阅读说明：本技术 一种加氢催化剂及其制备方法和在重油悬浮床加氢处理中的应用 (Hydrogenation catalyst, preparation method thereof and application thereof in heavy oil suspension bed hydrogenation treatment ) 是由 涂椿滟 毋肖卓 刘昌伟 陈奇 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在重油悬浮床加氢处理中的应用,所述加氢催化剂包括载体、金属组分钼、至少一种选自第VIII族的非贵金属组分和助剂组分,所述助剂组分包括硼或硼与磷的组合物,所述载体是拟薄水铝石,催化剂的≥350℃红外总酸量为40-350μmol/g；所述催化剂采用XRD表征时,在2θ=26<Sup>o</Sup>时没有出现MoO<Sub>3</Sub>特征峰。与现有技术相比,采用本发明提供的催化剂进行重油的悬浮床加氢处理,催化剂具有更好的加氢脱硫、脱氮效果。(The invention discloses a hydrogenation catalyst and a preparation method thereof and application thereof in heavy oil suspension bed hydrogenation treatment, wherein the hydrogenation catalyst comprises a carrier, a metal component molybdenum, at least one non-noble metal component selected from VIII group and an auxiliary agent component, the auxiliary agent component comprises boron or a composition of boron and phosphorus, the carrier is pseudo-boehmite, and the infrared total acid content of the catalyst at the temperature of more than or equal to 350 ℃ is 40-350 mu mol/g; the catalyst is characterized by XRD at 2 theta =26 o No MoO appeared 3 Characteristic peak. Compared with the prior art, the invention providesThe catalyst is used for the suspension bed hydrogenation treatment of heavy oil, and has better hydrodesulfurization and denitrification effects.)

1. A hydrogenation catalyst characterized by: comprises a carrier, a metal component molybdenum, at least one non-noble metal component selected from VIII group and an auxiliary agent component, wherein the auxiliary agent component comprises boron or a composition of boron and phosphorus; the carrier is pseudoboehmite.

2. The hydrogenation catalyst of claim 1, wherein: calculated by oxide and by taking the catalyst as 100 percent, the content of the metal component molybdenum is 8 to 45 percent by weight, the content of the metal component of the VIII group is 1 to 12 percent by weight, the content of the auxiliary agent component is 1 to 16 percent by weight, and the content of the carrier is 45 to 90 percent by weight, wherein the metal component of the VIII group is nickel or iron, and the auxiliary agent is selected from boric acid or boron phosphate; the infrared total acid content of the obtained catalyst at the temperature of more than or equal to 350 ℃ is 40-350 mu mol/g.

3. The hydrogenation catalyst of claim 2, wherein: calculated by oxide and by taking the catalyst as 100 percent, the content of the metal component molybdenum is 10 to 35 percent by weight, the content of the metal component of the VIII group is 2 to 10 percent by weight, the content of the auxiliary agent component is 2 to 12 percent by weight, the content of the carrier is 55 to 85 percent by weight, and the infrared total acid content of the obtained catalyst at the temperature of more than or equal to 350 ℃ is 50 to 280 mu mol/g.

4. The hydrogenation catalyst of claim 1, wherein: the catalyst is characterized by XRD at 2 theta =26^oNo MoO appeared₃Characteristic peak.

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

a) adding an aqueous solution or an alcohol solution containing an auxiliary agent into a hydrolysate of aluminum salt, wherein the water/aluminum molar ratio in the hydrolysate is 50: 1-150: 1, the concentration of the assistant solution is 10-50 wt%, and the molar ratio of aluminum to phosphorus is 2.2: 1-16: 1;

b) adding an aqueous solution containing a metal component molybdenum and at least one compound selected from non-noble 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.

6. The method for producing a hydrogenation catalyst according to claim 5, wherein: the aluminum salt is aluminum nitrate, aluminum sulfate or aluminum isopropoxide, the auxiliary agent is boric acid or boron phosphate, the alcohol is ethanol or isopropanol, the molybdenum salt is ammonium molybdate tetrahydrate, and the VIII group metal salt is nickel nitrate hexahydrate or ferric nitrate nonahydrate.

7. The method for producing a hydrogenation catalyst according to claim 5, wherein: in the step c), the aging temperature is 10-70 ℃, the aging time is 1-10 days, the liquid phase heat treatment solvent is liquid paraffin, the heat treatment temperature is 200-400 ℃, and the heat treatment time is 2-10 hours.

8. Use of a hydrogenation catalyst according to any one of claims 1 to 4 in the hydroprocessing of heavy oil suspended beds.

9. Use according to claim 8, 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;

the conditions of the heavy oil suspension bed hydrogenation treatment comprise: the reaction temperature is 350-480 ℃, the reaction pressure is 5-16MPa, and the reaction time is 0.5-6 hours.

10. Use according to claim 8, characterized in that: the heavy oil is at least one of atmospheric residue, vacuum residue, catalytic cracking slurry oil or coal tar.

Technical Field

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

Background

With the development of the world economy and the enhancement of environmental awareness, the demand of each country for clean fuels is continuously increased, and the efficient processing and utilization of heavy oil become challenges for the oil refining industry. Heavy oil is enriched in impurities such as sulfur, nitrogen, metals, etc. in crude oil, which have important influence on subsequent processing and product properties and thus must be removed. Catalytic hydrotreating is one of the most widely used means. The fixed bed hydrogenation process is prone to local overheating and catalyst deactivation. Although the suspension bed hydrogenation reactor is not as efficient as a fixed bed reactor in the mass transfer process, the suspension bed hydrogenation reactor has the advantages of wide raw material adaptability, flexible operation, capability of transferring heat in time, uniform heat distribution and great improvement on the stability of the catalyst. The main source of catalytic activity in the supported suspension bed hydrogenation catalyst is active metal components selected from VIB group and VIII group loaded on an alumina carrier, and the catalytic activity promotes the reactions of hydrogen molecule activation, hydrocarbon molecule hydrogenolysis, desulfurization and denitrification and the like. Modulating the properties of the support is a common means of improving the performance of hydrogenation catalysts.

Chinese patent CN1040610A discloses a hydrofining catalyst for hydrocarbons, which takes gamma-alumina loaded with titanium oxide as a carrier and W-Mo-Ni as an 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 CN101314130A discloses a boron-containing hydrodesulfurization catalyst, which is prepared by impregnating an alumina carrier with a structure of or θ with a boron-containing aqueous solution to obtain a boron surface-modified alumina carrier, and then impregnating the carrier with a supported active metal component. The catalyst has a good hydrodesulfurization effect, but is limited by the maximum concentration of an impregnation liquid due to the use of a conventional impregnation method, the promotion space of the boron content and the active component content is small, metal aggregation is easily caused when the metal loading is high, the utilization rate of active metal is low, and the reaction activity of the catalyst is limited.

Disclosure of Invention

The invention aims to provide a novel heavy oil slurry bed hydrotreating catalyst with moderate surface acidity, high active metal dispersion degree and better desulfurization and denitrification effects and a preparation method thereof aiming at the defects of the prior art.

According to the invention, the boron or the composition of boron and phosphorus is added into the hydrolysate of the aluminum carrier precursor salt, the surface acidity of the catalyst is easy to adjust, and the adjustable range is wide. Active metal salt is added in the synthesis process of the aluminum carrier, so that active metal particles in the finally formed catalyst are small and uniformly dispersed on the surface of the carrier.

The invention provides a hydrogenation catalyst, which comprises a carrier, a metal component molybdenum, at least one non-noble metal component selected from VIII groups and an auxiliary component, wherein the auxiliary component comprises boron or a composition of boron and phosphorus.

In the obtained hydrogenation catalyst, the ratio of each component in the catalyst is calculated by oxide and by taking the catalyst as 100 percent: the content of the metal component molybdenum is 8-45 wt%, the content of the metal component of the VIII group is 1-12 wt%, the content of the auxiliary agent component is 1-16 wt% (calculated by boron or the sum of boron and phosphorus), and the content of the carrier is 45-90 wt%, wherein the metal component of the VIII group is nickel or iron, and the auxiliary agent is selected from boric acid or boron phosphate. The obtained catalyst has an infrared total acid content of 40-350 [ mu ] mol/g at a temperature of more than or equal to 350 ℃, the carrier is pseudo-boehmite, and the catalyst is characterized by XRD (X-ray diffraction) at a temperature of 2 theta =26^oNo MoO appeared₃Characteristic peak.

Further, the content of the metal component molybdenum is 10-35 wt%, the content of the metal component VIII is 2-10 wt%, the content of the auxiliary agent component is 2-12 wt% (based on the sum of boron or boron and phosphorus), the content of the carrier is 55-85 wt%, and the infrared total acid content of the catalyst at the temperature of more than or equal to 350 ℃ is 50-280 mu mol/g.

The preparation method of the hydrogenation catalyst provided by the invention comprises the following steps: a) adding an aqueous solution or an alcohol solution containing an auxiliary agent into a hydrolysate of aluminum salt, wherein the water/aluminum molar ratio in the hydrolysate is 50: 1-150: 1, the concentration of the assistant solution is 10-50 wt%, and the molar ratio of aluminum to phosphorus is 2.2: 1-16: 1, the aluminum salt is aluminum nitrate, aluminum sulfate or aluminum isopropoxide, the auxiliary agent is boric acid or boron phosphate, and the alcohol is ethanol or isopropanol; b) adding an aqueous solution containing a compound of a metal component molybdenum and at least one non-noble metal component selected from 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, wherein the molybdenum salt is ammonium molybdate tetrahydrate, and the group VIII metal salt is nickel nitrate hexahydrate or iron nitrate nonahydrate; c) and (c) aging and carrying out liquid phase heat treatment on the precursor prepared in the step b) under certain conditions to obtain the catalyst, wherein the aging temperature is 10-70 ℃, the aging time is 1-10 days, the liquid phase heat treatment solvent is liquid paraffin, the heat treatment temperature is 200-400 ℃, and the heat treatment time is 2-10 hours.

The invention also provides a heavy oil suspension bed hydrotreatment method, which comprises the following steps: under the condition of heavy oil suspension bed hydrogenation, heavy oil and hydrogen are contacted with the hydrogenation catalyst provided by the invention, and heavy oil suspension bed hydrogenation treatment is carried out.

In the above method for hydrotreating a heavy oil suspension bed, the heavy oil is at least one selected from atmospheric residue, vacuum residue, catalytic cracking slurry oil, and coal tar.

In the above method for hydroprocessing heavy oil in a suspended bed, the conditions for hydroprocessing heavy oil include: the reaction temperature is 350-480 ℃, the reaction pressure is 5-16MPa, and the reaction time is 0.5-6 hours.

The invention has the beneficial effects that:

according to the invention, the boron or boron and phosphorus auxiliary agent is introduced into the hydrolysate of the aluminum carrier precursor salt, the surface acidity of the catalyst is easy to adjust, and the adjustable range is wide; compared with the existing heavy oil hydrotreating catalyst, the hydrogenation catalyst of the invention has better hydrodesulfurization and denitrification effects when being used for heavy oil slurry bed hydrotreating.

Drawings

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

Detailed Description

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.