阅读说明：本技术 一种加氢催化剂及其制备方法和应用 (Hydrogenation catalyst, preparation method and application thereof ) 是由 涂椿滟 毋肖卓 陈奇 刘昌伟 黄伟 于 2020-05-11 设计创作，主要内容包括：本发明公开了一种加氢催化剂及其制备方法和应用。所述加氢催化剂包括载体、钼和至少一种选自第VIII族的活性金属组分,所述载体是SiO<Sub>2</Sub>-AlOOH复合物。本发明在铝盐的水解液中加入含硅源的水溶液,催化剂的表面酸性易于调节,B酸/L酸的摩尔比是0.5-3.2；在载体SiO<Sub>2</Sub>-AlOOH的合成过程中加入活性金属盐,使得最终形成的催化剂中活性金属在载体上均匀分散；合成的催化剂具有亲油性,容易在重油中均匀分散；与现有重油加氢处理催化剂相比,采用本发明的加氢催化剂能够获得更好的加氢脱硫、脱氮和裂化效果。(The invention discloses a hydrogenation catalyst, a preparation method and application thereof. The hydrogenation catalyst comprises a carrier, molybdenum and at least one active metal component selected from the VIII group, wherein the carrier is SiO 2 The invention adds the aqueous solution containing silicon source into the hydrolysate of aluminum salt, the surface acidity of the catalyst is easy to adjust, the molar ratio of B acid/L acid is 0.5-3.2, and SiO is carried on the carrier 2 Adding active metal salt in the synthesis process of AlOOH to ensure that the active metal in the finally formed catalyst is uniformly dispersed on the carrier; the synthesized catalyst has lipophilicity and is easy to uniformly disperse in heavy oil; compared with the prior heavy oil hydrotreating catalyst, the hydrogenation catalyst can be used for obtainingBetter hydrodesulfurization, denitrification and cracking effects.)

1. A hydrogenation catalyst characterized by: comprises a carrier, molybdenum and at least one active metal component selected from group VIII, wherein the carrier is SiO₂-an AlOOH complex; on the carrier SiO₂And adding an active metal salt in the AlOOH synthesis process, so that the active metal in the finally formed catalyst is uniformly dispersed on the carrier.

2. The hydrogenation catalyst of claim 1, wherein: calculated by oxide and based on the catalyst, the content of the metal component molybdenum is 5-45 wt%, the content of the metal component of the VIII group is 0.1-10 wt%, the content of the carrier is 45-92 wt%, and SiO₂2-50% of the carrier, wherein the metal component of the VIII group is nickel or cobalt.

3. The hydrogenation catalyst according to claim 1, wherein the obtained catalyst has a total infrared acid content of 40-350. mu. mol/g at 350 ℃ or higher, a molar ratio of B acid/L acid of 0.5-3.2, and the carrier is SiO₂-an AlOOH complex, the catalyst having the structure of AlOOH when characterized by XRD.

4. A method for preparing a hydrogenation catalyst according to any one of claims 1 to 3, characterized by comprising the steps of:

a) adding aqueous solution containing silicon source into aluminum salt hydrolysate, and stirring at 60-90 deg.C for 1-4 hr;

b) adding an aqueous solution containing a metal component molybdenum and at least one compound selected from hydrogenation active metal components of group VIII to the reaction mixture prepared in step a), and then stirring at a temperature of 60-100 ℃ for 1-10 hours to prepare a catalyst precursor;

c) aging and carrying out liquid phase heat treatment on the precursor prepared in the step b) to obtain the catalyst.

5. The method for producing a hydrogenation catalyst according to claim 4, wherein: in step a), the water/aluminum molar ratio of the hydrolysate is 50: 1-150: 1; with SiO₂The concentration of the silicon source solution is 20-50 wt%; the aluminum salt is one of aluminum nitrate, aluminum chloride, aluminum sulfate or aluminum isopropoxide, and the silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or silica sol.

6. The method for producing a hydrogenation catalyst according to claim 4, wherein: in the step c), the aging temperature is 20-100 ℃, and the aging time is 3 hours-7 days.

7. The method for producing a hydrogenation catalyst according to claim 4, wherein: in the step c), the liquid phase heat treatment solvent is liquid paraffin, the heat treatment temperature is 200-400 ℃, the heat treatment time is 2-8 hours, and the heat treatment pressure is normal pressure-5 MPa.

8. The application of the hydrogenation catalyst of any one of claims 1 to 3 in the heavy oil suspension bed hydrogenation treatment is characterized in that: the heavy oil is selected from at least one of catalytic cracking slurry oil, coal tar, deep drawing wax oil, atmospheric residue oil or vacuum residue oil.

9. Use according to claim 8The method is characterized in that: under the condition of heavy oil suspension bed hydrogenation, heavy oil and hydrogen are contacted with a hydrogenation catalyst, and heavy oil suspension bed hydrogenation treatment is carried out; in the continuous reaction device, the conditions of heavy oil suspension bed hydrogenation treatment are as follows: the reaction temperature is 350-480 ℃, the reaction pressure is 5-16MPa, and the volume space velocity is 0.1-4 hours^-1The volume ratio of hydrogen to oil is 200-; the adding amount of the catalyst is 0.1-1.5 wt% calculated by metal oxide.

10. Use according to claim 8, characterized in that: heavy oil, hydrogen and a hydrogenation catalyst are contacted, and heavy oil suspension bed hydrogenation treatment is carried out; in the batch reactor, the conditions of heavy oil suspension bed hydrogenation treatment are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 5-16MPa, and the reaction time is 1-6 hours; the adding amount of the catalyst is 0.3-2 wt% calculated by metal oxide.

Technical Field

The invention relates to a hydrogenation catalyst, a preparation method thereof and application thereof in heavy oil suspension bed hydrogenation, belonging to the technical field of catalyst preparation and application.

Background

In recent years, the crude oil deterioration degree in the global market is continuously increased, and with the continuous development of the world economy and the stricter environmental protection regulations of all countries, how to efficiently process the heavy crude oil poses a difficult problem to the oil refining industry. Heavy oil contains a large amount of impurities such as sulfur, nitrogen, metals and the like, which are not beneficial to the processing of subsequent products, so that the heavy oil needs to be treated. In the prior hydrogenation technology, the fixed bed hydrogenation process has small investment, but the catalyst is easy to be deactivated by local overheating, and although the suspension bed hydrogenation reactor has some technical defects, the operation is convenient, the heat transfer efficiency is high, the service life of the catalyst is greatly prolonged, and the heavy oil raw material can be processed. In the supported suspension bed hydrogenation catalyst, the main source of the catalytic activity of the catalyst is an active metal component selected from VIB group and VIII group loaded on an alumina carrier, and the catalyst can promote the activation of hydrogen molecules, the hydrogenolysis of hydrocarbon molecules, desulfurization and denitrification and other reactions. The acidity of the carrier has a large influence on the performance of the catalyst, and the acidity of the catalyst carrier is modulated by introducing an acidic component, which is beneficial to improving the hydrogenation activity of the catalyst.

Chinese patent CN1040610A discloses a hydrofining catalyst for hydrocarbons, which uses gamma-alumina containing titanium oxide as carrier and W-Mo-Ni as active component. The titanium oxide modified alumina can improve the performance of the catalyst to a certain extent, but the acid content of the carrier is low, which is not beneficial to the ring-opening fracture of the nitrogen heterocycle. When the raw material with high nitrogen content is processed, the denitrification effect is not obvious, and the long-term operation activity of the catalyst is not facilitated.

Chinese patent CN106925285A discloses a heavy oil hydrogenation catalyst using layered clay and silicon-containing alumina as carriers and W, Ni, Mo, and Co as active components, which is prepared by a saturation spray-dipping method, and the active metal solution is sprayed and dipped on the carriers. Chinese patent CN105749925A discloses a heavy oil hydrogenation catalyst, wherein a silicon or fluorine-containing alumina carrier is subjected to hydrothermal treatment under a closed condition, and then metal components of molybdenum, nickel and cobalt are loaded on the carrier in an impregnation mode, so that the obtained catalyst has good desulfurization, denitrification and carbon residue removal effects when being used for heavy oil hydrogenation treatment. However, the conventional impregnation method is adopted to load metal on the carrier, and the prepared catalyst is limited by the concentration of the impregnation liquid, so that the prepared catalyst is not easy to have higher active metal content and metal dispersity, and the improvement of the activity of the catalyst is influenced.

US6387248 uses a dry-mix kneading method to prepare a heavy oil hydrogenation catalyst, and the porous alumina support and the group VIB, VIII metal salt are ground in the presence of an acid (phosphoric acid, nitric acid or acetic acid), and then extruded, dried and calcined. Since the metal component is added to the alumina powder in the form of metal salt powder, the active metal is likely to be unevenly distributed on the carrier.

In addition, the catalysts provided by the technology have poor lipophilicity, and when the catalysts are used for the hydrotreatment of a heavy oil suspended bed, the dispersion process of the catalysts is complex and the energy consumption is high.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a novel hydrogenation catalyst with moderate surface acidity, uniformly dispersed active metals and good hydrodesulfurization, denitrification and cracking effects and a preparation method thereof, and also provides application of the catalyst in the hydrogenation treatment of a heavy oil suspension bed with dispersed oil phase.

The invention adds the aqueous solution containing silicon source into the aluminum salt hydrolysate, which is easy to adjust the surface acidity of the catalyst. On the carrier SiO₂Active metal salt is added in the synthesis process of AlOOH, so that the catalyst with high active metal content can be obtained, and the active metal is uniformly dispersed on the carrier. The catalyst precursor is heat treated in oil phase to form lipophilic catalyst, which is easy to disperse in heavy oil for hydrogenating suspension bed.

The invention provides a hydrogenation catalyst, which comprises a carrier, molybdenum and at least one active metal component selected from VIII groups.

In the hydrogenation catalyst, the metal component molybdenum contains molybdenum in terms of oxide and based on the catalystIn an amount of 5 to 45 wt%, a group VIII metal component in an amount of 0.1 to 10 wt%, a carrier in an amount of 45 to 92 wt%, SiO₂The catalyst is prepared with the catalyst, and through reaction of catalyst with catalyst in the temperature higher than 350 deg.c and in the infrared total acid amount of 40-350 micron mol/g, acid B/L ratio of 0.5-3.2, and the carrier is SiO₂-an AlOOH complex, the catalyst having the structure of AlOOH when characterized by XRD and at 2 θ =26^oNo MoO appeared₃Characteristic peak.

The invention provides a preparation method of the hydrogenation catalyst, which comprises the following steps:

a) adding aqueous solution containing silicon source into hydrolysate of aluminum salt, stirring for 1-4 hours at the temperature of 60-90 ℃, wherein the molar ratio of water to aluminum in the hydrolysate is 50: 1-150: 1, the concentration of the silicon source solution is 20-50 wt% (based on SiO)₂Aluminum salt is one of aluminum nitrate, aluminum chloride, aluminum sulfate or aluminum isopropoxide, and a silicon source is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or silica sol;

b) adding an aqueous solution containing a metal component molybdenum and at least one compound selected from hydrogenation active metal components of group VIII to the reaction mixture prepared in step a), and then stirring at a temperature of 60-100 ℃ for 1-10 hours to prepare a catalyst precursor;

c) aging and liquid phase heat treatment are carried out on the precursor prepared in the step b) to obtain the catalyst, wherein the aging temperature is 20-100 ℃, the aging time is 3 hours-7 days, the liquid phase heat treatment solvent is liquid paraffin, the heat treatment temperature is 200-400 ℃, the heat treatment time is 2-8 hours, and the heat treatment pressure is normal pressure-5 MPa.

The invention provides an application of the hydrogenation catalyst in the hydrogenation treatment of a heavy oil suspended bed. The heavy oil is selected from at least one of catalytic cracking slurry oil, coal tar, deep drawing wax oil, atmospheric residue oil or vacuum residue oil.

Under the condition of heavy oil suspension bed hydrogenation, heavy oil and hydrogen are contacted with a hydrogenation catalyst, and heavy oil suspension bed hydrogenation treatment is carried out; in a continuous reaction apparatus, heavy oil is suspendedThe bed hydrotreating conditions were: the reaction temperature is 350-480 ℃, the reaction pressure is 5-16MPa, and the volume space velocity is 0.1-4 hours^-1The volume ratio of hydrogen to oil is 200-; the adding amount of the catalyst is 0.1-1.5 wt% calculated by metal oxide.

Heavy oil, hydrogen and a hydrogenation catalyst are contacted, and heavy oil suspension bed hydrogenation treatment is carried out; in the batch reactor, the conditions of heavy oil suspension bed hydrogenation treatment are as follows: the reaction temperature is 350-450 ℃, the reaction pressure is 5-16MPa, and the reaction time is 1-6 hours; the adding amount of the catalyst is 0.3-2 wt% calculated by metal oxide.

The invention has the beneficial effects that:

according to the invention, the aqueous solution containing the silicon source is added into the aluminum salt hydrolysate, so that the surface acidity of the catalyst is easy to adjust; on the carrier SiO₂Active metal salt is added in the synthesis process of AlOOH, so that the catalyst with high active metal content can be obtained, and the active metal is uniformly dispersed on the carrier; the synthesized catalyst has lipophilicity and is easy to uniformly disperse in heavy oil; compared with the existing heavy oil hydrotreating catalyst, the hydrogenation catalyst of the invention is used for heavy oil suspension bed hydrotreating, and can obtain better hydrodesulfurization, denitrification and cracking effects.

Drawings

FIG. 1 is an XRD spectrum of hydrogenation catalyst C-1 prepared in example 1 of the present invention.

Detailed Description

The invention will now be further illustrated by the following examples, but is not limited thereto. The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

According to the invention, the crystallographic phase diagram of X-ray diffraction (XRD) is obtained by Shimadzu XRD 7000X measurement under the test conditions of Cu target, K α radiation, Ni filter, super-energy detector, tube voltage of 40KV and tube current of 40 mA.