CN111744516A

CN111744516A - Hydrotreating catalyst and application thereof

Info

Publication number: CN111744516A
Application number: CN201910248441.6A
Authority: CN
Inventors: 王锦业; 李明丰; 王哲; 聂红; 胡志海; 任亮; 张锐; 张润强; 李坚; 王轶凡
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-03-29
Filing date: 2019-03-29
Publication date: 2020-10-09
Anticipated expiration: 2039-03-29
Also published as: CN111744516B

Abstract

The invention relates to a hydrotreating catalyst and a hydrotreating method, wherein the hydrotreating catalyst comprises a formed carrier, a hydrogenation active metal component loaded on the formed carrier, an optional phosphorus auxiliary agent and an optional organic additive; the preparation method of the catalyst comprises the following steps: introducing a VIB group metal into a formed carrier and pre-vulcanizing to obtain a catalyst intermediate; the group VIII metal is then introduced into the catalyst intermediate, dried, optionally calcined or optionally sulfided, to obtain the catalyst, wherein an optional phosphorus promoter and/or organic additive is introduced at the time of introduction of the group VIB metal and/or group VIII metal. Compared with the prior art, the catalyst provided by the invention has higher hydrodesulfurization activity when being used for hydrotreating.

Description

Hydrotreating catalyst and application thereof

Technical Field

The invention belongs to the field of hydrogenation catalysts, and particularly relates to a hydrogenation catalyst and application of the catalyst in hydrogenation treatment.

Background

Nitrogen Oxides (NO) in motor vehicle exhaust gases_X) Not only acid rain in cities and surrounding areas is formed, but also the ozone layer of the earth is seriously damaged; particulate Matter (PM) in the exhaust gas contains various substances which are listed as possibly carcinogenic substances by international research institutes; sulfur-containing compounds in diesel fuel also have a great influence on the emission of automotive pollutants, especially on NO_XAnd PM, Sulfur Oxides (SO) generated during combustion of sulfur-containing compounds_X) Not only is the main reason for the formation of acid rain, but also can cause the poisoning of the catalyst for purifying the tail gas of the motor vehicle. The aromatic hydrocarbon in the diesel oil has a plurality of adverse effects on the properties of the diesel oil, and the aromatic hydrocarbon can cause carbon monoxide and NO in the automobile exhaust_XAnd PM and other pollutants, and aromatic hydrocarbons can also reduce the cetane number of diesel oil. Fused aromatic hydrocarbons represented by 3, 4-benzopyrene in paraffin are considered carcinogenic substances.

Related technologies such as hydrotreating catalysts aimed at the upgrading of petroleum distillates and the like have been rapidly developed in order to improve the quality of petroleum products. In addition, as petroleum resources are gradually reduced, coal liquefaction technology is developed, wherein the coal direct liquefaction oil contains more nitrogen-containing compounds, oxygen-containing compounds, aromatic hydrocarbons and olefin substances, and needs to be subjected to hydrotreating before use; olefins and oxygenates contained in coal-based and natural gas-based synthetic (fischer-tropsch) oils also need to be hydrotreated prior to upgrading; the preparation of biodiesel or bio-kerosene from vegetable oils by the hydroisomerization process also requires a prior hydrotreatment.

Active component of hydrotreating catalystTypically group VIB (often referred to as the main agent, e.g. Mo and W) and group VIII (often referred to as the promoter, e.g. Co and Ni) metals, and the support is typically γ -Al₂O₃. According to the research in the field, the hydrotreating catalyst has a certain difference in activity selectivity according to the combination of active metals therein. For example, the cobalt molybdenum combination is most active for direct hydrodesulfurization reactions; the nickel-tungsten combination has the highest activity for hydrodenitrogenation and aromatic hydrocarbon (or olefin) hydrogenation; the nickel molybdenum combination has the highest activity for the hydrodeoxygenation reaction. Therefore, in order to adjust the activity of the catalyst and adapt to different applications, the art generally divides hydrotreating catalysts into bimetallic system catalysts, trimetallic system catalysts and tetrametallic system catalysts according to the active metal species. In the preparation of hydroprocessing catalysts, gamma-Al is generally impregnated with a salt solution containing the active metal component₂O₃The carrier is dried and/or calcined. Then, the mixture is vulcanized into gamma-Al₂O₃A supported sulfide catalyst. The sulfurization method comprises in-situ presulfurization or out-situ presulfurization, wherein the in-situ presulfurization is carried out on a catalyst by injecting a sulfurizing agent into a hydrogenation reactor before the catalyst is started and presulfurizing the catalyst under the conditions of certain hydrogen partial pressure and temperature; the latter is that the catalyst is presulfurized under a certain condition after the catalyst is produced, and the catalyst is directly started after being loaded into a hydrogenation reactor without adding a vulcanizing agent or is started after being activated by hydrogen under a certain condition.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a new hydrotreating catalyst with further improved performance. Specifically, the present invention includes the following:

the invention provides a hydrotreating catalyst, which comprises a forming carrier, a hydrogenation active metal component loaded on the forming carrier, an optional phosphorus additive and an optional organic additive, wherein the hydrogenation active metal component is a VIII group metal and a VIB group metal, and the VIII group metal content is 2.2-10 wt%, preferably 2.5-7 wt% calculated by oxides based on the catalyst; the group VIB metal content, calculated as sulphide, is between 14 and 32 wt.%, preferably between 16 and 28 wt%Amount%; with P₂O₅The content of the phosphorus auxiliary agent is 0 to 10 weight percent, and preferably 2.0 to 8 weight percent; the content of the organic additive is 0-12 wt%, preferably 2-10 wt%; the preparation method of the catalyst comprises the following steps: introducing a VIB group metal into a formed carrier and pre-vulcanizing to obtain a catalyst intermediate; then introducing the group VIII metal into the catalyst intermediate, and drying, optionally roasting or optionally vulcanizing, preferably not roasting and not vulcanizing to obtain the catalyst; wherein, when introducing the VIB group metal and/or the VIII group metal, an optional phosphorus auxiliary agent and/or an organic additive is introduced.

In order to further improve the activity of the catalyst, a phosphorus-containing auxiliary agent and/or an organic additive in the catalyst are preferably selected, wherein the catalyst is taken as a reference, and P is taken as₂O₅The calculated content of the phosphorus auxiliary agent is 2-10 wt%, more preferably 2-8 wt%, and the content of the organic additive is 2-12 wt%, more preferably 2-10 wt%; accordingly, the catalyst preparation method preferably comprises the step of introducing a phosphorus promoter and/or an organic additive into the carrier, and further preferably, the phosphorus promoter and the VIII group metal are introduced simultaneously through an impregnation method.

The invention also provides a hydrotreating method, comprising the step of contacting raw oil with the catalyst, wherein the contacting conditions comprise that: the reaction temperature is 200-^-1Preferably 1 to 2 hours^-1The volume ratio of hydrogen to oil is 50-2000, preferably 100-1000, and the raw oil is one or more of various mineral oils, synthetic oils and distillate oils.

Compared with the existing hydrogenation catalyst, the performance of the catalyst provided by the invention is improved. For example, the present invention provides catalysts having higher hydrodesulfurization activity than the prior art catalysts under the same reaction conditions.

Detailed Description

The following detailed description and examples are intended to further illustrate the invention, but should not be construed as limiting the invention.

The hydrotreating catalyst of the invention is obtained by introducing any VIB group active metal component and any VIII group active metal component on an alumina forming carrier in sequence and carrying out a pre-sulfurization step between the introduction of the two active metal components. The VIB group active metal component in the catalyst obtained by the invention is selected from molybdenum or tungsten, the VIII group metal is selected from cobalt or nickel, and the active metal contained in the finally obtained catalyst is nickel-molybdenum, cobalt-molybdenum or nickel-tungsten.

The shaped support of the present invention is preferably an alumina shaped support, more preferably gamma-Al₂O₃Can be a commercial industrial forming carrier or gamma-Al₂O₃The precursor is prepared by the steps of molding, drying, activating and the like. The gamma-Al₂O₃The precursor of (a) may be amorphous aluminum hydroxide, pseudoboehmite, gibbsite, boehmite or pseudoboehmite, preferably pseudoboehmite. The molding can be carried out by conventional methods, such as tabletting, rolling ball, extruding strip and the like. For example, when extruding, the mixture of alumina precursors may be mixed with an appropriate amount of water and added with an appropriate amount of extrusion aid and/or adhesive, and then extruded. The types and the amounts of the extrusion aid and the peptizing agent are conventional in the field. The drying step is carried out at 100-160 ℃ for 4-8 hours. The activation step is to carry out roasting treatment on the dried strip for 3-8 hours at the temperature of 500-800 ℃ and under the condition of introducing air, preferably, the roasting temperature is 500-650 ℃ and the roasting time is 3-5 hours.

In one embodiment, the final catalyst performs better when the shaped support is an alumina support containing a hydrogenation metal element. The hydrogenation metal element is a VIII group metal element and/or a VIB group metal element, the VIII group metal element is cobalt or nickel, and the VIB group metal element is molybdenum or tungsten. Calculated by oxide and based on the formed carrier, the content of the hydrogenation metal element is 0.3-15 wt%, wherein the content of the VIII group metal element is 0.1-5 wt%, and the content of the VIB group metal element is 0.2-10 wt%. More preferably, the hydrogenation metal element is a group VIB metal element, such as molybdenum or tungsten, in an amount of 0.2 to 10 wt.%, preferably 1 to 8 wt.%, calculated as oxide and based on the shaped support.

The shaped carrier in the above embodiment may be obtained by introducing a hydrogenation metal element with a specified content by using a conventional alumina carrier through an impregnation method, and then drying and calcining the introduced hydrogenation metal element. Wherein the drying operation condition is conventional, such as temperature of 40-350 deg.C and time of 1-24 hr; the roasting operation conditions are as follows: the temperature is more than 300 and less than or equal to 900 ℃, preferably 360-800 ℃, more preferably 380-650 ℃, and the time is 1-10 hours, preferably 2-9 hours, more preferably 2.5-8 hours.

The shaped support of the above embodiment may be prepared by mixing a hydrated alumina P containing pseudo-boehmite with a carrier₁And P₁Modified product P of (2)₂Mixing, forming, drying and roasting, wherein P is a compound of formula₁And P₂The weight mixing ratio of (A) is 20-95: 5-80, P₂Contains hydrogenation metal elements; calculated as oxide and based on the shaped support, P₂The dosage of the metal element is 0.2 to 10 weight percent of the hydrogenation metal element in the final forming carrier; the drying and calcining conditions are the same as those for preparing the shaped support from conventional alumina. In this embodiment, P is₁Modification to P₂The method can be as follows: (1) the hydrated alumina P containing the pseudo-boehmite is treated₁Molding, drying and roasting; (2) impregnating the carrier obtained in the step (1) with impregnation liquid containing hydrogenation metal elements, drying, roasting, grinding and screening all or part of the carrier to obtain a modified substance P₂(ii) a The hydrogenation metal element is introduced in such an amount that the content of the hydrogenation metal element is calculated as an oxide and is calculated as a modifier P₂On the basis, the content of the hydrogenation metal element is 1-8 wt%; the drying conditions in the step (1) comprise: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is 300-900 ℃ and the time is 1-10 hours; the drying conditions in the step (2) comprise: the temperature is 100 ℃ and 250 ℃ for1-10 hours, the roasting conditions include: the temperature is 360-500 ℃ and the time is 1-10 hours. The catalyst obtained by the embodiment has better activity stability.

When the alumina carrier modified by the hydrogenation metal element is adopted, the selection of the carrier and the selection of the later introduced active metal enable the hydrogenation active metal in the final catalyst to be a VIII group active metal component and a VIB group active metal component.

In the hydrotreating catalyst provided by the invention, preferably, the VIII group metal is cobalt or nickel, and the VIII group metal content is 2.2-10 wt% calculated by oxide and based on the catalyst; the group VIB metal is molybdenum or tungsten, and the content of the group VIB metal is 14-32 wt% calculated by sulfide and based on the catalyst.

The present invention does not particularly require the manner of introduction, provided that it is sufficient to introduce the active metal component to the support and control the amount of introduction, and preferably, the introduction may be carried out by an impregnation method. Specifically, it comprises preparing a solution, preferably an aqueous solution, containing the active metal, and then impregnating the support or catalyst intermediate with the solution, followed by drying, with or without calcination. The active metal can be introduced by one-time impregnation or can be impregnated for multiple times, and when the impregnation is carried out for multiple times, the active metal is dried, roasted or not roasted after each impregnation. After the introduction of the group VIB active metal, calcination is preferred; after introduction of the group VIII active metal, it is preferably not calcined.

In a specific embodiment, the drying and calcining conditions are conventional, for example, the drying temperature is 100-; the roasting temperature is 300-550 ℃, preferably 300-400 ℃, and the roasting time is 1-10 hours, preferably 2-8 hours.

The aqueous solution containing the active metal component is an aqueous solution containing an active metal compound, and the nickel-containing compound is selected from one or more soluble nickel-containing compounds, for example, one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble nickel complex compounds, and preferably basic nickel carbonate and nickel acetate; the cobalt-containing compound is selected from one or more soluble cobalt-containing compounds, for example, one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and soluble cobalt complex compounds, preferably basic cobalt carbonate and cobalt nitrate; the tungsten-containing compound is one or more selected from soluble compounds of tungsten, such as tungstate and metatungstate, preferably ammonium metatungstate; the molybdenum-containing compound is one or more selected from soluble compounds of molybdenum, such as molybdate and paramolybdate, preferably ammonium paramolybdate.

According to the catalyst provided by the invention, after the group VIB metal component is introduced into the carrier, pre-sulfidation is carried out. In a specific embodiment, the presulfiding may be contacting the group VIB metal-containing support with a sulfiding medium, which is a mixed gas containing hydrogen sulfide and hydrogen or a solution containing sulfide and an organic solvent, under conditions comprising: the pressure is 1-15 MPa, preferably 4-12 MPa, and the temperature is 300-450 ℃, preferably 300-400 ℃. Preferably, H in the mixed gas₂The volume fraction of S is 5-20%; the mass fraction of sulfide in the sulfide and organic solvent-containing solution is 1-10 wt%; the organic solvent is cyclohexane and C₆-C₁₀One or more of normal paraffin, kerosene or straight-run diesel oil with low end point; h in the mixed gas₂The volume fraction of S is 5-15%; the mass fraction of sulfide in the sulfide and organic solvent-containing solution is 2 to 6 wt%.

After presulfiding, the group VIII metal is introduced into the catalyst intermediate by the same method as previously described, followed by optional calcination; preferably without calcination or vulcanization. If a vulcanization step is included, said vulcanization is a conventional operation, for example the same methods and conditions as for the prevulcanisation described above can be used.

The catalyst may contain a phosphorus promoter or an organic additive, or may contain both a phosphorus promoter and an organic additive, and preferably contains both a phosphorus promoter and an organic additive. When both the phosphorus adjuvant and the organic additive are contained, the preparation method comprises the step of introducing the phosphorus adjuvant and the organic additive.

In one embodiment, the catalyst contains an organic additive. The organic additive is one or more selected from oxygen-containing or nitrogen-containing organic compounds, and the preferable oxygen-containing organic compound is one or more selected from organic alcohol and organic acid; the preferable nitrogen-containing organic compound is one or more selected from organic amines. For example, the oxygen-containing organic compound may include one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight 200-1500), diethylene glycol, butylene glycol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid, and the nitrogen-containing organic compound may include ethylenediamine, EDTA, and ammonium salts thereof. Accordingly, the catalyst preparation process includes a step of introducing an organic additive, and the method of introducing the organic additive may be any method, such as a method of impregnating the support after separately preparing the organic additive into a solution, or a method of impregnating the support with a solution containing the metal component, drying, calcining or not, and then continuing impregnation with a solution containing the organic additive and drying. The drying can be carried out by a conventional method, and is not particularly limited, and for example, the drying temperature is preferably 100 ℃ to 300 ℃, the drying time is preferably 1 to 12 hours, and more preferably the drying temperature is 100 ℃ to 250 ℃, and the drying time is 2 to 8 hours. The calcination conditions are also conventional, for example, the calcination temperature is 350-550 ℃, preferably 400-500 ℃, and the calcination time is 1-10 hours, preferably 2-8 hours. In particular, the organic additive may be introduced before or simultaneously with or after the introduction of the group VIII metal component and/or the group VIB metal component, preferably the additive is introduced simultaneously with the introduction of the group VIII metal component or the group VIB metal component.

In another embodiment, the catalyst contains a phosphorus promoter. When the catalyst contains a phosphorus auxiliary agent, the introduction method of the phosphorus can be any existing method, for example, a phosphorus-containing compound can be directly introduced when an alumina carrier is prepared and molded; phosphorus and hydrogenation active metal can be respectively introduced into the carrier, for example, a phosphorus-containing compound solution is firstly contacted with the carrier and then is roasted, the roasting temperature is 250-600 ℃, preferably 350-500 ℃, the roasting time is 2-8 hours, preferably 3-6 hours, and then the phosphorus-containing compound solution is contacted with a solution containing the hydrogenation active metal component; furthermore, the phosphorus promoter may be introduced before, simultaneously with, or after the introduction of the group VIII metal component, preferably simultaneously with the introduction of the group VIII metal component. Specifically, an aqueous solution containing a group VIII metal component and a phosphorus-containing compound is prepared, and then the carrier is impregnated. The phosphorus-containing compound is selected from one or more of phosphoric acid, phosphorous acid, phosphate and phosphite, and phosphoric acid is preferred.

The invention also provides a hydrocarbon oil hydrotreating method, wherein the hydrotreating reaction conditions are conventional hydrocarbon oil hydrotreating reaction conditions, for example, the hydrotreating reaction conditions include: the reaction temperature is 200-^-1Preferably 1 to 2 hours^-1The volume ratio of hydrogen to oil is 50-2000, preferably 100-1000. Wherein, it is easy to understand for those skilled in the art that the raw oil or the target product may be different according to the processing.

The hydrotreating reaction apparatus may be carried out in any reactor sufficient to contact-react the feedstock oil with the catalyst under hydrotreating reaction conditions, for example, in the fixed bed reactor, a moving bed reactor, or an ebullating bed reactor.

The catalyst provided by the invention is suitable for hydrotreating hydrocarbon raw materials to produce high-quality hydrocarbon fractions. The hydrocarbon feedstock may be various mineral oils or synthetic oils or their mixed distillates, such as straight run gas oils, vacuum gas oils, demetallized oils, atmospheric residues, deasphalted vacuum residues, coker distillates, catalytically treated distillates, shale oils, tar sand oils, coal-to-coal liquefaction oils, vegetable oils, and the like.

The following examples further illustrate the invention.

The reagents used in the examples are all chemically pure reagents, unless otherwise specified. The following examples and comparative examples the sources of pseudoboehmite or alumina used to prepare the supports include:

changling dry glue powder P₀Is pseudo-boehmite produced by China petrochemical catalyst ChangLing division, the dry basis is 0.73, the specific surface area is 300 m²G, pore volume 0.97 ml/g.

Vector S₁Is a common industrial alumina produced by China petrochemical catalyst ChangLing division, and has a specific surface area of 260 m²In g, the pore volume was 0.71 ml/g.

The SD powder is pseudo-boehmite produced by Shandong aluminum plant, the dry basis is 69 percent, and the specific surface area is 220 meters²G, pore volume 0.48 ml/g.

SB powder is pseudo-boehmite powder produced by Sasol company of Germany, the dry basis is 74 percent, and the specific surface area is 230 meters²G, pore volume 0.50 ml/g.

Dry glue powder P₁Also is pseudo-boehmite produced by China petrochemical catalyst ChangLing division, with the pore volume of 1.3 ml/g and the specific surface of 350 m²G, dry basis is 69%.

The method for measuring the content of active metal components in the catalyst is shown in petrochemical analysis method (RIPP test method), scientific publishing company, 1990, 371-379, and the diesel hydrodesulfurization is generally regarded as a 1.65-grade reaction and can be expressed as the following formula:

wherein k is a reaction rate constant, C_p，C_fThe sulfur content of the product and the raw material respectively, and LHSV is the hourly space velocity of the reaction liquid.

The relative hydrodesulfurization activity of a catalyst is expressed as the ratio of the hydrodesulfurization reaction rate constant for diesel over the catalyst to the hydrogenation reaction rate constant over the comparative catalyst.

Example 1

Weighing S₁200.0 g of carrier is immersed in 168.0 ml of aqueous solution containing 68.8 g of ammonium paramolybdate for 1 hour, dried at 120 ℃ for 6 hours and roasted at 360 ℃ for 4 hoursTo obtain a catalyst intermediate Z₁. Taking half weight of Z₁Intermediate to contain H₂H with S volume fraction of 10.0%₂Sulfurizing at 400 deg.C and normal pressure for 4 hr to obtain intermediate Z of catalyst₂. Z was further treated with 55.0mL of an aqueous solution containing 10.4 grams of basic nickel carbonate and 8.1 grams of phosphoric acid₂Soaking the intermediate for 1 hr, and drying at 100 deg.C for 8 hr under nitrogen to obtain C₁The catalyst was stored under nitrogen atmosphere for further use. C₁Medium NiO and MoS₂And P₂O₅The contents by weight of (A) are respectively 3.6%, 21.1% and 4.0%.

Comparative example 1

Taking half weight of Z₁The intermediate was impregnated with 55.0mL of an aqueous solution containing 10.4 g of basic nickel carbonate and 8.1 g of phosphoric acid for 1 hour, and then dried at 100 ℃ under nitrogen for 8 hours to give D₁The catalyst was stored under nitrogen atmosphere for further use. D₁Medium NiO and MoO₃And P₂O₅The contents by weight of (a) are 3.7%, 19.4% and 4.1%, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in table 1.

TABLE 1

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₁	118
D₁	100

Example 2

Weighing 1000 g longLing dry glue powder P₀Extruding into clover-shaped strips with the diameter of the circumscribed circle of 1.6mm, and drying for 8 hours at 110 ℃. Introducing air, heating to 600 ℃ at the speed of 3 ℃/min, and roasting for 3 hours to obtain the aluminum oxide S₂。

Weighing S₂200.0 g of carrier is impregnated with 180.0 ml of an aqueous solution containing 6.1 g of ethylenediaminetetraacetic acid (EDTA) and 59.5 g of ammonium paramolybdate for 1 hour, dried at 130 ℃ for 5 hours, and calcined at 330 ℃ for 6 hours to obtain a catalyst intermediate Z₃. Taking half weight of Z₃Intermediate to contain CS₂Sulfurizing cyclohexane solution with mass fraction of 2.0% at 320 deg.C under 6.0 MPa for 6 hr to obtain catalyst intermediate Z₄. Z was continued with 61.0mL of an aqueous solution containing 9.2 grams of basic nickel carbonate, 6.4 grams of phosphoric acid, and 6.1 grams of EDTA₄Soaking the intermediate for 1 hr, and drying at 130 deg.C under nitrogen for 4 hr to obtain C₂The catalyst was stored under nitrogen atmosphere for further use. C₂Medium NiO and MoS₂、P₂O₅And the weight contents of the organic additive were 3.2%, 18.3%, 3.2% and 4.1%, respectively.

Comparative example 2

Taking half weight of Z₃The intermediate was impregnated with 61.0mL of an aqueous solution containing 9.2 g of basic nickel carbonate, 6.4 g of phosphoric acid and 6.1 g of EDTA for 1 hour, and then dried at 130 ℃ under nitrogen for 4 hours to obtain D₂The catalyst was stored under nitrogen atmosphere for further use. D₂Medium NiO and MoO₃、P₂O₅And the organic additive was present in amounts of 3.3%, 16.8%, 3.3% and 4.2% by weight, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in table 2.

TABLE 2

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₂	124
D₂	100

Example 3

200.0 g of SD powder and 800.0 g of Changling dry rubber powder P are weighed₀Mixing, extruding into clover strips with circumscribed circle diameter of 1.6mm, and drying at 130 deg.C for 6 hr. Introducing air, heating to 580 deg.C at 2.5 deg.C/min, and calcining for 4 hr to obtain alumina carrier S₃。

Weighing S₃200.0 g of carrier, impregnated with 172.0 ml of aqueous solution containing 91.5 g of ammonium paramolybdate, 13.4 g of phosphoric acid and 18.0 g of citric acid for 1 hour, dried at 120 ℃ for 6 hours, and calcined at 380 ℃ for 3 hours to obtain catalyst intermediate Z₅. Taking half weight of Z₅Sulfurizing the intermediate in n-decane solution containing dimethyl disulfide (DMDS) 2.5 wt% at 330 deg.C under 6.0 MPa for 4 hr to obtain catalyst intermediate Z₆. Intermediate Z was then treated with a further 60.0mL of an aqueous solution containing 24.3 grams of cobalt acetate, 9.0 grams of citric acid and 6.7 grams of phosphoric acid₆Soaking for 1 hr, and drying at 120 deg.C for 6 hr under nitrogen to obtain C₃The catalyst was stored under nitrogen atmosphere for further use. C₃Medium CoO and MoS₂、P₂O₅And the organic additive was present in amounts of 4.1%, 23.1%, 5.5% and 4.5% by weight, respectively.

Comparative example 3

Taking half weight of Z₅The intermediate was immersed in 60.0mL of an aqueous solution containing 24.3 g of cobalt acetate, 9.0 g of citric acid and 6.7 g of phosphoric acid for 1 hour, and then dried at 110 ℃ under nitrogen for 8 hours to obtain D₃The catalyst was stored under nitrogen atmosphere for further use. D₃Medium CoO and MoO₃、P₂O₅And the organic additive was present in amounts of 4.2%, 21.3%, 5.6% and 4.6% by weight, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in table 3.

TABLE 3

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₃	118
D₃	100

Example 4

150.0 g of SB powder and 850.0 g of Changling dry rubber powder P are weighed₀Mixing, extruding into clover strips with circumscribed circle diameter of 1.6mm, and drying at 140 deg.C for 5 hr. Introducing air, heating to 570 ℃ at the speed of 2.0 ℃/min, and roasting for 6 hours to obtain the alumina carrier S₄。

Weighing S₄200.0 g of carrier is immersed in 174.0 ml of aqueous solution containing 62.0 g of ammonium paramolybdate for 1 hour, dried at 120 ℃ for 6 hours and calcined at 400 ℃ for 3 hours to obtain catalyst intermediate Z₇. Taking half weight of Z₇Sulfurizing the intermediate with n-hexane solution containing dimethyl disulfide (DMDS) 2.0 wt% at 320 deg.C and 6.0 MPa for 6 hr to obtain catalyst intermediate Z₈. Intermediate Z was then treated with a further 60.0mL of an aqueous solution containing 8.3 grams of basic cobalt carbonate, 6.2 grams of glycerol and 7.7 grams of phosphoric acid₈Soaking for 1 hr, and drying at 110 deg.C for 6 hr under nitrogen to obtain C₄The catalyst was stored under nitrogen atmosphere for further use. C₄Medium CoO and MoS₂、P₂O₅And the organic additive is respectively 3.2%, 18.8%, 3.7% and 4.1％。

Comparative example 4

Taking half weight of Z₇The intermediate was impregnated with 60.0mL of an aqueous solution containing 8.3 g of basic cobalt carbonate, 6.2 g of glycerol and 7.7 g of phosphoric acid for 1 hour, and then dried at 110 ℃ under nitrogen for 6 hours to obtain D₄The catalyst was stored under nitrogen atmosphere for further use. D₄Medium CoO and MoO₃、P₂O₅And the weight contents of the organic additive were 3.3%, 17.2%, 3.8% and 4.2%, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in Table 4.

TABLE 4

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₄	123
D₄	100

Example 5

Weighing S₄200.0 g of carrier, soaking for 1 hour by 174.0 ml of aqueous solution containing 64.0 g of ammonium metatungstate, drying for 4 hours at 130 ℃, and roasting for 6 hours at 340 ℃ to obtain catalyst intermediate Z₉. Taking half weight of Z₉Sulfurizing the intermediate with n-hexane solution containing dimethyl disulfide (DMDS) 2.0 wt% at 320 deg.C and 6.0 MPa for 6 hr to obtain catalyst intermediate Z₁₀. Intermediate Z was then treated with a further 60.0mL of an aqueous solution containing 10.8 grams of basic nickel carbonate, 5.9 grams of glycerol and 8.3 grams of phosphoric acid₁₀Soaking for 1 hr, and introducing nitrogen at 110 deg.CDrying for 6 hours under the condition of air to obtain C₅The catalyst was stored under nitrogen atmosphere for further use. C₅Middle NiO, WS₂、P₂O₅And the weight contents of the organic additive were 3.7%, 18.7%, 4.0% and 3.9%, respectively.

Comparative example 5

Taking half weight of Z₉The intermediate was immersed in 60.0mL of an aqueous solution containing 10.8 g of basic nickel carbonate, 5.9 g of glycerol and 8.3 g of phosphoric acid for 1 hour, and then dried at 110 ℃ under nitrogen for 6 hours to obtain D₅The catalyst was stored under nitrogen atmosphere for further use. D₅Medium NiO and WO₃、P₂O₅And the weight contents of the organic additive were 3.7%, 17.7%, 4.1% and 4.0%, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in Table 5.

TABLE 5

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₅	118
D₅	100

Example 6

100.0 g of SB powder and 900.0 g of Changling dry rubber powder P are weighed₀Mixing, extruding into clover strips with circumscribed circle diameter of 1.6mm, and drying at 150 deg.C for 3 hr. Introducing air, heating to 610 deg.C at 3.5 deg.C/min, and calcining for 3 deg.C to obtain alumina carrier S₅。

Weighing S₅Carrier 200.0G, soaking in 176.0 ml of aqueous solution containing 90.8 g of ammonium metatungstate, 7.8 g of phosphoric acid and 15.0 g of citric acid for 1 hour, drying at 120 ℃ for 6 hours, and calcining at 420 ℃ for 4 hours to obtain catalyst intermediate Z₁₁. Taking half weight of Z₁₁Sulfurizing the intermediate in n-decane solution containing dimethyl disulfide (DMDS) 2.5 wt% at 330 deg.C under 6.0 MPa for 4 hr to obtain catalyst intermediate Z₁₂. Intermediate Z was then treated with a further 61.0mL of an aqueous solution containing 19.0 grams of nickel acetate, 7.5 grams of citric acid and 3.9 grams of phosphoric acid₁₂Soaking for 1 hr, and drying at 120 deg.C for 6 hr under nitrogen to obtain C₆The catalyst was stored under nitrogen atmosphere for further use. C₆Middle NiO, WS₂、P₂O₅And the weight contents of the organic additive were 3.4%, 23.8%, 3.4% and 2.0%, respectively.

Comparative example 6

Taking half weight of Z₁₁The intermediate was immersed in 61.0mL of an aqueous solution containing 19.0 g of nickel acetate, 7.5 g of citric acid and 3.9 g of phosphoric acid for 1 hour, and then dried at 120 ℃ under nitrogen for 6 hours to obtain D₆The catalyst was stored under nitrogen atmosphere for further use. D₆Medium NiO and WO₃、P₂O₅And the weight contents of the organic additive were 3.4%, 22.6%, 3.4% and 2.1%, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in Table 6.

TABLE 6

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₆	124
D₆	100

Example 7

From P₁Preparation of modified product P₃: weighing 5000 g of P₁Adding 7200 ml of aqueous solution containing 50.0 ml of nitric acid, mixing, extruding into clover-shaped strips with the external diameter phi of 1.6mm on a double-screw extruder, drying at 120 ℃ for 4 hours, roasting the dried strips at 600 ℃ for 4 hours to obtain a carrier intermediate P₂. 400.0 g of intermediate P are taken₂The carrier was impregnated with 492.0mL of an aqueous solution containing 43.1 g of ammonium paramolybdate and dried at 120 ℃ for 4 hours to give 443.1 g of the modified product P₃。

Preparation of support S₆: 221.5 g of P are taken₃Roasting at 600 ℃ for 3 hours to obtain the modified carrier S₆，S₆Medium MoO₃The content was 8.0 wt%.

Weighing S₆200.0 g of carrier is dipped in 240.0 ml of aqueous solution containing 80.2 g of ammonium paramolybdate for 1 hour, dried at 120 ℃ for 6 hours and roasted at 400 ℃ for 3 hours to obtain catalyst intermediate Z₁₃. Taking half weight of Z₁₃Sulfurizing the intermediate with n-hexane solution containing dimethyl disulfide (DMDS) 2.0 wt% at 330 deg.C and 6.0 MPa for 5 hr to obtain catalyst intermediate Z₁₄. Z was further treated with 84.0mL of an aqueous solution containing 13.0 grams of basic nickel carbonate, 11.4 grams of tartaric acid, and 11.2 grams of phosphoric acid₁₄Soaking the intermediate for 1 hr, and drying at 110 deg.C for 6 hr under nitrogen to obtain C₇The catalyst was stored under nitrogen atmosphere for further use. C₇Medium NiO and MoS₂、P₂O₅And the organic additive was present in amounts of 4.0%, 27.1%, 4.8% and 6.7% by weight, respectively.

Comparative example 7

Taking half weight of Z₁₃The intermediate was impregnated with 84.0mL of an aqueous solution containing 13.0 g of basic nickel carbonate, 11.4 g of tartaric acid and 11.2 g of phosphoric acid for 1 hour, and then dried at 110 ℃ under nitrogen for 6 hours to give D₇The catalyst was stored under nitrogen atmosphere for further use. D₇Medium NiO and MoO₃、P₂O₅And the organic additive was present in amounts of 4.0%, 24.9%, 4.9% and 6.9% by weight, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in Table 7.

TABLE 7

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₇	120
D₇	100

Example 8

Preparation of support S₇。

Taking 400.0 g of modified intermediate P₂The carrier was impregnated with 492.0mL of an aqueous solution containing 42.6 g of ammonium metatungstate, and dried at 120 ℃ for 4 hours to obtain 437.1 g of modified product P₄. Weighing 800.0 g of P₁And 218.6 g of modifier P₄After uniform mixing, 900 ml of aqueous solution containing 10.0 ml of nitric acid is added, and a butterfly-shaped bar with the external diameter phi of 1.6mm is extruded on a double-screw extruder. Drying the wet strip at 120 deg.C for 4 hr to obtain a molded product, and calcining the molded product at 600 deg.C for 3 hr to obtain a carrier S₇。S₇WO of Zhong₃The content was 2.27% by weight.

Weighing S₇200.0 g of carrier, soaking for 1 hour by 244.0 ml of aqueous solution containing 69.4 g of ammonium metatungstate, drying for 6 hours at 120 ℃, and roasting for 5 hours at 360 ℃ to obtain catalyst intermediate Z₁₅. Taking half weight of Z₁₅The intermediate contains dimethyl disulfide (DMDS) 2.0 wt%Sulfurizing the normal hexane solution at 330 deg.C and 6.0 MPa for 5 hr to obtain catalyst intermediate Z₁₆. Z was further treated with 85.2mL of an aqueous solution containing 12.5 grams of basic nickel carbonate, 7.6 grams of tartaric acid, and 9.8 grams of phosphoric acid₁₆Soaking the intermediate for 1 hr, and drying at 110 deg.C for 6 hr under nitrogen to obtain C₃The catalyst was stored under nitrogen atmosphere for further use. C₈Middle NiO, WS₂、P₂O₅And the organic additive was present in amounts of 4.1%, 21.0%, 4.5% and 4.8% by weight, respectively.

Comparative example 8

Taking half weight of Z₁₅The intermediate was impregnated with 85.2mL of an aqueous solution containing 12.5 g of basic nickel carbonate, 7.6 g of tartaric acid and 9.8 g of phosphoric acid for 1 hour, and then dried at 110 ℃ under nitrogen for 6 hours to give D₈The catalyst was stored under nitrogen atmosphere for further use. D₈Medium NiO and WO₃、P₂O₅And the organic additive was present in amounts of 4.1%, 19.9%, 4.6% and 4.9% by weight, respectively.

The relative hydrodesulfurization activity of the catalysts is shown in Table 8.

TABLE 8

Catalyst and process for preparing same	Relative hydrodesulfurization activity/% of catalyst
		C₈	121
D₈	100

Claims

1. A hydroprocessing catalyst comprisingThe catalyst comprises a molded carrier, a hydrogenation active metal component loaded on the molded carrier, an optional phosphorus assistant and an optional organic additive, wherein the hydrogenation active metal component is a VIII group metal and a VIB group metal, the VIII group metal content is 2.2-10 wt% calculated by oxides, the VIB group metal content is 14-32 wt% calculated by sulfides, and the P is P₂O₅The content of the phosphorus additive is 0-10 wt%, and the content of the organic additive is 0-12 wt%; the preparation method of the catalyst comprises the following steps: introducing a VIB group metal into a formed carrier and pre-vulcanizing to obtain a catalyst intermediate; then introducing the VIII group metal into the catalyst intermediate, and drying, optionally roasting or optionally vulcanizing to obtain the catalyst; wherein, when introducing the VIB group metal and/or the VIII group metal, an optional phosphorus auxiliary agent and/or an organic additive is introduced.

2. The catalyst of claim 1 wherein the group VIII metal is cobalt or nickel and is present in an amount of from 2.5 to 7 weight percent, calculated as oxide and based on the catalyst; the group VIB metal is molybdenum or tungsten, and the content of the group VIB metal is 14-28 wt% calculated by sulfide and based on the catalyst.

3. The catalyst according to claim 1, wherein the method for introducing the group VIB metal and optionally the phosphorus promoter and/or the organic additive into the support is an impregnation method comprising impregnating the support with an aqueous solution of a group VIB metal-containing compound, optionally a phosphorus-containing compound, optionally an organic additive, followed by drying and optionally calcining, the drying conditions comprising: the temperature is 100 ℃ and 300 ℃, and the time is 1-12 hours; the roasting conditions comprise: the temperature is 300 ℃ and 550 ℃, and the time is 1-10 hours.

4. The catalyst of claim 3, wherein the drying conditions comprise: the temperature is 100 ℃ and 280 ℃, and the time is 2-8 hours; the roasting conditions comprise: the temperature is 300 ℃ and 400 ℃, and the time is 2-8 hours.

5. The catalyst of claim 1, wherein the presulfiding comprises contacting the group VIB metal-containing support with a sulfiding medium, the sulfiding medium being a mixed gas comprising hydrogen sulfide and hydrogen, or a solution comprising sulfides and an organic solvent, the conditions of the contacting comprising: the pressure is 1-15 MPa and the temperature is 300-450 ℃.

6. The catalyst of claim 5, wherein the contacting conditions are: the pressure is 4-12 MPa and the temperature is 300-400 ℃.

7. The catalyst according to claim 5 or 6, wherein H in the mixed gas₂The volume fraction of S is 5-20%; the mass fraction of sulfide in the sulfide and organic solvent-containing solution is 1-10 wt%; the organic solvent is cyclohexane and C₆-C₁₀The normal paraffin, the lamp oil, the kerosene or the straight-run diesel oil with low end point.

8. The catalyst of claim 7, wherein H in the mixed gas₂The volume fraction of S is 5-15%; the mass fraction of sulfide in the sulfide and organic solvent-containing solution is 2 to 6 wt%.

9. The catalyst of claim 1 wherein the method of introducing the group VIII metal and optional phosphorus promoter and/or organic additive to the catalyst intermediate is an impregnation method comprising impregnating the catalyst intermediate with a solution comprising a group VIII metal containing compound, an optional phosphorus containing compound, an optional organic additive, followed by drying and optional sulfiding, the drying conditions comprising: the temperature is 100 ℃ and 300 ℃, and the time is 1-12 hours.

10. A hydroprocessing method comprising contacting a feedstock oil with the catalyst of any one of claims 1-9, said contacting being under a condition comprisingComprises the following steps: the reaction temperature is 200-^-1Preferably 1 to 2 hours^-1The volume ratio of hydrogen to oil is 50-2000, preferably 100-1000, and the raw oil is one or more of various mineral oils, synthetic oils and distillate oils.