中得到的以石墨烯为载体的汽油加氢脱硫催化剂；所述第一金属组分为选自第VIB族的金属,所述第二金属组分为选自第VIII族的金属。该催化剂的脱硫活性高,能够在较缓和的条件下对工业催化裂化汽油进行深度脱硫。(The disclosure relates to a preparation method of a gasoline hydrodesulfurization catalyst, the gasoline hydrodesulfurization catalyst and an application thereof, wherein the method comprises the following steps: a. filling a mixed material containing a first metal component, a second metal component and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod; b. b, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a mixed atmosphere containing hydrogen and helium, and collecting a gasoline hydrodesulfurization catalyst which is obtained in the arc discharge device and takes graphene as a carrier after the anode graphite rod is consumed; the first metal component is a metal selected from a VIB group, and the second metal component is a metal selected from a VIII group. The catalyst has high desulfurization activity and can deeply desulfurize industrial catalytic cracking gasoline under mild conditions.)

1. A method for preparing a gasoline hydrodesulfurization catalyst, comprising the steps of:

a. filling a mixed material containing a first metal component, a second metal component and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod;

b. b, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a mixed atmosphere containing hydrogen and helium, and collecting a gasoline hydrodesulfurization catalyst which is obtained in the arc discharge device and takes graphene as a carrier after the anode graphite rod is consumed;

the first metal component is a metal selected from a VIB group, and the second metal component is a metal selected from a VIII group.

2. The method of claim 1, wherein in step a, the first metal component is used in an amount of 3 to 15 wt%, the second metal component is used in an amount of 2 to 10 wt%, and the catalytic slurry oil is used in an amount of 75 to 95 wt%, based on the total weight of the mixture.

3. The method of claim 2, wherein in step a, the first metal component is used in an amount of 10 to 13 wt%, the second metal component is used in an amount of 5 to 7 wt%, and the catalytic slurry oil is used in an amount of 82 to 85 wt%, based on the total weight of the mixture.

4. The method of claim 1, wherein the first metal component is Mo and/or W and the second metal component is Ni and/or Co.

5. The method of claim 1, wherein in the step a, the aromatic hydrocarbon content of the catalytic slurry oil is 50-60 wt%.

6. The method according to claim 1, wherein in the step a, the first metal component and the second metal component are respectively simple substances, and the particle size of each of the first metal component and the second metal component is 140-160 μm.

7. The method of claim 1, wherein in step b, the arc discharge conditions comprise: the distance between the anode graphite rod and the cathode graphite rod is 2-4 mm, the discharge voltage is 20-40V, the discharge current is 130-150A, and the absolute pressure is 0.01-0.03 MPa; the content of hydrogen in the mixed atmosphere is 25-75 vol%, preferably 40-60 vol%.

8. The method according to claim 1, wherein the graphite rod with the cavity has a length of 60 to 80mm and a diameter of 7 to 10 mm; the cavity extends along the axial direction of the graphite rod, the axial length of the cavity is 40-60 mm, and the inner diameter of the cavity is 4-6 mm;

the cathode graphite rod is a solid graphite rod, the length of the solid graphite rod is 10-30 mm, and the diameter of the solid graphite rod is 8-20 mm.

9. A gasoline hydrodesulfurization catalyst prepared by the method of any one of claims 1 to 8.

10. The gasoline hydrodesulfurization catalyst of claim 9 wherein the graphene has a specific surface area of 140 to 290m²/g。

11. Use of a catalyst according to claim 9 or 10 in the hydrodesulphurisation of gasoline.

12. The application of claim 11, wherein the application comprises: contacting industrial catalytic cracking gasoline with the gasoline hydrodesulfurization catalyst for reaction to obtain low-sulfur gasoline;

the sulfur content of the industrial catalytic cracking gasoline is 300-1000 mug/g;

the reaction conditions include: the reaction temperature is 200-450 ℃, the reaction pressure is 1-6 MPa, and the weight hourly space velocity is 5-20 h^-1The volume ratio of hydrogen to oil is 50-500.

Technical Field

The disclosure relates to a preparation method of a gasoline hydrodesulfurization catalyst, the gasoline hydrodesulfurization catalyst and application thereof.

Background

Sulfur-containing compounds in gasoline present a number of hazards: the sulfur oxides generated by combustion at high temperature can be converted into acid to corrode and damage engine parts, so that a three-way catalyst of an engine tail gas purification system generates irreversible poisoning, and NO in emissions_XAnd CO_XThe content of SO is obviously increased and in addition, SO discharged into the atmosphere_XAcid rain can also result. Therefore, many countries in the world have made strict regulations on the sulfur content of mogas by regulation. From 1 month and 1 day in 2017, the China motor vehicle has comprehensively implemented the national fifth emission standard (the limit value of the sulfur content index is 10 mug/g), and the more strict national sixth standard is also made. Therefore, the development of the gasoline deep desulfurization technology is imminent to produce gasoline with low sulfur content.

The ultra-deep Hydrodesulfurization (HDS) technology is the most dominant gasoline desulfurization technology in the gasoline processing of oil refineries. Development and modification of equipment is one way to achieve HDS, but the investment is very large, and in comparison, development of catalysts and change of refinery process conditions are relatively economic options. The method for carrying out ultra-deep Hydrodesulfurization (HDS) under the premise of not improving equipment at present is to improve the reaction processTemperature and pressure. However, at too high a temperature and pressure, Al is present₂O₃A supported hydrodesulfurization catalyst can be permanently deactivated. Because of Al at high temperature and high pressure₂O₃The Al atoms in the catalyst undergo an atom transfer reaction with metal atoms (such as Ni, Mo, etc.) in the metal active center supported by the Al atoms, so that the molecular structure of the catalyst is changed, and the catalyst loses activity. Therefore, in recent years, many scientists have sought new carriers to replace Al₂O₃。

Disclosure of Invention

The purpose of the present disclosure is to provide a preparation method of a gasoline hydrodesulfurization catalyst, a gasoline hydrodesulfurization catalyst and applications thereof, wherein the catalyst has high desulfurization activity and can deeply desulfurize industrial catalytic cracking gasoline under mild conditions.

To achieve the above object, a first aspect of the present disclosure: a method for preparing a gasoline hydrodesulfurization catalyst is provided, which comprises the following steps:

a. filling a mixed material containing a first metal component, a second metal component and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod;

b. b, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a mixed atmosphere containing hydrogen and helium, and collecting a gasoline hydrodesulfurization catalyst which is obtained in the arc discharge device and takes graphene as a carrier after the anode graphite rod is consumed;

the first metal component is a metal selected from a VIB group, and the second metal component is a metal selected from a VIII group.

Optionally, in the step a, based on the total weight of the mixture, the amount of the first metal component is 3 to 15 wt%, the amount of the second metal component is 2 to 10 wt%, and the amount of the catalytic slurry oil is 75 to 95 wt%.

Optionally, in step a, based on the total weight of the mixture, the amount of the first metal component is 10 to 13 wt%, the amount of the second metal component is 5 to 7 wt%, and the amount of the catalytic slurry oil is 82 to 85 wt%.

Optionally, the first metal component is Mo and/or W and the second metal component is Ni and/or Co.

Optionally, in the step a, the aromatic hydrocarbon content of the catalytic slurry oil is 50-60 wt%.

Optionally, in the step a, the first metal component and the second metal component are respectively simple substances, and the particle size of each of the first metal component and the second metal component is 140 to 160 μm.

Optionally, in step b, the arc discharge condition includes: the distance between the anode graphite rod and the cathode graphite rod is 2-4 mm, the discharge voltage is 20-40V, the discharge current is 130-150A, and the absolute pressure is 0.01-0.03 MPa; the content of hydrogen in the mixed atmosphere is 25-75 vol%, preferably 40-60 vol%.

Optionally, the length of the graphite rod with the cavity is 60-80 mm, and the diameter of the graphite rod with the cavity is 7-10 mm; the cavity extends along the axial direction of the graphite rod, the axial length of the cavity is 40-60 mm, and the inner diameter of the cavity is 4-6 mm;

the cathode graphite rod is a solid graphite rod, the length of the solid graphite rod is 10-30 mm, and the diameter of the solid graphite rod is 8-20 mm.

In a second aspect of the present disclosure: there is provided a gasoline hydrodesulphurisation catalyst prepared by the process according to the first aspect of the present disclosure.

The specific surface area of the graphene is 140-290 m²/g。

Optionally, the third aspect of the present disclosure: there is provided the use of a catalyst according to the second aspect of the present disclosure in the hydrodesulphurisation of gasoline.

Optionally, the applying comprises: contacting industrial catalytic cracking gasoline with the gasoline hydrodesulfurization catalyst for reaction to obtain low-sulfur gasoline;

the sulfur content of the industrial catalytic cracking gasoline is 300-1000 mug/g;

the reaction conditions include: the reaction temperature is 200-450 ℃, the reaction pressure is 1-6 MPa, and the weight hourly space velocity is 5-20 h^-1The volume ratio of hydrogen to oil is 50-500.

According to the technical scheme, the catalytic slurry oil is used as a carbon source for preparing the graphene, and the metal-loaded gasoline hydrodesulfurization catalyst using the graphene as a carrier is prepared. The method provides an effective way for solving the processing and utilization problems of the catalytic slurry oil, and has the advantages of simple process, high graphene yield and uniform metal component loading. Compared with the gasoline desulfurization catalyst in the prior art, the catalyst disclosed by the invention has higher desulfurization activity, and can realize deep desulfurization of industrial catalytic cracking gasoline under a milder condition.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

FIG. 1 is a TEM photograph of a gasoline hydrodesulfurization catalyst C2 prepared in example 2.

FIG. 2 is a TEM photograph of gasoline hydrodesulfurization catalyst C7 prepared in example 7.

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

The first aspect of the disclosure: a method for preparing a gasoline hydrodesulfurization catalyst is provided, which comprises the following steps:

a. filling a mixed material containing a first metal component, a second metal component and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod;

b. and c, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a mixed atmosphere containing hydrogen and helium, and collecting the gasoline hydrodesulfurization catalyst which is obtained in the arc discharge device and takes the graphene as a carrier after the anode graphite rod is consumed. The first metal component is a metal selected from a VIB group, and the second metal component is a metal selected from a VIII group. Further, the first metal component may be Mo and/or W, and the second metal component may be Ni and/or Co.

The catalytic slurry oil is used as a carbon source for preparing graphene, and the metal-loaded gasoline hydrodesulfurization catalyst using graphene as a carrier is prepared. The method provides an effective way for solving the processing and utilization problems of the catalytic slurry oil, and has the advantages of simple process, high graphene yield and uniform metal component loading.

In order to achieve the desired effect, in step a, the first metal component may be used in an amount of 3 to 15 wt%, preferably 10 to 13 wt%, based on the total weight of the mixture; the second metal component may be used in an amount of 2 to 10 wt%, preferably 5 to 7 wt%; the amount of the catalytic slurry oil used may be 75 to 95 wt%, preferably 82 to 85 wt%.

The meaning of the catalytic slurry oil is well known to those skilled in the art in light of this disclosure and generally refers to the residue oil discharged from a catalytic cracking unit of a refinery. The catalytic slurry oil in a refinery has the processing and utilization problems due to the factors of poor reaction property, high solid particle content and the like, and can only be thrown out of a device. In the research of the inventor of the present disclosure, it is found that the aromatic hydrocarbon content in the catalytic slurry oil is high, and the catalytic slurry oil is an ideal component for preparing the carbon nano two-dimensional material. Specifically, in the step a, the aromatic hydrocarbon content of the catalytic slurry oil may be 50 to 60 wt%. The content of other components in the catalytic slurry oil is not particularly limited, and for example, 10 to 20 wt% of saturated hydrocarbon, 20 to 30 wt% of colloid, 2 to 8 wt% of asphaltene and the like may be contained.

According to the present disclosure, in step a, the first metal component and the second metal component are respectively simple substances. Furthermore, the first metal component and the second metal component can be powdery metal particles respectively, and the particle diameters of the first metal component and the second metal component can be 140-160 micrometers respectively, so that the first metal component and the second metal component can be more uniformly loaded on graphene, agglomeration is avoided, and the desulfurization activity of the catalyst is further improved.

The process of preparing graphene using an arc discharge method according to the present disclosure may be conventional in the art. For example, after the anode graphite rod and the cathode graphite rod are placed in an arc discharge device, the arc discharge device can be purged by nitrogen firstly, and then the arc discharge device can be purged by a mixed gas containing hydrogen and helium; then introducing a mixed atmosphere containing hydrogen and helium into the arc discharge device to reach the required absolute pressure; in order to further improve the purity of the graphene, cooling water can be introduced into the device after the steps; then starting a direct current power supply, and enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a certain condition; and after the anode graphite rod is consumed, turning off the power supply, stopping introducing cooling water, and collecting the gasoline hydrodesulfurization catalyst taking the graphene as the carrier in the arc discharge device (such as on the wall surface of the device). Further, the step of purging the apparatus with nitrogen may be performed a plurality of times (e.g., 34 times), and the step of purging the apparatus with a mixture of hydrogen and helium may be performed 1 time, to exclude air from the arc discharge apparatus. The arc discharge device is not particularly limited by the present disclosure and may be various conventional apparatuses well known to those skilled in the art.

According to the present disclosure, in step b, the arc discharge condition may include: the distance between the anode graphite rod and the cathode graphite rod is 2-4 mm, the discharge voltage is 20-40V, the discharge current is 130-150A, the absolute pressure is 0.01-0.03 MPa, and the discharge time can be 5-15 min. The content of hydrogen in the mixed atmosphere may be 25 to 75% by volume, preferably 40 to 60% by volume.

Generally, according to the present disclosure, the anode graphite rod has a smaller diameter, while the cathode graphite rod has a larger diameter. Specifically, the length of the graphite rod with the cavity can be 60-80 mm, and the diameter can be 7-10 mm; the cavity is followed the axial extension of graphite rod, the axial length of cavity can be 40 ~ 60mm, and the internal diameter can be 4 ~ 6 mm. The cathode graphite rod is a solid graphite rod, the length of the solid graphite rod can be 10-30 mm, and the diameter of the solid graphite rod can be 8-20 mm.

In a second aspect of the present disclosure: there is provided a gasoline hydrodesulphurisation catalyst prepared by the process according to the first aspect of the present disclosure. Compared with the gasoline desulfurization catalyst in the prior art, the catalyst disclosed by the invention has higher desulfurization activity, and can realize deep desulfurization of industrial catalytic cracking gasoline under a milder condition. Further, the catalyst may include 3 to 15 wt% of the first metal component, 2 to 10 wt% of the second metal component, and 80 to 95 wt% of graphene, based on the dry weight of the catalyst. Preferably, the catalyst comprises 9-12 wt% of the first metal component, 5-6 wt% of the second metal component, and 83-86 wt% of graphene, based on the dry weight of the catalyst. The graphene in the gasoline hydrodesulfurization catalyst has a suitable specific surface area, so that gasoline hydrodesulfurization is facilitated, and specifically, the specific surface area of the graphene can be 140-290 m²Preferably 230 to 290 m/g²/g。

A third aspect of the disclosure: there is provided the use of a catalyst according to the second aspect of the present disclosure in the hydrodesulphurisation of gasoline.

According to the present disclosure, the applying may include: and (3) contacting industrial catalytic cracking gasoline with the gasoline hydrodesulfurization catalyst to react to obtain the gasoline with low sulfur content. The conditions of the reaction may include: the reaction temperature is 200-450 ℃, the reaction pressure is 1-6 MPa, and the weight hourly space velocity is 5-20 h^-1The volume ratio of hydrogen to oil is 50-500. The sulfur content of the industrial catalytic cracking gasoline can be 300-1000 mug/g. The reaction can be carried out in a fixed bed reaction device, and the fixed bed reaction device can realize continuous feeding and sampling operation. The catalyst disclosed by the invention can still keep a high desulfurization rate (for example, more than 90 wt%) after a long reaction time (for example, 100 h); preferably, the steam after the reactionThe sulfur content of the oil can reach the national V gasoline standard.

The following examples further illustrate the methods provided by the present disclosure, but are not intended to limit the disclosure thereto.