CN112570038A - Reduced bulk catalyst and process for preparing same - Google Patents

Reduced bulk catalyst and process for preparing same Download PDF

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Publication number
CN112570038A
CN112570038A CN202011297688.6A CN202011297688A CN112570038A CN 112570038 A CN112570038 A CN 112570038A CN 202011297688 A CN202011297688 A CN 202011297688A CN 112570038 A CN112570038 A CN 112570038A
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reduced bulk
group
catalyst
bulk catalyst
reaction
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李荣观
侯远东
舒颖琦
马安
葛少辉
赵秦峰
王月
孙立明
张若霖
陈菲
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a reduced bulk catalyst for use in hydroprocessing of hydrocarbon feedstocks, particularly in hydrodearomatization applications, and a process for its preparation. The catalyst contains at least one group VIII metal element and at least one group VIB metal element, and can be obtained by a method comprising the following steps: forming a slurry containing at least one group VIII metal element in a system with a certain pH value; reacting the slurry at a temperature; after cooling, adding a VIB group element compound, and uniformly mixing; then putting the mixed solution into a closed container for hydrothermal reaction, filtering and drying to obtain a catalyst precursor; forming, drying and optionally roasting the precursor to form a formed catalyst; and then reduced to form a reduced bulk catalyst. The reduced bulk phase catalyst can meet the requirements of safety, environmental protection, greenness and low carbon, and the catalyst product has relatively stable quality and high hydrogenation activity.

Description

Reduced bulk catalyst and process for preparing same
Technical Field
The invention belongs to the field of hydrocarbon raw material hydrogenation dearomatization treatment, and particularly relates to a reduced bulk phase catalyst and a preparation method thereof.
Background
The bulk phase catalyst means: the metal active component and the molding component are mixed and molded, and the obtained catalyst is a bulk phase catalyst. Unlike conventional supported catalysts, supported catalysts require the metal active component to be formulated as a solution and then impregnated onto the support of the catalyst. This process is limited by both the solution formulation and the ability of the support to contain the metal active ingredient. Thus, conventional supported catalysts have a metal oxide mass (based on the weight of the overall catalyst) of no more than 40%. Correspondingly, the content of the metal active component in the bulk catalyst can be adjusted according to the forming mode of the bulk catalyst. Typically, the bulk catalyst has a metal oxide active component content (based on the weight of the bulk catalyst) of from 60% to 90%. Therefore, the bulk catalyst can have higher catalytic activity per unit volume than the supported catalyst.
Compared with the traditional sulfuration state bulk phase catalyst, the reduced bulk phase catalyst has the advantage that sulfur element cannot be introduced into products in the hydrotreating process aiming at the hydrocarbon raw material containing trace sulfur in the processing raw material. Is more suitable for the fields of solvent oil dearomatization and the like.
CN 106040255A discloses a bio-oil hydrodeoxygenation catalyst and a preparation method thereof. The catalyst used was a reduced bulk catalyst. The catalyst takes a nickel-tungsten composition as a main active component, rare earth metals such as lanthanum and cerium as auxiliaries, silicon dioxide as a dispersion medium, and elemental fluorine is added to modify the catalyst.
The preparation process of the method is relatively complex, and is mainly embodied in that all reaction solvents are required to be evaporated and then reduced in the preparation process to obtain the reduced bulk phase catalyst. The energy consumption in the reaction process is large, and the method is not suitable for industrial production and low-carbon environmental protection.
WO 00/41810 and WO 00/41811 disclose the synthesis of various sulfided bulk catalysts. The catalyst is a bulk catalyst of bulk catalyst particles of at least one VIII group metal and at least one VIB group metal, and elements such as niobium and the like are taken as auxiliary agents. The sulfide phase catalyst is synthesized by a method in which at least one metal compound is at least partially kept in a solid state and at least one compound is in a dissolved state, a method in which both the metal compounds are kept in a solid state, and a method in which both the dissolved compounds are coprecipitated, and then filtering, molding and vulcanizing.
The preparation method is simple in preparation process, but the problems of metal ion recovery in the bulk phase catalyst reaction filtrate, filtrate recycling and the like are not considered in the preparation process. Easily generate a large amount of wastewater containing metal ions, and is not beneficial to the cost control of catalyst production and safety and environmental protection.
CN110975908A and CN110975910A disclose a method for synthesizing bulk phase catalyst by recycling filtrate and not generating filtrate, aiming at the problems of metal ion recovery and filtrate recycling in bulk phase catalyst reaction filtrate.
The preparation method is simple in preparation process and safer and more environment-friendly, but in the preparation process, because the compound containing the VIII group element and the compound containing the VIB group element are treated simultaneously in the hydrothermal process, the reaction process of the compound containing the VIII group element and the compound containing the VIB group element is uncontrollable, the concentration of metal ions in the filtrate is relatively high, and the quality of the catalyst product after the filtrate is recycled is not maintained.
Most of the prior art references are designed for sulfided bulk catalysts. The bulk phase catalyst synthesis process is relatively complicated or filtrate recycling in the synthesis process is not considered, so that environmental protection and product quality are influenced in the production process. In the aspect of design of a reduced bulk catalyst, few references in the prior art are provided, and in few references, the synthesis process needs an evaporation process involving a reaction solvent, which is not favorable for low carbon and environmental protection of the bulk catalyst.
Thus, a gap in the prior art is the design of a reduced bulk catalyst for hydrocarbon feedstocks having trace amounts of sulfur in the process feedstock. The synthesis process of the catalyst needs to meet the requirements of safety, environmental protection, green and low carbon, and has higher stability of the quality of the catalyst product and higher activity of the hydrogenation treatment of hydrocarbon raw materials, particularly the hydrogenation dearomatization.
Disclosure of Invention
The invention mainly aims to provide a reduced bulk phase catalyst, a preparation method thereof and a hydrogenation catalyst containing the reduced bulk phase catalyst, so as to overcome the defects that the synthesis process of the catalyst in the prior art does not meet the requirements of safety, environmental protection, greenness and low carbon, and the quality of the catalyst product is relatively unstable and the hydrogenation activity is low.
In order to achieve the above objects, the present invention provides a method for preparing a reduced bulk catalyst for use in a process for hydrotreating a hydrocarbon feedstock, comprising the steps of:
step 1: mixing a compound containing VIII group elements with a protic liquid, placing the mixture in a closed container for reaction, and cooling after the reaction is finished to obtain a reacted solution;
step 2: mixing a compound containing a VIB group element with the reacted solution obtained in the step (1), placing the mixture in a closed container for reaction, filtering and drying to obtain a catalyst precursor;
and step 3: forming, drying and roasting the catalyst precursor to obtain a formed catalyst; and
and 4, step 4: and reducing the molded catalyst to obtain a reduced bulk phase catalyst.
The invention can also be detailed as follows:
the preparation method comprises the following steps:
step 1, preparing a certain volume of protic liquid with a pH value of 6-11;
step 2, mixing a compound containing the VIII group element with the liquid to form slurry;
step 3, placing the mixed solution obtained in the step 2 in a closed container for reaction, wherein the reaction time is at least 1 hour, the reaction temperature is not lower than 80 ℃, and then cooling;
step 4, mixing a compound containing VIB group elements with the liquid in the step 3;
step 5, placing the mixed solution obtained in the step 4 in a closed container for reaction, wherein the reaction time is at least 1 hour, the reaction temperature is 50-200 ℃, and filtering and drying to obtain a catalyst precursor;
step 6, forming, drying and optionally roasting the catalyst precursor to form a formed catalyst; and
and 7, reducing the molded catalyst at 200-600 ℃ to form a reduced bulk phase catalyst.
In the preparation method of the bulk phase catalyst, the filtrate obtained by filtering in the step 5 can be reused as a component of the protic liquid in the step 1.
The preparation method of the bulk phase catalyst comprises the following steps of preparing one or more of a filtrate, an acidic substance, an alkaline substance and water obtained by filtering in the step 5; the acidic substance is nitric acid, acetic acid or ammonium nitrate, and the alkaline substance is ammonia water, urea or ammonium carbonate.
The bulk phase catalyst is prepared by taking a compound containing a VIII group element as a group VIII element, taking a compound containing a VIB group element as a group VIB element, wherein the molar ratio of the compound containing the VIII group element to the compound containing the VIB group element is 20: 1-1: 20, and the VIII group element in the compound containing the VIII group element is cobalt and/or nickel; the VIB group element in the compound containing the VIB group element is molybdenum and/or tungsten; the molar ratio of the compound containing the VIII group element to the compound containing the VIB group element is 4: 1-1: 4.
In the preparation method of the bulk phase catalyst, the compound containing the VIII group element is an inorganic substance which has a valence of +2 or +3 and is insoluble in the protic liquid in the step 1; the compound containing the VIB group element is an inorganic substance which has a valence of the VIB group element of +4 or +6 and is dissolved in the protic liquid obtained in the step (1), and the compound containing the VIII group element is one or a combination of more than two of basic nickel carbonate, basic cobalt carbonate and nickel carbonate; the compound containing the group VIB element is ammonium heptamolybdate and/or ammonium metatungstate.
In the preparation method of the bulk phase catalyst, the volume of the protic liquid in the step 1 is larger than the saturated water absorption volume of the compound containing the VIII group element, and preferably 3-5 times of the saturated water absorption volume.
The preparation method of the bulk phase catalyst provided by the invention has the advantages that the reaction temperature in the step 3 is 80-120 ℃, and the reaction time is 2-12 hours.
In the preparation method of the bulk phase catalyst, the temperature in the step 3 is required to be reduced to a temperature at which the compound containing the VIB group element is not decomposed in the step 4, and the preferable temperature is 20-40 ℃.
According to the preparation method of the bulk phase catalyst, the reaction temperature in the step 5 is 50-150 ℃, and the reaction time is 2-12 hours.
The process for the preparation of the bulk catalyst according to the invention, wherein the shaping process in step 6 comprises one or more of the following process steps:
a) mixing a catalyst precursor with one or more materials selected from the group consisting of: extrusion aid materials, adhesive materials, alumina, silica and molecular sieves;
b) grinding, dry and/or wet mixing; and
c) and (5) forming.
In the forming process, the dry mass content of the catalyst precursor accounts for 30-90% of the total dry mass of the added substances.
According to the preparation method of the bulk phase catalyst, the reduction temperature in the step 7 is 250-390 ℃, the reduction atmosphere is hydrogen, and the reduction time is not less than 1 hour.
The invention also provides a bulk phase catalyst obtained by the preparation method of the reduced bulk phase catalyst.
The invention has the beneficial effects that:
the reduced bulk phase catalyst of the invention does not contain sulfur element, and hydrocarbon raw materials containing trace sulfur in the raw materials are processed, thus having the advantage that the sulfur element can not be introduced into the product in the hydrotreating process. Is more suitable for the fields of solvent oil dearomatization and the like.
In the filtrate obtained by filtering, the total weight of the metal atoms is less than one ten-thousandth of the feeding amount of the metal atoms, and the quality of the filtrate is stable. Therefore, the quality of the reduced bulk phase catalyst prepared by recycling the filtrate in the invention is stable, so that no waste liquid is generated in the preparation process of the catalyst provided by the invention.
In the preparation of the reduced bulk phase catalyst, the solid-liquid separation adopts a filtering operation method, the main component of the protic liquid is water, and the preparation method is safe, low-carbon and environment-friendly.
Drawings
FIG. 1 is an XRD pattern of solid components A-1 to A-6 obtained by mixing a compound containing a group VIII element with a protic liquid and hydrothermal reaction in examples 1 to 3 of the present invention.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention provides a process for the preparation of a reduced bulk catalyst for use in the hydroprocessing of hydrocarbon feedstocks, the process comprising the steps of:
step 1, preparing a certain volume of protic liquid with a pH value of 6-11;
step 2, mixing a compound containing the VIII group element with the liquid to form slurry;
step 3, placing the mixed solution obtained in the step 2 in a closed container for reaction, wherein the reaction time is at least 1 hour, the reaction temperature is not lower than 80 ℃, and then cooling;
step 4, mixing a compound containing VIB group elements with the liquid in the step 3;
step 5, placing the mixed solution obtained in the step 4 in a closed container for reaction, wherein the reaction time is at least 1 hour, the reaction temperature is 50-200 ℃, and filtering and drying to obtain a catalyst precursor;
step 6, forming, drying and optionally roasting the catalyst precursor to form a formed catalyst; and
and 7, reducing the molded catalyst at 200-600 ℃ to form a reduced bulk phase catalyst.
Wherein, the filtrate obtained by filtering in the step 5 can be reused as the component of the protic liquid in the step 1.
Wherein the component for preparing the protonic liquid is one or more of the filtrate obtained by filtering in the step 5, acidic substances, alkaline substances and water; the acidic substance is nitric acid, acetic acid or ammonium nitrate, and the alkaline substance is ammonia water, urea or ammonium carbonate.
The compound containing the VIII group element is calculated by the VIII group element, the compound containing the VIB group element is calculated by the VIB group element, the molar ratio of the compound containing the VIII group element to the compound containing the VIB group element is 20: 1-1: 20, and the VIII group element in the compound containing the VIII group element is cobalt and/or nickel; the VIB group element in the VIB group element-containing compound is molybdenum and/or tungsten; the molar ratio of the compound containing the VIII group element to the compound containing the VIB group element is 4: 1-1: 4.
Wherein the compound containing the VIII group element is an inorganic substance which has a valence of the VIII group element of +2 or +3 and is insoluble in the protic liquid in the step 1; the VIB group element-containing compound is an inorganic substance with a valence of +4 or +6 of the VIB group element, and is dissolved in the protic liquid in the step 1, and the VIII group element-containing compound is one or a combination of more than two of basic nickel carbonate, basic cobalt carbonate and nickel carbonate; the group VIB element-containing compound is ammonium heptamolybdate and/or ammonium metatungstate.
Wherein the volume of the protic liquid in step 1 is greater than the saturated water absorption volume of the group VIII element-containing compound, and preferably 3 to 5 times the saturated water absorption volume.
Wherein the reaction temperature in the step 3 is 80-120 ℃, and the reaction time is 2-12 hours.
In the cooling step in the step 3, the temperature needs to be reduced to a temperature at which the compound containing the group VIB element in the step 4 is not decomposed, and the preferred temperature is 25-40 ℃.
Wherein the reaction temperature in the step 5 is 50-150 ℃, and the reaction time is 2-12 hours.
Wherein the shaping in step 6 comprises one or more of the following method steps:
a) mixing a catalyst precursor with one or more materials selected from the group consisting of: extrusion aid materials, adhesive materials, alumina, silica and molecular sieves;
b) milling, dry or wet mixing or combinations thereof; and
c) and (5) forming.
In the forming process, the dry mass content of the precursor accounts for 30-90% of the total dry mass of the added substances.
And 7, wherein the reduction temperature in the step 7 is 250-390 ℃, the reduction atmosphere is hydrogen, and the reduction time is not less than 1 hour.
The reduced bulk catalyst of the present invention strictly controls the catalyst preparation process. Under normal conditions, the synthesis process of the bulk catalyst is to treat a compound containing a group VIII element and a compound containing a group VIB element simultaneously in a hydrothermal process, and the process can cause uncontrollable reaction processes of the compound containing the group VIII element and the compound containing the group VIB element. In the invention, the synthesis process of the bulk phase catalyst is firstly carried out the hydrothermal process of the compound containing the VIII group element, and the solid product after hydrothermal process is separated, dried and subjected to X-ray diffraction characterization. Taking the VIII group element as Ni as an example, the characterization result shows that the solid product obtained after hydrothermal treatment is Ni (HCO)3)2(PDF-No. 00-015-. As is well known, Ni (HCO)3)2Is weak base and weak acid salt, and is easy to generate double hydrolysis reaction in aqueous solution to generate Ni (OH)2And H2CO3(H2CO3Will decompose into H under appropriate conditions2O+CO2) And thus cannot be stably present in an aqueous system. However, during the synthesis of the bulk catalyst of the present invention, Ni (HCO) was successfully detected during hydrothermal process of the compound of the group VIII element3)2Stable in aqueous systems. It can be shown that water-soluble Ni (HCO) is present in the present system3)2Water-soluble Ni (OH)2With Ni in solution2+The chemical reaction equilibrium of (1). Due to Ni (HCO) in the aqueous solution3)2In a reaction equilibrium state, thereby making Ni (HCO)3)2Can still exist in the aqueous solution in a molecular state, further, due to Ni (HCO)3)2The molecules are in a supersaturated state in solution, thereby making Ni (HCO)3)2A large amount of the solid exists in the solid components after the hydrothermal reaction in a solid form, and then the solid components can be obtained by X-ray diffraction characterization and detection. Ni (HCO)3)2(iii) presence of (1) indicates that Ni (HCO) dissolved in water in the solution after hydrothermal treatment of the compound of the group VIII element3)2N dissolved in wateri(OH)2With Ni in solution2+Is in equilibrium. Even if a compound of a group VIB element is added to the system in the next step to effect a reaction, Ni (HCO) present in the system in a solid form3)2Ni (HCO) dissolved in water in the system before the reaction is completed3)2Water-soluble Ni (OH)2With Ni in solution2+The equilibrium of (c) still exists. Therefore, in this example, the hydrothermal process of the group VIII element-containing compound is performed to help generate a stable water-soluble Ni (HCO)3)2Water-soluble Ni (OH)2With Ni in solution2+The balance system of (a) further contributes to the control of the reaction process of the compound containing the VIII group element and the compound containing the VIB group element. Finally, the purposes of reducing the concentration of metal ions in the filtrate, stabilizing the quality of the catalyst product and improving the hydrogenation performance of the catalyst are achieved.
The bulk catalyst of the invention is a reduced bulk catalyst and is easy to react with sulfur-containing compounds, so that the sulfur content of the hydrocarbon raw material is not more than 5ppm in the process of processing the hydrocarbon raw material. The reaction conditions under which the hydrogenation catalyst is used in the petroleum product in the hydrotreating process are not particularly limited, and for example, the reaction conditions for the hydrodearomatization of benzene are: reaction temperature: 100 ℃; reaction pressure; 0.2 Mpa; liquid benzene space velocity: 2.0h-1(ii) a Amount ratio of hydrogen to benzene species: 6:1.
The technical solution of the present invention will be further described with specific examples.
Example 1
160mL of water was weighed, the pH of the system was adjusted to 8 with aqueous ammonia, and 37.62g of basic nickel carbonate was mixed with the above liquid to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 100 ℃ for 2 hours, and then cooled to 30 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and recorded as A-1. And the other part is mixed with 22.24g of ammonium metatungstate, then the mixture is placed in a closed reaction kettle, and is subjected to hydrothermal reaction for 4 hours at the temperature of 120 ℃, and then the mixture is cooled and filtered. The filtrate was collected and recorded as B-1. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 8 hours at the temperature of 380 ℃ to obtain the reduced bulk phase catalyst C-1.
Adding a certain amount of water into the B-1 to make the volume of the water to be 160mL, and adding a certain mass of nitric acid to obtain a solution with the pH value of 8. 37.62g of basic nickel carbonate was mixed with the above liquid to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 100 ℃ for 2 hours, and then cooled to 30 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and recorded as A-2. And the other part is mixed with 22.24g of ammonium metatungstate, then the mixture is placed in a closed reaction kettle, and is subjected to hydrothermal reaction for 4 hours at the temperature of 120 ℃, and then the mixture is cooled and filtered. The filtrate was collected and recorded as B-2. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 8 hours at the temperature of 380 ℃ to obtain a reduced bulk phase catalyst C-2.
Example 2
160mL of water was weighed, and after adjusting the pH of the system to 6 with acetic acid, 33.86g of basic nickel carbonate and 0.49g of basic cobalt carbonate were mixed with the above liquid to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 80 ℃ for 4 hours, and then cooled to 20 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and scored as A-3. And the other part is mixed with 4.04g of ammonium metatungstate, then the mixture is placed in a closed reaction kettle, hydrothermal reaction is carried out for 6 hours at the temperature of 100 ℃, and then cooling and filtering are carried out. The filtrate was collected and recorded as B-3. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 6 hours at 290 ℃ to obtain a reduced bulk phase catalyst C-3.
A certain amount of water was added to B-3 to make the volume 160mL, a certain mass of acetic acid was added to obtain a solution having a pH of 6, and 33.86g of basic nickel carbonate and 0.49g of basic cobalt carbonate were mixed with the above liquid to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 80 ℃ for 4 hours, and then cooled to 20 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and recorded as A-4. And the other part is mixed with 4.04g of ammonium metatungstate, then the mixture is placed in a closed reaction kettle, hydrothermal reaction is carried out for 6 hours at the temperature of 100 ℃, and then cooling and filtering are carried out. The filtrate was collected and recorded as B-4. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 6 hours at 290 ℃ to obtain a reduced bulk phase catalyst C-4.
Example 3
160mL of water was weighed and 37.62g of basic nickel carbonate was mixed with the water to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 110 ℃ for 2 hours, and then cooled to 35 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and recorded as A-5. The other part was mixed with 6.74g of ammonium metatungstate and 0.54g of ammonium heptamolybdate, and then placed in a closed reaction vessel, subjected to hydrothermal reaction at 150 ℃ for 12 hours, and then cooled and filtered. The filtrate was collected and recorded as B-5. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 4 hours at 330 ℃ to obtain a reduced bulk phase catalyst C-5.
Adding a certain amount of water into the B-5 to make the volume of the water to be 160mL, and adding a certain mass of nitric acid to obtain a solution with the pH value of 7. 37.62g of basic nickel carbonate was mixed with the above solution to form a slurry. The slurry was placed in a closed reaction vessel, subjected to hydrothermal reaction at 110 ℃ for 2 hours, and then cooled to 35 ℃. Then, the system after the reaction was divided into two equal parts by mass. One portion was filtered and the solid product was collected and dried at 120 ℃ for 6 hours and recorded as A-6. The other part was mixed with 6.74g of ammonium metatungstate and 0.54g of ammonium heptamolybdate, and then placed in a closed reaction vessel, subjected to hydrothermal reaction at 150 ℃ for 12 hours, and then cooled and filtered. The filtrate was collected and recorded as B-6. The filter cake was dried at 120 ℃ for 6 hours to obtain a catalyst precursor. And (3) after the catalyst precursor is molded and dried, reducing for 4 hours at 330 ℃ to obtain a reduced bulk phase catalyst C-6.
In the reduced bulk catalysts obtained in examples 1 to 3 above, the mass of the active component accounted for 64% of the total catalyst mass.
In the above examples 1 to 3, the slurry containing Ni salt and Co salt was reacted at not lower than 80 ℃ in the hydrothermal reaction to obtain compounds A-1 to A-6 different from those involved in the reaction. The X-ray diffraction patterns of A-1 to A-6 are shown in FIG. 1. As shown by comparison of XRD spectrum library, Ni (HCO) is mainly generated in the step3)2(PDF-No. 00-015-. The reactant basic nickel carbonate has the chemical formula: NiCo3·2Ni(OH)2·4H2And O. Thus, it can be concluded that the process has undergone the following chemical reactions: 2 (NiCO)3·2Ni(OH)2·4H2O)＝Ni(HCO3)2+5Ni(OH)2+6H2And O. However, due to Ni (HCO)3)2If the double hydrolysis reaction is liable to occur in water, the following reaction must be present in the system: ni (HCO)3)2+2H2O＝Ni(OH)2+2H2CO3. Meanwhile, Ni (OH)2With Ni (HCO)3)2In aqueous solution, there is a dissociation equilibrium, namely: ni (OH)2＝Ni2++2OH-；Ni(HCO3)2＝Ni2++2HCO3 -Thus, water-soluble Ni (HCO) is present in the system3)2Water-soluble Ni (OH)2With Ni in solution2+The equilibrium state of (2) is beneficial to controlling the reaction process of the system with Mo salt and W salt. Finally, the purposes of reducing the concentration of metal ions in the filtrate, stabilizing the quality of the catalyst product and improving the hydrogenation performance of the catalyst are achieved.
Comparative example 1
Reference is made to the preparation method of CN 106040255 a: a) preparing a mixed aqueous solution containing 0.75mol of urea and 1mol of nickel nitrate, adding 2.3mol of ethyl orthosilicate into the mixed aqueous solution, stirring the mixed aqueous solution until the mixed aqueous solution is uniform and transparent, adding 6g of ammonium fluoride, stirring the mixture uniformly, standing the mixture until gel is formed, putting the gel into a closed container, heating the gel to 90 ℃, reacting the gel for 2 hours, drying the gel for 4 hours at the temperature of 80 ℃, drying the gel for 4 hours at the temperature of 140 ℃, and crushing the gel to obtain Ni/SiO2A precursor; b) preparing the mixture containing 0.14mol of ammonium metatungstate and 0.1mol of nitreMixing nickel acid with water solution, adding 30g ethylene glycol into the mixture, stirring, and adding Ni/SiO2Adding the precursor powder into the mixed solution, and sealing and standing for 12 hours; c) placing the mixed system into a crystallization kettle, and sealing and crystallizing for 4 hours at the temperature of 140 ℃; d) after crystallization is finished, evaporating the solvent, drying at 120 ℃ for 4 hours, roasting at 380 ℃ for 3 hours, and reducing with hydrogen at 375 ℃ for 3 hours to obtain NiW/SiO2Catalyst, noted D-1.
The above examples differ from the preparation of comparative example 1 as follows: comparative example 1 the synthesis process was relatively complex, involving 1 gel drying process and 1 solution evaporation process. The energy consumption in the synthesis process is large, and low carbon and environmental protection are not facilitated. Through calculation, the mass content of the D-1 active component accounts for 64 percent of the total mass of the catalyst.
Comparative example 2
Reference to the preparation method of CN 110975908A: 8.83g of ammonium heptamolybdate and 13.48g of ammonium metatungstate were weighed and added to 30g of water to prepare a homogeneous mixed solution. In the system, ammonia water with the mass concentration of 25% is dripped until the pH value of the solution is 9, and then the solution and 12.54g of basic nickel carbonate are stirred uniformly. And (3) placing the system in a closed reaction kettle, reacting for 2 hours at 35 ℃, then heating to 150 ℃, reacting for 2 hours, and then cooling, filtering and washing. The filtrate was designated as E-1 and the filter cake was dried at 120 ℃ for 4h to give the bulk catalyst. In the preparation method of this patent, there is no bulk catalyst reduction process, but it is apparent from the reduction method of the prior art document that the bulk catalyst in comparative example 2 is reduced to a reduced bulk catalyst. Therefore, in order to compare the activity of the catalyst of comparative example 2 with that of the example, the bulk catalyst synthesis method of comparative example 2 was combined with the reduction method of comparative example 1. Namely: the bulk catalyst of comparative example 2 was shaped, calcined at 380 ℃ for 3 hours, and then reduced with hydrogen at 375 ℃ for 3 hours to give a reduced bulk catalyst designated D-2.
After E-1 was diluted to 30mL, 8.83g of ammonium heptamolybdate and 13.48g of ammonium metatungstate were weighed and added to the filtrate diluent to prepare a homogeneous mixed solution. In the system, ammonia water with the mass concentration of 25% is dripped until the pH value of the solution is 9, and then the solution and 12.54g of basic nickel carbonate are stirred uniformly. And (3) placing the system in a closed reaction kettle, carrying out hydrothermal reaction for 2h at 35 ℃, then heating to 150 ℃, reacting for 2h, then cooling, filtering and washing. The filtrate was designated as E-2 and the filter cake was dried at 120 ℃ for 4 h. The resulting bulk catalyst was calcined at 380 ℃ for 3 hours after formation and then reduced with hydrogen at 375 ℃ for 3 hours to give the reduced bulk catalyst, noted D-3.
Wherein the mass of the D-2 and D-3 active components accounts for 64 percent of the total mass of the catalyst.
The above examples differ from the preparation of comparative example 2 as follows: inductively coupled plasma atomic emission spectroscopy characterization was performed on the filtrates B-1 to B-6 in example 1-3 and the filtrates E-1 and E-2 in comparative example 2, and the mass contents of various metal elements in B1 to B-6, E-1 and E-2 were obtained. The mass of each metal element in B1-B-6, E-1 and E-2 can be calculated according to the metal content and the mass of the filtrate. Further, by combining the total amount of metal elements added in the process of synthesizing the bulk catalyst in examples 1 to 3 and comparative example 2, the percentage of the metal elements in the filtrate to the total amount of the metal elements added can be calculated. The ratio is shown in table 1. As can be seen from the data in table 1, the percentage of the metal element in the filtrate of examples 1 to 3 to the total amount of the metal element added was 4 orders of magnitude lower than that of comparative example 2. The filtrate in the illustrated example has less influence on the product quality and the catalyst quality of different batches is more stable in the recycling process.
TABLE 1 percentage of metal element in different filtrates based on the total amount of metal element added
Figure BDA0002784591430000111
Figure BDA0002784591430000121
The reduced bulk catalysts obtained in examples 1 to 3 and comparative examples 1 and 2 were evaluated for their benzene hydrodearomatization activity. The results are shown in table 2. Benzene hydrogenation dearomatization reaction stripThe parts are as follows: reaction temperature: 100 ℃; reaction pressure: 0.2 Mpa; liquid benzene space velocity: 2.0h-1(ii) a Amount ratio of hydrogen to benzene species: 6:1. C-1 to C-6 are catalysts prepared by the technical scheme of the invention, and D-1 to D-3 are catalysts prepared by the prior art in comparative example 1 and comparative example 2. The catalysts evaluated possessed the same metal components and metal contents. As can be seen from Table 2, the conversion rates of benzene in the C-1-C-6 catalysts prepared by the technical scheme of the invention are higher than those in D-1-D-3, which shows that the catalytic performance of the reduced bulk phase catalyst prepared by the technical scheme of the invention has obvious advantages. Furthermore, the C-2, C-4, C-6 and D-3 catalysts are bulk catalysts prepared by using the filtrates obtained in the preparation of the C-1, C-3, C-5 and D-2 catalysts, respectively. As can be seen from table 2, the conversion rate of benzene is close to that of the catalyst prepared by the technical scheme of the present invention, and compared with the technical scheme of the comparative example 2, the catalyst prepared by the technical scheme of the present invention has stable product quality.
Table 2 evaluation data of the activity of different reduced bulk catalysts
Figure BDA0002784591430000122
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (17)

1. A process for the preparation of a reduced bulk catalyst for use in a process for the hydroprocessing of hydrocarbon feedstocks, comprising the steps of:
step 1: mixing a compound containing VIII group elements with a protic liquid with the pH value of 6-11, and placing the mixture in a closed container for reaction, wherein the reaction temperature is greater than or equal to 80 ℃; cooling after the reaction is finished to obtain a solution after the reaction;
step 2: mixing a compound containing a VIB group element with the solution obtained in the step 1, and placing the mixture in a closed container for reaction, wherein the reaction temperature is 50-200 ℃; filtering and drying to obtain a catalyst precursor;
and step 3: forming, drying and roasting the catalyst precursor to obtain a formed catalyst; and
and 4, step 4: and reducing the molded catalyst at 200-600 ℃ to obtain a reduced bulk phase catalyst.
2. The method for preparing a reduced bulk catalyst according to claim 1, wherein the filtrate obtained by filtration in step 2 is recycled as a component of the protic liquid in step 1.
3. The method of preparing a reduced bulk catalyst according to claim 1, wherein the component for preparing the protic liquid is at least one of the filtrate obtained by the filtration in step 2, an acidic substance, a basic substance, and water; the acidic substance is nitric acid, acetic acid or ammonium nitrate, and the alkaline substance is ammonia water, urea or ammonium carbonate.
4. The method for preparing a reduced bulk catalyst according to claim 1, wherein the group VIII element-containing compound is calculated as a group VIII element, the group VIB element-containing compound is calculated as a group VIB element, and the molar ratio of the group VIII element-containing compound to the group VIB element-containing compound is 20:1 to 1: 20.
5. A method of preparing a reduced bulk catalyst according to claim 4 wherein the group VIII element in the group VIII element-containing compound is cobalt and/or nickel; the VIB group element in the VIB group element-containing compound is molybdenum and/or tungsten; the molar ratio of the compound containing the VIII group element to the compound containing the VIB group element is 4: 1-1: 4.
6. The method for preparing a reduced bulk catalyst according to claim 1, wherein the valence of the group VIII element in the group VIII element-containing compound is +2 or +3, and the group VIII element-containing compound is insoluble in the protic liquid in the step 1; the valence of the VIB group element in the VIB group element-containing compound is +4 or +6, and the VIB group element is dissolved in the protic liquid in the step 1.
7. The method of preparing a reduced bulk catalyst according to claim 6 wherein the group VIII element-containing compound is at least one of basic nickel carbonate, basic cobalt carbonate, and nickel carbonate; the group VIB element-containing compound is ammonium heptamolybdate and/or ammonium metatungstate.
8. The method for producing a reduced bulk catalyst according to claim 1, wherein the volume of the added amount of the protic liquid in step 1 is larger than the saturated water absorption volume of the group VIII element-containing compound.
9. The method of producing a reduced bulk catalyst according to claim 8, wherein the volume of the added amount of the protic liquid in step 1 is 3 to 5 times the saturated water absorption volume of the group VIII element-containing compound.
10. The method for preparing a reduced bulk catalyst according to claim 1, wherein in the step 1, the reaction time is 1 hour or more, preferably 2 to 12 hours; the reaction temperature is 80-120 ℃.
11. The method for producing a reduced bulk catalyst according to claim 1, wherein in the step 1, the temperature is lowered to a temperature at which the compound containing the group VIB element is not decomposed.
12. The method of preparing a reduced bulk catalyst according to claim 11, wherein the temperature reduction in step 1 is performed by reducing the temperature to 20 to 40 ℃.
13. The method for preparing a reduced bulk catalyst according to claim 1, wherein in the step 2, the reaction time is 1 hour or more, preferably 2 to 12 hours; the reaction temperature is 50-150 ℃.
14. The method for preparing a reduced bulk catalyst according to claim 1, wherein in step 3, the shaping method comprises one or more of the following steps:
a) mixing the catalyst precursor with at least one selected from the group consisting of an extrusion aid, a binder, alumina, silica and a molecular sieve;
b) grinding, dry and/or wet mixing; and
c) and (5) forming.
15. A method of preparing a reduced bulk catalyst according to claim 14 wherein the catalyst precursor has a dry mass content of from 30% to 90% of the total dry mass of the added material.
16. The method for preparing a reduced bulk catalyst according to claim 1, wherein in the step 4, the reduction temperature is 250 to 390 ℃, the reduction atmosphere is hydrogen, and the reduction time is 1 hour or more.
17. A reduced bulk catalyst obtainable by a process for the preparation of a reduced bulk catalyst according to any one of claims 1 to 16.
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