CN107486251B

CN107486251B - Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same

Info

Publication number: CN107486251B
Application number: CN201610409241.0A
Authority: CN
Inventors: 龙湘云; 刘学芬; 刘清河; 张乐; 李明丰; 聂红; 胡志海; 梁家林
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2016-06-12
Filing date: 2016-06-12
Publication date: 2019-12-27
Anticipated expiration: 2036-06-12
Also published as: CN107486251A

Abstract

A preparation method of a hydrogenation catalyst and the catalyst prepared by the method, the preparation method comprises the steps of contacting an impregnation solution with a carrier, and then drying, roasting or not roasting to obtain the hydrogenation catalyst, and is characterized in that the preparation method of the impregnation solution comprises the following steps: (1) preparing a first solution comprising at least one group VIII metal-containing compound and at least one first group VIB metal-containing compound; (2) activating the first solution under the pressure of more than 0.1MPa to less than or equal to 10MPa, wherein the treatment temperature is 65-200 ℃ and the treatment time is 0.5-36 hours; (3) and after the temperature of the activated first solution is reduced to room temperature to 50 ℃, introducing at least one compound containing a second VIB metal into the first solution to obtain the impregnation solution. Compared with the prior art, the hydrogenation catalyst provided by the invention has obviously improved hydrofining or hydrotreating performance.

Description

Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same

Technical Field

The invention relates to a preparation method of a hydrogenation catalyst and the hydrogenation catalyst obtained by the method.

Background

The hydrogenation catalyst is a very important catalyst in the field of petroleum refining, is widely applied to various hydrogenation processes in the field of petroleum refining, and is used for producing clean fuel, improving the feeding property of an oil refining process and improving the yield and quality of oil products. The hydrogenation catalyst has a hydrogenation function, and the hydrogenation performance of the hydrogenation catalyst is influenced by various factors such as active metals, carriers, a preparation method and the like. The active metals in the hydrogenation catalyst are metals in VIB group and VIII group of the periodic table of elements, and the active metals are usually supported on a carrier with a porous structure. The common method for loading active metals on catalyst carriers is an impregnation method, i.e. an impregnation solution containing active metal components is contacted with the carrier, so that the active metal components enter the surface or pore channels of the carrier, thereby realizing the purpose of loading the active metals. In this process. The preparation of the impregnation solution is a very important link, and different preparation methods may cause differences in the existing forms of the metal components in the obtained impregnation solution and the physicochemical properties of the impregnation solution, thereby further affecting the performance of the hydrogenation catalyst prepared by the impregnation method. Therefore, the improvement and optimization of the preparation method of the impregnation solution may become an important way for improving the performance of the hydrogenation catalyst, and more attention is paid in recent years.

CN 96109702 discloses a co-immersion liquid for preparing hydrocracking catalyst, which comprises the following components: 25-65g WO₃100ml solution, 3-20g NiO/100ml solution, wherein at least one organic acid or ammonium salt is contained in the solution, and the content is 0.5-15g/100ml solution. The impregnation liquid is obtained by dissolving ammonium metatungstate and nickel nitrate in deionized water, and then adding organic acid or ammonium salt for dissolution.

CN 201010211884 discloses an impregnation solution of hydrogenation catalyst and a preparation method thereof, wherein the impregnation solution contains water-soluble VIB group metals, water-soluble organic acid salts of VIII group metals, and water-soluble organic additives. Also provided is a preparation method for preparing the hydrogenation catalyst by contacting the impregnation liquid with a catalyst carrier. The method for preparing the impregnation solution is not particularly limited as long as the respective components of the impregnation solution of the hydrogenation catalyst are uniformly mixed.

CN 201110317245 provides an impregnating solution of hydrogenation catalyst and a preparation method thereof, and the method comprises the steps of preparing a VIII group metal compound and a first organic complexing agent into an aqueous solution A; preparing a VIB group metal compound into an aqueous solution B; mixing the aqueous solution A and the aqueous solution B; wherein the ligand of the first organic complexing agent at least contains a coordination atom N.

CN 00110464 relates to a preparation method of a hydrocarbon hydrofining catalyst, which is prepared by dipping, drying and roasting dipping solution containing metal components of VIB group and VIII group, organic carboxylic acid and polyalcohol mixed complexing agent and auxiliary agent B. The preparation method of the impregnation liquid comprises the following steps: putting a soluble VIB metal compound, an organic carboxylic acid complexing agent and a boron-containing compound into the same beaker, adding deionized water, heating and dissolving under stirring, adding phosphoric acid and a soluble VIII metal compound after dissolving, and preparing a co-leaching solution.

CN 200510064751 provides a hydrogenation catalyst and a preparation method thereof. The catalyst contains Ni, Mo, W active metal components and an alumina carrier. There is no limitation on the method of metal introduction, and a preferred method includes a method of impregnating the alumina support with a solution containing Mo, Ni and W compounds, either alone or simultaneously, with or without drying, firing or calcining after completion of the impregnation. The preparation of the impregnation solution is not described or limited.

Literature ("W-Incorporated CoMo/γ -Al)₂O₃Hydrodesuifugation Catalyst ", Journal of catalysis 1996, vol.159, p.212-218) reports a CoMoW/Al₂O₃The preparation method of the catalyst comprises the steps of loading W and CoMo on an alumina carrier step by adopting an impregnation method, wherein the impregnation sequence of the W and the CoMo can be changed, and drying and roasting are carried out after impregnation.

Disclosure of Invention

The invention provides a preparation method of a hydrogenation catalyst and the catalyst prepared by the method. The method for preparing the hydrogenation catalyst comprises the steps of contacting an impregnation solution with a carrier, and then drying, roasting or not roasting to obtain the hydrogenation catalyst, and is characterized in that the preparation method of the impregnation solution comprises the following steps:

(1) preparing a first solution comprising at least one group VIII metal-containing compound and at least one first group VIB metal-containing compound;

(2) activating the first solution under the pressure of more than 0.1MPa to less than or equal to 10MPa, wherein the treatment temperature is 65-200 ℃ and the treatment time is 0.5-36 hours;

(3) and cooling the activated first solution to room temperature to 50 ℃, and introducing at least one compound containing a second VIB metal into the first solution to obtain the impregnation solution.

Compared with the prior art, the hydrogenation catalyst provided by the invention has obviously improved hydrofining or hydrotreating performance. For example, when a straight diesel/catalytic diesel mixed oil is subjected to hydrofining, the catalyst provided by the invention and a comparative catalyst are subjected to comparative evaluation, and the activity of the comparative catalyst is 100%, the relative hydrodesulfurization activity of the catalyst provided by the invention can reach 147%, and the relative hydrodenitrogenation activity of the catalyst can reach 125%.

Detailed Description

The invention provides a preparation method of a hydrogenation catalyst, which comprises the steps of contacting an impregnation solution with a carrier, and then drying, roasting or not roasting to obtain the hydrogenation catalyst, and is characterized in that the preparation method of the impregnation solution comprises the following steps:

(1) preparing a first solution containing at least one group VIII metal and at least one first group VIB metal;

(3) and cooling the activated first solution to room temperature to 50 ℃, and introducing at least one second VIB metal into the first solution to obtain the impregnation solution.

According to the process of the present invention, the support is selected from a variety of supports suitable for use in the preparation of hydrogenation-type catalysts. The support may be in the form of a shaped or unshaped refractory inorganic oxide, inorganic silicate and molecular sieve and mixtures thereof.

The present invention does not specifically require the kind of the heat-resistant inorganic oxide, and can be carried out with reference to the prior art, and examples thereof include one or more of alumina, silica, titania, magnesia, silica-alumina, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, and clay, and among these, alumina and/or silica are preferable.

The invention has no special requirement on the type of the molecular sieve, and can be one or more of zeolite or non-zeolite molecular sieves. The zeolite molecular sieve may be one or more of erionite, ZSM-34 zeolite, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, L zeolite, Y zeolite, X zeolite, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, zeolite Beta and zeolite omega. The non-zeolitic molecular sieve may be one or more of a phosphoaluminosilicate molecular sieve, a titanium silicalite molecular sieve, and a silicoaluminophosphate (e.g., SAPO) molecular sieve. According to the present invention, the molecular sieve is preferably a hydrogen form molecular sieve, which is either commercially available or can be prepared by conventional methods. For example, the sodium type molecular sieve may be ion exchanged by a conventional ammonium ion exchange method and dried to form an ammonium type molecular sieve, which is then calcined to form the hydrogen type molecular sieve.

According to the preparation method of the hydrogenation catalyst, the catalyst carrier can also contain clay, the type of the clay can be selected according to needs, and the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

According to the preparation method of the hydrogenation catalyst, the catalyst carrier can further contain a modification auxiliary agent, and the modification auxiliary agent compound is preferably one or more of a silicon-containing compound, a fluorine-containing compound, a phosphorus-containing compound, a titanium-containing compound and a boron-containing compound. The method for introducing the auxiliary agent can be carried out according to the prior art, for example, the auxiliary agent can be introduced in the process of synthesizing or forming the carrier, and the auxiliary agent can also be introduced into the catalyst carrier by an impregnation or mixing method. As will be appreciated by those skilled in the art, further description is omitted here.

According to the preparation method of the hydrogenation catalyst, the catalyst carrier can be powder, clover-shaped, butterfly-shaped, cylindrical, hollow cylindrical, quadralobe-shaped, asymmetric quadralobe-shaped, pentalobate-shaped or spherical.

According to the preparation method of the hydrogenation catalyst, the contact conditions can be selected from a wide range, and for the invention, the contact conditions preferably comprise: the contact temperature is between room temperature and 80 ℃, and preferably between room temperature and 60 ℃; the time is 0.1 to 24 hours, preferably 0.5 to 10 hours. The contacting method may be spraying, dipping, adsorption method known in the art, preferably dipping and adsorption. The impregnation method is adopted in the embodiment of the invention.

The impregnation method of the present invention has no special requirements, and can be various impregnation methods in the prior art, such as spray impregnation, saturated impregnation or excess liquid impregnation.

According to the preparation method of the hydrogenation catalyst, the method preferably further comprises a step of filtering or not filtering (generally, the filtering is not required when the catalyst is saturated and impregnated, and the method is known by those skilled in the art), and then drying or drying and roasting.

The invention has no special requirements on the drying and roasting conditions, and can be carried out by referring to the prior art. For example, the drying temperature is generally 60 to 250 ℃, preferably 90 to 180 ℃, and the time is 1 to 24 hours, preferably 2 to 12 hours; the temperature of the calcination is generally 300-700 deg.C, preferably 300-550 deg.C, for 0.5-12 hours, preferably 1-8 hours.

In order to realize the present invention, it is necessary to prepare the impregnation solution of the present invention, and a specific preparation method of the impregnation solution will be described in detail below.

According to the preparation method of the impregnation solution provided by the invention, the non-noble metal selected from the group VIII metals can be one or more of nickel, cobalt and iron, and is preferably one or two of nickel and cobalt.

According to the preparation method of the impregnation solution provided by the invention, the VIB group metal can be chromium, molybdenum and tungsten, and preferably, the first VIB group metal is molybdenum, and the second VIB group metal is tungsten.

The group VIII and group VIB metals may be introduced into the solution in the form of compounds containing the respective metals. The compound containing the VIII group metal is selected from one or more of nitrate, carbonate, basic carbonate, phosphate, phosphite, hypophosphite and organic carboxylate, and the compound containing the VIB group metal is selected from one or more of oxide, inorganic acid and inorganic acid salt. When the group VIB metal is molybdenum, the molybdenum-containing compound is one or more selected from molybdenum trioxide, molybdic acid, paramolybdic acid, phosphomolybdic acid, phosphomolybdate, molybdate, paramolybdate, dimolybdate and tetramolybdate. Among the molybdenum-containing salts, molybdenum-containing ammonium salts are further preferable; when the group VIB metal is tungsten, the tungsten-containing compound is a water-soluble tungsten compound, preferably at least one of tungstic acid, metatungstic acid, ethyl metatungstic acid, phosphotungstic acid, silicotungstic acid, tungstate, phosphotungstate, silicotungstate, ethyl metatungstate, and further preferably an ammonium salt containing tungsten among the tungsten-containing salts.

According to the preparation method of the impregnation solution provided by the invention, the solution can contain at least one inorganic auxiliary agent, the inorganic auxiliary agent is selected from inorganic acid or a mixture of inorganic acid and inorganic acid salt, the inorganic acid can be at least one of nitric acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, phosphorous acid and boric acid, and preferably, the inorganic acid is at least one of phosphoric acid, hypophosphorous acid, phosphorous acid and boric acid. Preferably, the inorganic acid salt is an ammonium salt of the aforementioned inorganic acid, and more preferably, the inorganic acid salt is at least one selected from the group consisting of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphite, ammonium dihydrogen hypophosphite, ammonium borate, ammonium metaborate, and ammonium tetraborate. When the solution contains both the inorganic acid and the inorganic acid salt, the molar ratio of the inorganic acid to the inorganic acid salt is preferably greater than 1. Preferably, the molar ratio of the inorganic auxiliary agent to the first group VIB metal-containing compound is 0.05 to 3.0, and more preferably 0.1 to 2.5.

According to the preparation method of the impregnation solution provided by the invention, the impregnation solution can contain at least one organic auxiliary agent. The organic auxiliaries are added in part for the purpose of solubilizing and stabilizing the solution. Preferably, the organic auxiliary agent is selected from one or more of organic acid, a mixture of organic acid and organic acid ammonium salt, and non-acidic oxygen-containing organic matter containing C-O bond and/or C ═ O bond, and more preferably, the organic auxiliary agent is a mixture of organic acid and organic alcohol.

The organic acid includes aminocarboxylic acid, alkylcarboxylic acid, aldehyde-containing carboxylic acid, hydroxyl-containing carboxylic acid. More specifically, the organic acid is one or more of cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, ethylenediamine tetraacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, maleic acid, tartaric acid, salicylic acid, malic acid and the like, and the ammonium salt of the organic acid comprises one or more of the ammonium salts of the organic acids. The non-acidic oxygen-containing organic matter containing C-O bonds and/or C ═ O bonds is selected from water-soluble organic alcohols, organic ethers, organic ketones, organic esters and mixtures thereof. More preferably, the second type of organic auxiliary is selected from water-soluble organic alcohols. Particularly preferably, such organic auxiliaries are selected from C1-C8 organic alcohols and/or polyethylene glycols having a weight average molecular weight of 120-4000, for example from one or more of methanol, ethanol, ethylene glycol, diethylene glycol, propanol, isopropanol, glycerol, butanol, butanediol, pentanol, pentanediol, hexanol, hexanediol, octanol, methylcyclohexanol, cyclohexanediol, diethylene glycol, sorbitol and polyethylene glycols having a weight average molecular weight of 200-1000.

Preferably, the organic assistant is used in an amount such that the molar ratio of the organic assistant to the group VIII metal-containing compound in the solution is 0.05 to 5, and more preferably, the molar ratio of the organic assistant to the group VIII metal-containing compound is 0.1 to 4.

According to the method for preparing the impregnation solution provided by the invention, the impregnation solution is preferably an aqueous solution. The preparation of the solution is well known to those skilled in the art and will not be described in detail.

The method for preparing the impregnation solution according to the present invention comprises a step of subjecting the first solution to an activation treatment. The activation treatment is performed under a pressure condition of more than 0.1MPa to 10MPa or less, preferably, under a pressure condition of 0.15 to 7MPa, and further preferably, under a pressure condition of 0.2 to 5 MPa.

Various methods commonly used in the art can be employed to subject the treatment to the specified pressure conditions.

In one embodiment of the invention, the treatment is carried out at the autogenous pressure of the solution in the closed container.

In another embodiment of the invention, the method comprises introducing a gaseous medium into the containment vessel prior to or during the treatment to provide additional pressure. Preferably the gaseous medium is an inert gas. The additional pressure may be adjusted by controlling the amount of inert gas input. The pressure for processing is the sum of the autogenous pressure of the solution in the closed container and the additional pressure.

The pressure of the treatment may be measured by a method commonly used in the art, and is not specifically described.

In the present invention, the inert gas refers to a gas that does not chemically interact with the solution during the treatment process, and may be various inert gases commonly used in the art. Preferably, the inert gas is selected from the group consisting of air, nitrogen, inert gases, carbon dioxide and C₁-C₅The hydrocarbon of (1).

The time and temperature of the treatment according to the method of the invention may be chosen as is conventional in the art, provided that the pressure of the treatment meets the requirements mentioned hereinbefore. Preferably, the temperature of the treatment may be 65-200 ℃; the time for the hydrothermal treatment may be 0.5 to 36 hours, preferably 1 to 24 hours.

The inventors of the present invention speculate that the treatment process may promote further reactions between the components in the first solution, thereby altering the presence and binding of the components in the solution.

The method for preparing the impregnation solution according to the present invention further comprises the step of introducing a compound containing a second group VIB metal into the first solution after the activation treatment. The water-soluble compound containing the second group VIB metal can be directly added into the activated first solution for dissolving, or the water solution containing the second group VIB metal can be mixed with the activated first solution to obtain the final dipping solution.

According to the preparation method of the impregnation solution provided by the invention, before introducing the compound containing the second VIB group metal, the temperature of the activated first solution is required to be reduced, so that the temperature of the solution is between room temperature and 50 ℃, and preferably between room temperature and 45 ℃. The room temperature in the present invention refers to the ambient temperature of the place where the impregnation solution is prepared, and the impregnation solution can exist in a solution state under the room temperature condition. After the activation treatment is finished, the aim can be achieved by natural cooling or forced cooling. The reason for controlling the temperature of the first solution is that when the temperature of the first solution is too high, the second group VIB metal-containing compound added may undergo a precipitation reaction with the metal compound of the first solution, thereby destroying the stability of the solution.

According to the preparation method of the impregnation solution provided by the invention, after the temperature of the treated first solution is reduced to the specified temperature, the step of further introducing an organic auxiliary agent can be included. The organic assistant can be introduced before, simultaneously with or after the introduction of the second group VIB metal, and can be added directly in the form of an organic assistant compound or in the form of an aqueous solution of the organic assistant. The organic auxiliary agent is selected from organic acid and organic alcohol. The preference of organic acids and organic alcohols can be found in the above description and will not be described in detail. The molar ratio of the organic auxiliary agent introduced in the step to the group VIII metal compound in the solution is 0-4, and preferably the molar ratio of the organic auxiliary agent introduced in the step to the group VIII metal compound is 0.05-2.5.

The invention provides a hydrogenation catalyst prepared by the preparation method of the hydrogenation catalyst.

According to the catalyst obtained by the method, in the preparation process, the use amounts of the carrier and the metal components are based on the final catalyst, and calculated by oxides, the content of the VIII group metal is 1-9 wt%, the content of the first VIB group metal is 1-30 wt%, the content of the second VIB group metal is 2-36 wt%, and the balance is the carrier. Wherein, the VIII group metal is preferably at least one of Co and Ni, the first VIB group metal is preferably Mo, and the second VIB group metal is preferably W.

The catalyst obtained by the method of the invention optionally contains at least one inorganic auxiliary agent, wherein the inorganic auxiliary agent is preferably selected from phosphorus, boron, fluorine, titanium and silicon, and the content of the inorganic auxiliary agent is 0-13 wt% in terms of elements based on the weight of the catalyst, and more preferably, the content of the inorganic auxiliary agent is 1-10 wt%.

The catalyst obtained by the method comprises at least one organic auxiliary agent, wherein the organic auxiliary agent is selected from organic acids, mixtures of the organic acids and organic acid ammonium salts, and non-acidic oxygen-containing organic matters containing C-O bonds and/or C ═ O bonds. Wherein, the content of the organic auxiliary agent is 0.5-10 wt%, preferably 1-8 wt%, and more preferably 1-6 wt% based on the weight of the catalyst and calculated by carbon element.

According to the conventional method in the art, the catalyst provided by the present invention can be presulfided with sulfur, hydrogen sulfide or other sulfur-containing raw materials before use, usually in the presence of hydrogen gas at the temperature of 140 ℃ and 370 ℃, the presulfiding can be carried out outside the reactor or in situ inside the reactor to convert the catalyst into a sulfide type, and in this regard, the present invention can be carried out according to the prior art, and the present invention has no special requirements and is not described herein again.

Compared with the existing hydrogenation catalyst, the catalyst provided by the invention has higher hydrofining activity, and the catalyst is suitable for hydrofining processes of petroleum, coal liquefaction distillate oil and biomass oil, or raw material pretreatment of other catalytic processes such as a catalytic cracking process and a hydrocracking process.

The invention is further illustrated by the following examples, which are not intended to be limiting.

Examples 1-4 are provided to illustrate the preparation of the impregnating solutions provided by the present invention and the resulting impregnating solutions. The sources of the raw materials used to prepare the impregnation solution were as follows: citric acid monohydrate (analytical grade, product of tianjin Hengxing chemical reagent Co., Ltd.), phosphoric acid (analytical grade, product of Beijing chemical plant Co., Ltd.), nitrilotriacetic acid (analytical grade, product of Beijing Hengzhong far-reaching chemical industry Co., Ltd.), ethylenediaminetetraacetic acid (analytical grade, product of Shantou Wen Longhua chemical plant Co., Ltd.), diammonium ethylenediaminetetraacetate (purity 99% by weight, product of Changzhou Yirun chemical Co., Ltd.), glycerol (analytical grade, product of Beijing chemical plant Co., Ltd.), diethylene glycol (analytical grade, product of Beijing Xin Pengfei flying technology development Co., Ltd.), ammonium dihydrogen phosphate (analytical grade, product of Beijing chemical reagent Co., Ltd.), nickel hydroxycarbonate (product of Yixing Shensheng catalyst Co., Ltd., NiO content 51% by weight), molybdenum trioxide (product of Tianjin Sifang chemical reagent Co., Ltd.), ammonium paramolybdate (national drug group chemical reagent Co., analytical grade diamond), ammonium metatungstate tungsten tungstate (product of Zhongzhou tungsten product of Zhongzho, WO₃91 wt.%), cobalt carbonate hydroxide (product of science and technology limited of nuclear industry, jiang west, CoO content 57 wt.%).

The source and properties of the support used to prepare the catalyst are as follows:

vector S1: 350 g of alkaline silica sol (SiO, product of Beijing Feilong Makou Co., Ltd.)₂30 percent by weight) and 549 g of pseudoboehmite (a product of Changling division of a Chinese petrochemical catalyst, the water content of which is 28 percent), extruded into trilobal strips with the circumscribed circle diameter of 1.6 mm, dried for 4 hours at 120 ℃ and roasted for 4 hours at 600 ℃ to obtain the carrier S1. The silica content of S1 was 21 wt%, and the alumina content was 79 wt%.

Vector S2: 493 g of SB powder (Sasol product, Germany, water content of 27%), 26.3 g of USY (water content of 24 wt%) and 25.6 g of ASA40 amorphous silica powder (water content of 22 wt%) were mixed, extruded into trilobal strips with circumscribed circle diameter of 1.6 mm, the wet strips were dried at 120 ℃ for 4 hours, and calcined at 520 ℃ for 4 hours to obtain a carrier S2, the alumina content in S2 was 90%, the USY molecular sieve content was 5%, and the ASA40 content was 5%.

Vector S3: 31.4 g of ammonium fluoride (analytically pure, product of a chemical plant of denna), 350 g of titanium-containing alumina powder (product of tianjin Kaiyitt technologies, Inc., titanium dioxide content 15 wt%, water content 28%), 154.3 g of pseudo-boehmite (product of Shandong aluminum industry, water content 30%) were mixed, extruded into trilobal strips with circumscribed circle diameter of 1.6 mm, the wet strips were dried at 120 ℃ for 4 hours, and calcined at 560 ℃ for 4 hours to obtain the carrier S3. S3 contained 4 wt% of fluorine (calculated as element), 13 wt% of titanium dioxide and 83 wt% of alumina.

Vector S4: 550 g of pseudo-boehmite (a product of China petrochemical catalyst Chang Ling division, with 29% of water content) is mixed, extruded into a trilobal strip with the circumscribed circle diameter of 1.6 mm, the wet strip is dried at 120 ℃ for 4 hours, and is roasted at 650 ℃ for 4 hours to obtain the alumina carrier S4.

Example 1

253 g of citric acid monohydrate was added to an open vessel containing 600ml of water, and after dissolution by stirring, 176.4 g of nickel hydroxycarbonate and 60 g of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolution was achieved, giving a first solution. And then, placing the first solution in a high-pressure reaction kettle, and sealing the reaction kettle for treatment. The treatment conditions are as follows: the temperature is 120 ℃, the pressure is the autogenous pressure of a solution system in the high-pressure reaction kettle, the value is 0.2MPa, and the processing time is 18 hours. After the solution was naturally cooled to room temperature after the completion of the treatment, 659.1 g of ammonium metatungstate was added to the treated first solution, and after dissolution by stirring, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S1 carrier was taken, and the S1 carrier was impregnated with 123ml of the above impregnation solution for 1 hour, followed by drying at 120 ℃ for 6 hours to obtain catalyst C-1, the catalyst properties being shown in Table 1.

Comparative example 1

253 g of citric acid monohydrate was added to an open vessel containing 600ml of water, and after dissolution by stirring, 176.4 g of nickel hydroxycarbonate and 60 g of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolution was achieved, giving a first solution. 659.1 g of ammonium metatungstate was then added to the above solution, and after dissolution with stirring, the solution was made to have a volume of 1000ml by adding water to prepare an impregnation solution.

150 g of S1 carrier is taken, and the S1 carrier is soaked for 1 hour by 123ml of the above soaking solution, and then dried for 6 hours at 120 ℃ to prepare the catalyst DC-1, wherein the property parameters of the catalyst are shown in Table 1.

Comparative example 2

176.4 grams of basic nickel carbonate and 60 grams of molybdenum trioxide were added to an open vessel containing 600ml of water, stirred and heated until dissolved, yielding a first solution. And then 659.1 g of ammonium metatungstate is added into the solution, the solution is stirred and dissolved, and then the solution is placed into a high-pressure reaction kettle and is sealed for treatment. The treatment conditions were: the temperature is 120 ℃, the pressure is the autogenous pressure of a solution system in the high-pressure reaction kettle, the value is 0.2MPa, and the processing time is 18 hours. And after the treatment is finished, naturally cooling the solution to room temperature, and supplementing water to make the volume of the solution reach 1000ml, thereby preparing the impregnation solution.

150 g of S1 carrier was taken, and the S1 carrier was impregnated with 123ml of the above impregnation solution for 1 hour, and then dried at 120 ℃ for 6 hours to obtain catalyst DC-2, the catalyst property parameters are shown in Table 1.

Example 2

48.7 g of phosphoric acid and 253 g of citric acid monohydrate were added to an open vessel containing 600ml of water, and after dissolution by stirring, 176.4 g of nickel hydroxycarbonate and 60 g of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolution was achieved, giving a first solution. And then, placing the first solution in a high-pressure reaction kettle, and sealing the reaction kettle for treatment. The treatment conditions are as follows: the temperature is 120 ℃, the pressure is the autogenous pressure of a solution system in the high-pressure reaction kettle, the value is 0.2MPa, and the processing time is 18 hours. After the solution was naturally cooled to room temperature after the completion of the treatment, 659.1 g of ammonium metatungstate was added to the treated first solution, and after dissolution by stirring, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S1 carrier was taken, and the S1 carrier was impregnated with 123ml of the above impregnation solution for 1 hour, followed by drying at 120 ℃ for 6 hours to obtain catalyst C-2, the catalyst properties parameters of which are shown in Table 1.

Comparative example 3

The preparation method is the same as that of example 2, except that the autoclave treatment step is not performed after the first solution is prepared, the obtained catalyst is DC-3, and the property parameters of the catalyst are shown in Table 1.

Example 3

52.4 grams of phosphoric acid and 206.6 grams of nitrilotriacetic acid were added to an open vessel containing 650ml of water, after dissolution with stirring, 79.1 grams of basic nickel carbonate and 193.7 grams of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolved to give a first solution. And then, placing the first solution in a high-pressure reaction kettle, sealing and treating. The conditions of the treatment include: after the temperature is 80 ℃, the time is 8 hours, and after the treatment temperature is in place, nitrogen is introduced into the high-pressure reaction kettle to ensure that the pressure in the high-pressure reaction kettle reaches 4.0 MPa. After the solution was naturally cooled to room temperature after the completion of the treatment, 35.5 g of ammonium metatungstate was added to the treated first solution, and after the solution was dissolved by stirring, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S2 carrier was taken, and S2 carrier was impregnated with 114ml of the above impregnation solution for 1 hour, followed by drying at 200 ℃ for 2 hours to obtain catalyst C-3, the catalyst properties parameters of which are shown in Table 1.

Comparative example 4

The preparation method is the same as that of example 3, except that the autoclave treatment step is not performed after the first solution is prepared, the obtained catalyst is DC-4, and the property parameters of the catalyst are shown in Table 1.

Comparative example 5

52.4 grams of phosphoric acid and 206.6 grams of nitrilotriacetic acid were added to an open vessel containing 650ml of water, after dissolution with stirring, 79.1 grams of basic nickel carbonate and 226.0 grams of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolved to give a first solution. And then, placing the first solution in a high-pressure reaction kettle, sealing and treating. The conditions of the treatment include: after the temperature is 80 ℃, the time is 8 hours, and after the treatment temperature is in place, nitrogen is introduced into the high-pressure reaction kettle to ensure that the pressure in the high-pressure reaction kettle reaches 4.0 MPa. And after the treatment is finished, naturally cooling the solution to room temperature, and supplementing water to make the volume of the solution reach 1000ml, thereby preparing the impregnation solution.

150 g of S2 carrier was taken, and the S2 carrier was impregnated with 114ml of the above impregnation solution for 1 hour, and then dried at 200 ℃ for 2 hours to obtain catalyst DC-5, the catalyst property parameters are shown in Table 1.

Comparative example 6

52.4 grams of phosphoric acid and 206.6 grams of nitrilotriacetic acid were added to an open vessel containing 650ml of water, after dissolution with stirring, 79.1 grams of basic nickel carbonate and 193.7 grams of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolved to give a first solution. And then, placing the first solution in a high-pressure reaction kettle, sealing and treating. The conditions of the treatment include: after the temperature is 80 ℃, the time is 8 hours, and after the treatment temperature is in place, nitrogen is introduced into the high-pressure reaction kettle to ensure that the pressure in the high-pressure reaction kettle reaches 4.0 MPa. After the solution had cooled naturally to room temperature after the completion of the treatment, 39.9 g of ammonium paramolybdate was added to the treated first solution with water to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S2 carrier was taken, and the S2 carrier was impregnated with 114ml of the above impregnation solution for 1 hour, and then dried at 200 ℃ for 2 hours to obtain catalyst DC-6, the catalyst property parameters are shown in Table 1.

Example 4

117.6 g of phosphoric acid, 59.1 g of ammonium dihydrogen phosphate and 195.3 g of citric acid were put into an open vessel containing 600ml of water, and after dissolution by stirring, 243.6 g of basic nickel carbonate and 190.5 g of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolution was achieved, followed by addition of 38.2 g of glycerol to obtain a first solution. And then, placing the first solution in a high-pressure reaction kettle, and sealing the reaction kettle for treatment. The treatment conditions are as follows: the temperature is 190 ℃, the pressure is the autogenous pressure of the solution system in the high-pressure reaction kettle, the value is 2.1MPa, and the processing time is 2 hours. After the solution was naturally cooled to room temperature after the completion of the treatment, 227.5 g of ammonium metatungstate was added to the treated first solution, and after dissolution by stirring, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S3 carrier was taken, and S3 carrier was impregnated with 105ml of the above impregnation solution for 1 hour, followed by drying at 120 ℃ for 3 hours to obtain catalyst C-4, the catalyst properties parameters of which are shown in Table 1.

Comparative example 7

The preparation method is the same as that of example 4, except that the autoclave treatment step is not performed after the first solution is prepared, the obtained catalyst is DC-7, and the property parameters of the catalyst are shown in Table 1.

Example 5

76.4 g of phosphoric acid, 28.8 g of ethylenediaminetetraacetic acid, 10.7 g of diammonium ethylenediaminetetraacetate and 96.4 g of basic cobalt carbonate were added to an open vessel containing 600ml of water, and after heating, stirring and dissolving, 313.9 g of molybdenum trioxide was added to the above solution, and stirring and heating were continued until dissolving, to obtain a first solution. And then, placing the first solution in a high-pressure reaction kettle, sealing and treating. The conditions of the treatment include: after the temperature is 150 ℃, the time is 4 hours, and after the treatment temperature is in place, nitrogen is introduced into the high-pressure reaction kettle to ensure that the pressure in the high-pressure reaction kettle reaches 7.0 MPa. After the solution was naturally cooled to room temperature after the completion of the treatment, 86.2 g of ammonium metatungstate was added to the solution, and after the solution was dissolved by stirring, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S4 carrier was taken, and the S4 carrier was impregnated with 140ml of the above impregnation solution for 1 hour, followed by drying at 150 ℃ for 4 hours to obtain catalyst C-5, the catalyst properties parameters of which are shown in Table 1.

Comparative example 8

The preparation method is the same as that of example 5, except that the autoclave treatment step is not performed after the first solution is prepared, the obtained catalyst is DC-8, and the property parameters of the catalyst are shown in Table 1.

Example 6

177 grams of phosphoric acid and 59.3 grams of citric acid monohydrate were added to an open vessel containing 600ml of water, after dissolution with stirring, 124.6 grams of nickel hydroxycarbonate and 436 grams of molybdenum trioxide were mixed and added to the above solution, and stirring and heating were continued until dissolution to give a first solution. And then, placing the first solution in a high-pressure reaction kettle, sealing and then carrying out activation treatment. The conditions of the activation treatment are as follows: the temperature is 105 ℃, the pressure is the autogenous pressure of a solution system in the high-pressure reaction kettle, the value is 0.3MPa, and the processing time is 10 hours. After the activation treatment was completed, the solution was naturally cooled to room temperature, and then 55.3 g of ammonium metatungstate and 98.8 g of diethylene glycol were added to the first solution subjected to the activation treatment, and after stirring and dissolution, water was added to make the volume of the solution 1000ml, thereby preparing an impregnation solution.

150 g of S4 carrier was taken, and the S4 carrier was impregnated with 140ml of the above impregnation solution for 1 hour, followed by drying at 120 ℃ for 4 hours to obtain catalyst C-6, the catalyst properties parameters of which are shown in Table 1.

Comparative example 9

The preparation method is the same as example 6, except that the autoclave treatment step is not performed after the first solution is prepared, the obtained catalyst is DC-9, and the property parameters of the catalyst are shown in Table 1.

TABLE 1

Examples 7-12 are provided to illustrate the catalytic activity of hydrogenation catalysts C-1-C-6 provided by the present invention, and comparative examples 10-18 are provided to illustrate the catalytic activity of comparative catalysts DC-1-DC-9.

The first evaluation method comprises the following steps: the method is used for evaluating the catalytic diesel oil hydrotreating performance of the catalyst and the contrast agent, and comprises the following specific steps: the catalyst was crushed to 2-4 mm and evaluated on a 30 ml hydrogenation unit using feed oil and evaluation conditions as shown in Table 2. The method for measuring sulfur is SH/T0689-2000, and the method for measuring nitrogen is SH/T0657-2007. The hydrodesulfurization activity of the catalyst was calculated according to the 1.65-stage reaction, and the hydrodenitrogenation activity was calculated according to the 1-stage reaction. The calculation formula involved is as follows.

TABLE 2

Properties of crude oil	Catalytic diesel fuel
		Density (20 ℃ C.), g/cm³	0.9242
S，ppm	6800
		N，ppm	902
Reaction conditions
		Partial pressure of hydrogen, Mpa	6.0
Volume of catalyst, ml	30
		Temperature, C	340
Volumetric space velocity h^-1	2.0
		Hydrogen to oil ratio, v/v	300

Examples 7 and 8 and comparative examples 10 to 12 were conducted in accordance with evaluation method one for illustrating the hydrodesulfurization and hydrodenitrogenation activities of the catalysts C-1 and C-2 and the comparative agents DC-1 to DC-3, and the evaluation results are shown in Table 3.

TABLE 3

The results in table 3 show that: the hydrodesulfurization and hydrodenitrogenation performances of the catalyst provided by the invention are obviously superior to those of a comparative catalyst.

And a second evaluation method: the method is used for evaluating the residual oil hydrotreating performance of the catalyst and the contrast agent, and comprises the following steps: the catalyst is crushed into particles of 2-4 mm, the reaction is carried out on a hydrogenation device of 250 ml, and raw oil adopts the slag from the middle east China, the sulfur content is 4.7%, the nitrogen content is 0.29%, and the carbon residue is 12.6%. The reaction conditions are as follows: the reaction temperature is 385 ℃, the hydrogen partial pressure is 15.0 MPa, and the volume space velocity is 0.5h^-1. The analysis method of the carbon residue is GB/T17144-1997, the hydrogenation carbon residue removal activity is calculated according to the 1-stage reaction, and the related calculation formula is as follows.

Example 9 and comparative examples 13 to 15

The residue oil hydrodecarbonization performance of the catalyst C-3 and the contrast agents DC-4, DC-5 and DC-6 is illustrated by the evaluation method II, and the evaluation results are shown in Table 4.

TABLE 4

Numbering	Catalyst and process for preparing same	Relative hydrogenation to remove carbon residue activity%
			Example 9	C-3	122
Comparative example 13	DC-4	100
			Comparative example 14	DC-5	113
Comparative example 15	DC-6	108

The results in Table 4 show that the catalyst C-3 of the present invention has a higher residue hydrodecarbonization activity than the comparative catalysts DC-4, DC-5 and DC-6.

The third evaluation method comprises the following steps: the method is used for evaluating the coal liquefaction oil hydrotreating performance of the catalyst and the contrast agent, and comprises the following specific steps: the catalyst was crushed to 2-4 mm size and evaluated on a 250 ml hydrogenation unit using feed oil properties and reaction conditions as shown in Table 5. The hydrodesulfurization activity of the catalyst is calculated according to the 1.65-level reaction, the hydrodenitrogenation activity is calculated according to the 1-level reaction, and the calculation formula and the sulfur and nitrogen analysis method are the same.

TABLE 5

Properties of crude oil	Coal liquefaction oil
		Density (20 ℃ C.), g/cm³	0.9934
S，ppm	133
		N，ppm	3500
Colloid, m%	8.0
		Reaction conditions
Partial pressure of hydrogen, MPa	12.0
		Catalyst volume, mL	100
Temperature, C	380
		Volumetric space velocity h^-1	1.4

Example 10 and comparative example 16

The hydrodenitrogenation and hydrodesulfurization activities of catalyst C-4 and comparative agent DC-7 were evaluated according to evaluation method three, and the results are shown in Table 6.

TABLE 6

The results in Table 6 show that the coal liquefaction oil hydrotreating performance of catalyst C-4 of the present invention is significantly better than that of comparative catalyst DC-7.

The fourth evaluation method comprises the following steps: the method is used for evaluating the coking wax oil hydrotreating performance of the catalyst and the contrast agent, and comprises the following specific steps: the catalyst was crushed to 2-4 mm size and evaluated on a 250 ml hydrogenation unit using feed oil properties and reaction conditions as shown in Table 7.

TABLE 7

Properties of crude oil	Coker gas oil
		Density (20 ℃ C.), g/cm³	0.9205
S，ppm	8300
		N，ppm	6100
MCR，m％	0.32
		Reaction conditions
Partial pressure of hydrogen, MPa	10.0
		Catalyst volume, mL	100
Temperature, C	365
		Volumetric space velocity h^-1	1.4
Hydrogen to oil ratio, v/v	600

The method for measuring sulfur is SH/T0689-2000, and the method for measuring nitrogen is SH/T0704-2001. The hydrodesulfurization activity of the catalyst was calculated according to the 1.5-stage reaction, and the calculation formula was as follows, and the hydrodenitrogenation activity was calculated according to the 1-stage reaction, and the calculation formula was the same as in example 7.

Example 11 and comparative example 17

The evaluation was carried out in accordance with the fourth evaluation method to show the hydrodenitrogenation and hydrodesulfurization activities of the catalyst C-5 and the comparative agent DC-8, and the evaluation results are shown in Table 8.

TABLE 8

The results in Table 8 show that the coker gas oil hydrotreating performance of catalyst C-5 of the present invention is significantly better than that of comparative catalyst DC-8.

The evaluation method five: the method is used for evaluating the hydrofining performance of the catalyst and the contrast agent of the mixed diesel oil, and comprises the following specific steps: the catalyst was crushed to 2-4 mm size and evaluated on a 250 ml hydrogenation unit using feed oil properties and reaction conditions as shown in Table 9. The hydrodesulfurization activity of the catalyst is calculated according to the 1.65-level reaction, the hydrodenitrogenation activity is calculated according to the 1-level reaction, and the calculation formula and the sulfur and nitrogen analysis method are the same.

TABLE 9

Properties of crude oil	Straight diesel/catalytic diesel mixed oil
		Density (20 ℃ C.), g/cm³	0.8630
S，ppm	9800
		N，ppm	390
Reaction conditions
		Partial pressure of hydrogen, MPa	6.4
Catalyst volume, mL	100
		Temperature, C	355
Volumetric space velocity h^-1	2.0

Example 12 and comparative example 18

The hydrodenitrogenation and hydrodesulfurization activities of catalyst C-6 and comparative agent DC-9 were evaluated according to evaluation method five, and the results are shown in Table 10.

Watch 10

The results in Table 10 show that the hydrorefining performance of the mixed diesel oil of the catalyst C-6 provided by the invention is obviously superior to that of the comparative catalyst DC-9.

Claims

1. A preparation method of a hydrogenation catalyst comprises the steps of contacting an impregnation solution with a carrier, and then drying, roasting or not roasting to obtain the hydrogenation catalyst, and is characterized in that the preparation method of the impregnation solution comprises the following steps:

2. The method of claim 1, wherein the operating conditions of the contacting comprise: the temperature is between room temperature and 80 ℃, and the contact time is 0.1 to 24 hours.

3. The method according to claim 1, wherein the drying operating conditions comprise: the temperature is 60-250 ℃ and the time is 1-24 hours; the roasting operation conditions comprise: the temperature is 300 ℃ and 700 ℃ and the time is 0.5-12 hours.

4. The method according to any one of claims 1 to 3, wherein the group VIII metal is at least one selected from the group consisting of Fe, Co and Ni.

5. The method according to any one of claims 1 to 3, wherein the group VIII metal-containing compound is selected from one or more of nitrates, carbonates, hydroxycarbonates, phosphates, hypophosphites and organic carboxylates thereof.

6. The process according to any one of claims 1 to 3, characterized in that the first group VIB metal component is molybdenum and the second group VIB metal component is tungsten.

7. The process according to claim 6, wherein the first VIB-metal-containing compound is selected from molybdenum trioxide, molybdic acid, paramolybdic acid, molybdate, phosphomolybdic acid, phosphomolybdate, paramolybdate, dimolybdate, tetramolybdate, and the second VIB-metal-containing compound is selected from tungstic acid, metatungstic acid, ethyl metatungstic acid, phosphotungstic acid, silicotungstic acid, phosphotungstate, silicotungstate, ethyl metatungstate, tungstate, metatungstate.

8. The method according to any one of claims 1 to 3, wherein the first solution further contains at least one inorganic acid or a mixture of at least one inorganic acid and at least one inorganic acid salt.

9. The method according to claim 8, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, and boric acid, and the inorganic acid salt is an ammonium salt of the inorganic acid.

10. The preparation method according to any one of claims 1 to 3, characterized in that the first solution further comprises at least one organic auxiliary agent, wherein the organic auxiliary agent is one or more of organic acid, organic alcohol and organic acid ammonium salt.

11. The method as claimed in claim 10, wherein the organic acid is selected from one or more of aminocarboxylic acid, alkylcarboxylic acid, carboxylic acid containing aldehyde and carboxylic acid containing hydroxyl, the organic alcohol is selected from one or more of C1-C8 organic alcohol and/or polyethylene glycol having a weight average molecular weight of 120-4000, and the ammonium salt of the organic acid is selected from one or more of the ammonium salts of the foregoing organic acids.

12. The production method according to any one of claims 1 to 3, wherein the treatment is performed at a pressure of 0.15 to 7 MPa.

13. The method as claimed in any one of claims 1 to 3, wherein the pressure of the treatment is the autogenous pressure and/or the input pressure of the solution in the closed container.

14. The method of claim 13, wherein the input pressure is generated from gaseous species introduced into the closed vessel, the gaseous species introduced into the closed vessel being air, nitrogen, an inert gas, carbon dioxide, a hydrocarbon from C1 to C5.

15. The method according to any one of claims 1 to 3, wherein the impregnating solution is an aqueous solution.

16. The process according to any one of claims 1 to 3, characterized in that the introduction of the second metal VIB-containing compound into the treated first solution in step (3) is carried out directly or in the form of an aqueous solution.

17. The method according to claim 1 or 16, wherein the temperature of the first solution after cooling is between room temperature and 45 ℃ when the second group VIB metal component is introduced.

18. The method according to claim 1, wherein an organic auxiliary is further introduced in step (3), and the organic auxiliary is introduced before, simultaneously with or after the compound containing the second VIB metal.

19. A hydrogenation catalyst obtainable by the process of any one of claims 1 to 18.

20. The catalyst of claim 19, wherein the carrier and the metal component are used in amounts such that, in terms of oxides, the group VIII metal content is 1 to 9 wt.%, the first VIB metal content is 1 to 30 wt.%, the second VIB metal content is 2 to 36 wt.%, and the balance is the carrier, based on the final catalyst during the preparation.