CN107961796B - Hydrofining catalyst and preparation method thereof - Google Patents

Hydrofining catalyst and preparation method thereof Download PDF

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Publication number
CN107961796B
CN107961796B CN201610917600.3A CN201610917600A CN107961796B CN 107961796 B CN107961796 B CN 107961796B CN 201610917600 A CN201610917600 A CN 201610917600A CN 107961796 B CN107961796 B CN 107961796B
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catalyst
size distribution
pore size
metal elements
pores
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CN107961796A (en
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陈文斌
龙湘云
李明丰
刘学芬
刘清河
李坚
鞠雪艳
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • C10G2300/70—Catalyst aspects

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a hydrofining catalyst, a preparation method thereof and a hydrofining catalyst prepared by the method, wherein the hydrofining catalyst contains a modified catalyst carrier and a hydrodesulfurization catalytic active component, and is characterized in that the modified catalyst carrier contains a porous heat-resistant inorganic oxide and water and/or an organic matter with a boiling point not higher than 150 ℃, the selection of the porous heat-resistant inorganic oxide and the content of each component enable the pore size distribution of small-size pores to be increased and the pore size distribution of larger-size pores to be reduced after the carrier is subjected to high-temperature treatment, the small size refers to 2-8nm, the larger size refers to more than 8nm, and the high-temperature treatment mode is heating at the temperature of more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours. The method of the invention can further improve the hydrodesulfurization and denitrification activity of the catalyst.

Description

Hydrofining catalyst and preparation method thereof
Technical Field
The invention relates to a hydrofining catalyst, a preparation method thereof and a hydrofining catalyst obtained by the method.
Background
Hydrogenation is a supporting technology in the modern oil refining industry, and plays an important role in the aspects of producing clean fuel, improving the product quality, fully utilizing petroleum resources, pretreating raw materials and the like. With the development of economy, environmental protection and society, oil refining enterprises continuously put forward higher requirements on the activity and stability of hydrotreating catalysts, and the activity and selectivity of hydrofining catalysts are continuously improved. Among them, the hydrodesulfurization activity is an important index for measuring the performance of the hydrorefining catalyst.
Generally speaking, the hydrofining catalyst uses sulfide of VIB group metal (Mo and/or W) as a main active component, and sulfide of VIII group metal (Co and/or Ni) as an auxiliary active component, and the rest components in the catalyst are carriers. Research shows that the carrier in the catalyst has an important effect on the performance of the catalyst. The carrier should not only have a large specific surface area to allow a high dispersion of the active phase center, but also have a suitable pore structure to accommodate the diffusion of the reactants, and at the same time, the carrier may also affect the intrinsic activity of the active phase center. Therefore, many patents and research have been directed to the development and study of vectors. With the deterioration of the hydrogenation raw material, the size of the reaction molecules is gradually increased, and a carrier with a larger pore channel structure is required to better meet the requirement of reactant diffusion.
The general preparation method of alumina is that pseudo-boehmite is used as raw material, extrusion aid and adhesive are added to make shaping. After molding, the alumina is prepared by drying at 100-200 ℃ and roasting at 400-1000 ℃. Common methods for increasing pore size mainly include the use of different pseudoboehmite mixtures (CN1488441A), or the use of pore-expanding agents (CN1160602A, US4448896, CN1055877C), etc. In the above pore-expanding method, the pore-expanding agent and the pseudo-boehmite are not uniformly mixed, so that the pore-expanding effect is not good, and the addition of the pore-expanding agent also increases the cost.
CN1087289A discloses a preparation method of a macroporous alumina carrier. The method makes the pseudo-boehmite under room temperature instantly placed in high temperature atmosphere with the high temperature range of 500-650 ℃, and the temperature is kept constant for 2-4 hours at the high temperature. The method uses the water which is rapidly evaporated at high temperature to expand the pores of the carrier, but the activity of the hydrogenation catalyst prepared by the carrier needs to be further improved.
Disclosure of Invention
The invention aims to further improve the hydrodesulfurization and denitrification activity of a hydrofining catalyst, and provides a hydrofining catalyst, a preparation method thereof and a hydrofining catalyst obtained by the method.
The invention provides a hydrofining catalyst which contains a modified catalyst carrier and a hydrodesulfurization catalytic active component, and is characterized in that the modified catalyst carrier contains a porous heat-resistant inorganic oxide and an organic matter with a boiling point not higher than 150 ℃ and water, the porous heat-resistant inorganic oxide is selected and the content of each component enables the pore size distribution of small-size pores to be increased and the pore size distribution of larger-size pores to be decreased after the carrier is subjected to high-temperature treatment, wherein the small-size pores refer to 2-8nm, the larger-size pores refer to more than 8nm, and the high-temperature treatment is carried out in a mode of heating at the temperature of more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours.
In another aspect, the present invention provides a method for preparing a hydrorefining catalyst, comprising the steps of:
(1) impregnating porous heat-resistant inorganic oxide with water and/or organic matter with the boiling point not higher than 150 ℃, and then drying to obtain a modified catalyst carrier, wherein the porous heat-resistant inorganic oxide is selected and dried under the condition that the pore size distribution of small-size pores is increased and the pore size distribution of larger-size pores is decreased after the carrier is subjected to high-temperature treatment, the small size refers to 2-8nm, the larger size refers to more than 8nm, and the high-temperature treatment is carried out by heating at the temperature of more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours;
(2) impregnating the modified catalyst carrier obtained in the step (1) with an impregnating solution, wherein the impregnating solution contains a hydrodesulfurization catalytic active component and one or more organic matters with molecular weight less than 80;
(3) and (3) drying the impregnated carrier in the step (2).
The invention also provides a hydrofining catalyst prepared by the method.
The active metal of the hydrofining catalyst is uniformly distributed in the pore channels of the carrier. In the reaction process, reactant molecules pass through the pore channels of the catalyst and contact with active metals in the pore channels to generate hydrogenation reaction so as to remove impurity elements. As the hydrogenated feedstock is degraded, the size of the molecules in the feedstock becomes larger. The smaller pore size in the catalyst will not accommodate diffusion of the reactant molecules and thus the metal in the smaller pores will not be utilized.
In general, the carrier is roasted at a high temperature of more than 500 ℃ for 2 to 8 hours in the preparation process, so that the pore structure of the carrier is basically not changed after the carrier is treated at a temperature of not more than 400 ℃.
The method provided by the invention can improve the pore channel structure of the carrier by simply dipping the liquid and then drying, so that the number of pore channels with smaller pore diameters in the carrier is less, and therefore, the active metal can be distributed in larger pore channels as far as possible, the utilization rate of the active metal in the catalyst can be improved, and the performance of the catalyst can be improved. As described above, the essence of the method of the present invention is that by impregnating a porous heat-resistant inorganic oxide with a liquid material such as water and a small-molecular organic substance, the liquid material in the large pores volatilizes first under dry conditions, and the liquid material in the small pores volatilizes at a higher temperature or for a longer time.
Specifically, distillate oil with a sulfur content of 9100ppm and a nitrogen content of 532ppm was hydrotreated according to the following examples, and the sulfur content of the oil treated by the catalyst prepared by using the modified catalyst carrier provided by the invention in example 1-1 was 12.0ppm and the nitrogen content was 1.5ppm, while the sulfur content of the oil obtained by using the carrier used in comparative example 1-1 without the above modification treatment was 35ppm and the nitrogen content was 7.8 ppm. Therefore, the method can obviously improve the hydrodesulfurization and denitrification activity of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect the invention provides a method of modifying the pore size distribution of a support, the method comprising impregnating the support with a liquid and then drying, the drying conditions being such that the support, after treatment at elevated temperature, has an increased pore volume for small sizes, i.e. from 2 to 8nm, and a reduced pore volume for larger sizes, i.e. greater than 8 nm.
According to a preferred embodiment of the invention, the drying conditions are such that the pore size distribution of the small-sized pores of the support after the high-temperature treatment is not increased by more than 50%, preferably 10-35%; the pore size distribution of the larger size pores is reduced by not more than 60%, preferably 10-40%.
The invention provides a hydrofining catalyst which comprises a modified catalyst carrier and a hydrodesulfurization catalytic active component, and is characterized in that the modified catalyst carrier contains a porous heat-resistant inorganic oxide and an organic matter with a boiling point not higher than 150 ℃ and water, the porous heat-resistant inorganic oxide is selected and the content of each component is such that after the carrier is subjected to high-temperature treatment, the pore size distribution of small-size pores is increased and the pore size distribution of larger-size pores is decreased, wherein the small-size pores refer to 2-8nm, the larger-size pores refer to more than 8nm, and the high-temperature treatment is performed by heating at more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours.
Preferably, the modified catalyst support is subjected to high temperature treatment to increase the pore size distribution of small-sized pores by no more than 50%, preferably 10-35%; the pore size distribution of the larger size pores is reduced by not more than 60%, preferably 10-40%.
According to a preferred embodiment of the present invention, the modified catalyst support has a pore size distribution of small-sized pores of 25 to 65%, preferably 30 to 60%, a pore size distribution of larger-sized pores of 35 to 75%, preferably 40 to 70%, a pore volume of 0.6 to 1.2mL/g, preferably 0.6 to 0.8mL/g, a specific surface area of 180-450m2The preferred value of/g is 220-270m2/g。
Preferably, the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 35 to 70%, preferably 40 to 66%, a pore size distribution of larger-sized pores of 30 to 65%, preferably 34 to 60%, a pore volume of 0.85 to 1.4mL/g, and a specific surface area of 200-2/g。
Preferably, the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania and zirconia, and the boiling point of the organic matter is 50-120 ℃, preferably one or more of methanol, ethanol, propanol and petroleum ether.
According to a preferred embodiment of the present invention, the hydrodesulfurization catalytic active components are group VIII and group VIB metallic elements, preferably nickel and/or cobalt and tungsten and/or molybdenum, and the group VIII metallic elements are present in the hydrofinishing catalyst in an amount of from 2 to 15%, preferably from 3 to 10%, based on the dry weight of the catalyst and calculated as oxides; the content of the group VIB metal elements is 15-60%, preferably 20-45%.
In the present invention, the pore size distribution of the small-sized pores means that the volume of pores having a pore diameter of 2 to 8nm is a percentage of the total pore volume. The larger size pore size distribution refers to the volume of pores with pore diameters greater than 8nm as a percentage of the total pore volume. The magnitude of increase in the pore size distribution of the small-sized pores is calculated according to the following formula:
the increase in pore size distribution of the small-sized pores (pore size distribution of the small-sized pores after the high-temperature treatment-pore size distribution of the small-sized pores of the support before the high-temperature treatment)/pore size distribution of the small-sized pores of the support before the high-temperature treatment × 100%.
Similarly, the reduction range of the pore size distribution of the larger size pores is (the pore size distribution of the larger size pores of the support before the high-temperature treatment-the pore size distribution of the larger size pores after the high-temperature treatment)/the pore size distribution of the larger size pores of the support before the high-temperature treatment × 100%.
Before the high temperature treatment, i.e. after the drying for the process provided by the present invention.
In the present invention, the pore distribution, pore diameter, pore volume (pore volume), and specific surface area of the catalyst and the carrier are measured by a low-temperature nitrogen adsorption method (see "analysis of petrochemical industry (RIPP test method)", eds "Yangcui et al, published by scientific publishers, 1990).
In the present invention, the high-temperature treatment means heating at more than 200 ℃ and less than or equal to 400 ℃, preferably 250 ℃ and 400 ℃ for 1 to 10 hours, preferably 1 to 5 hours. The heating atmosphere is not particularly limited, and reference may be made to the drying and calcining atmosphere in the usual catalyst preparation process.
As described above, the essence of the method of the present invention is that by impregnating a porous heat-resistant inorganic oxide with a liquid material such as water and a small-molecular organic substance, the liquid material in the large pores volatilizes first under dry conditions, and the liquid material in the small pores volatilizes at a higher temperature or for a longer time.
In the invention, the small molecular organic substance can be various small molecular liquid organic substances capable of entering the small pore channels (i.e. the pore channels with the pore diameter not more than 8 nm) of the porous heat-resistant inorganic oxide through impregnation, the boiling point is preferably 50-120 ℃, for example, the small molecular liquid organic substance can be one or more of methanol, ethanol, propanol and petroleum ether, and the liquid substance is preferably water.
According to a preferred embodiment of the present invention, the porous heat-resistant inorganic oxide is impregnated with water by a pore saturation impregnation method or a supersaturation impregnation method, and the conditions for drying to remove the liquid material include a drying temperature of 50 to 200 ℃, preferably 100 and 200 ℃, and a drying time of 1 to 10 hours, preferably 1 to 4 hours. The pore channels of the porous heat-resistant inorganic oxide impregnated with the aqueous solution are filled with the aqueous solution. After the porous heat-resistant inorganic oxide is dried, water molecules in the pore channels are evaporated. Due to the different size ranges of the pore diameters, water molecules in larger pore diameters can be preferentially removed during drying, and water molecules in smaller pore diameters can be slowly evaporated. Therefore, after mild drying at 50-200 ℃, water molecules in larger pore channels of the porous heat-resistant inorganic oxide are preferentially removed, and only the rest of the water molecules are in the larger pore channels. In this way, water molecules are selectively filled in the smaller pores. Thereby reducing the number of small pores in the porous heat-resistant inorganic oxide without a significant change in the number of larger pores. During the preparation of the catalyst, the amount of the impregnated active components in the smaller pore channels will be reduced, and more active components will be distributed in the larger pore channel structure. Therefore, the utilization rate of the active component can be improved, and the performance of the catalyst can be improved.
According to a preferred embodiment of the present invention, the porous heat-resistant inorganic oxide has a pore volume of 0.85 to 1.4mL/g and a specific surface area of 200-500m2(ii)/g, the average pore diameter is 6-20 nm.
According to a preferred embodiment of the present invention, the porous refractory inorganic oxide has a pore size distribution of small-sized pores of 35 to 70%, preferably 40 to 66%, and a pore size distribution of larger-sized pores of 30 to 65%, preferably 34 to 60%.
The manner of impregnating the liquid substance may be various conventional impregnation methods such as a pore saturation impregnation method or a supersaturation impregnation method.
The process of the present invention can be used to modify a variety of conventional catalyst supports, for example, one or more of alumina, silica, zirconia, alumina-titania and alumina-silica can be treated. The shape of the carrier may be any of the shapes known in the art for use as a catalyst carrier, for example, a granular shape, a bar shape, or a clover shape.
The invention also provides a preparation method of the hydrofining catalyst, which comprises the following steps:
(1) impregnating porous heat-resistant inorganic oxide with water and/or organic matter with the boiling point not higher than 150 ℃, and then drying to obtain a modified catalyst carrier, wherein the porous heat-resistant inorganic oxide is selected and dried under the condition that the pore size distribution of small-size pores is increased and the pore size distribution of larger-size pores is decreased after the carrier is subjected to high-temperature treatment, the small size refers to 2-8nm, the larger size refers to more than 8nm, and the high-temperature treatment is carried out by heating at the temperature of more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours;
(2) impregnating the modified catalyst carrier obtained in the step (1) with an impregnating solution, wherein the impregnating solution contains a hydrodesulfurization catalytic active component and one or more organic matters with molecular weight less than 80;
(3) and (3) drying the impregnated carrier in the step (2).
Compared with the conventional carrier, the carrier treated by the method in the step (1), namely the modified catalyst carrier, has less pore size distribution of pores. Preferably, the support treated in step (1) of the process of the present invention has a pore size distribution of small-sized pores of 25 to 65%, preferably 30 to 60%, a pore size distribution of larger-sized pores of 35 to 75%, preferably 40 to 70%, a pore volume of 0.6 to 1.2mL/g, preferably 0.6 to 0.8mL/g, and a specific surface area of 180-450m2The preferred value of/g is 220-270m2(ii)/g, the average pore diameter is 5-18 nm.
According to the invention, the impregnation liquid preferably contains organic substances having a molecular weight of less than 80, preferably not more than 75. Wherein the organic substance with molecular weight less than 80 can be various organic substances with molecular weight less than 80, preferably less than 75, and contains-OH, -NH2and-COOH, preferably not including an amide-based substance such as urea, and more preferably methanol, ethanol, propanol, isopropanol, butanol,Isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, ethanolamine, ethylamine, propylamine, butylamine, glycine and the like. The nitrogen-containing organic substance is preferably an alcohol or a carboxylic acid because of its toxicity.
According to the method provided by the invention, the impregnation liquid also contains a phosphorus-containing substance and/or ammonia, wherein the phosphorus-containing substance is one or more of phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate.
The phosphorus-containing material is used in an amount such that P is based on the dry weight of the final catalyst2O5The content of P is 0.5-8%. The ammonia is preferably used in the form of aqueous ammonia, the concentration of which preferably ranges from 10 to 25% by weight. The amount of ammonia is based on the amount of liquid in the impregnation solution required for impregnation. According to a preferred embodiment of the present invention, the impregnation solution further comprises at least one of a phosphorus-containing substance and ammonia, and the preparation process of the impregnation solution comprises adding an organic substance having a molecular weight of less than 80 and a precursor of the hydrodesulfurization catalytic active component to an aqueous solution of a phosphorus-containing compound and/or ammonia under stirring, and stirring at 40-100 ℃ for 1-8 hours until all the substances are dissolved.
Preferably, the hydrodesulfurization catalytic active components are group VIII metal elements and group VIB metal elements; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.2-5, preferably 0.5-3.
According to a preferred embodiment of the invention, the precursor of the hydrodesulphurization catalytically active component is used in such an amount that the resulting catalyst has a content of group VIII metal elements of from 2 to 15%, preferably from 3 to 10%, calculated as oxide and based on the weight of the catalyst on a dry basis; the content of the group VIB metal elements is 15-60%, preferably 20-45%.
In the present invention, the dry weight is the weight determined by baking the sample at 600 ℃ for 4 hours.
Examples of the group VIII metal element include, but are not limited to, one or more of iron, cobalt, nickel, ruthenium, rhodium, and palladium, more preferably nickel and/or cobalt. Examples of the group VIB metal elements include, but are not limited to, one or more of chromium, molybdenum and tungsten, more preferably tungsten and/or molybdenum. The above metal active components can be obtained in the catalyst by adding their precursors to the impregnation solution. The cobalt precursor includes but is not limited to one or more of cobalt nitrate, basic cobalt carbonate, cobalt acetate and cobalt oxide, the Mo precursor includes but is not limited to one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate and molybdenum oxide, the Ni precursor includes but is not limited to one or more of nickel nitrate, basic nickel carbonate, nickel acetate and nickel oxide, and the tungsten precursor includes but is not limited to one or more of ammonium metatungstate, ammonium ethylmetatungstate and tungsten oxide.
The impregnation method of the present invention is not particularly limited, and the impregnation can be carried out in various ways known to those skilled in the art. For example, the impregnated liquid compound is loaded on the catalyst carrier by impregnation, spraying, etc., and the specific process is well known to those skilled in the art and will not be described herein.
According to the preparation method of the hydrofining catalyst provided by the invention, the drying temperature after the impregnation can be 50-350 ℃, preferably 80-250 ℃, more preferably 100-200 ℃, and the time can be 2-10 hours, preferably 3-8 hours, more preferably 3-6 hours.
The invention also provides a hydrofining catalyst prepared by the method. The hydrorefining catalyst prepared by the method has higher hydrodesulfurization and denitrification activity.
The method of the invention can also be used for directly treating the prior industrial carrier, reducing the number of small holes, further promoting the distribution number of active components in larger hole diameter and playing a role in promoting the hydrogenation activity.
The invention will be further illustrated by the following examples, which are not intended to limit the invention. The aluminum hydroxide powder used in the following examples was pseudo-boehmite produced by a long distance catalyst plant. The composition of the catalyst is calculated according to the feeding amount. The pore size distribution, pore diameter and pore volume of the catalyst and the carrier were measured by low-temperature nitrogen adsorption method (see methods of analysis of petrochemical industry (RIPP test method), eds., Yangcui et al, science publishers, 1990). The pores with the diameter of 2-4nm refer to pores with the diameter of more than or equal to 2nm and less than 4nm, the pores with the diameter of 4-6nm refer to pores with the diameter of more than or equal to 4nm and less than 6nm, the pores with the diameter of 6-8nm refer to pores with the diameter of more than or equal to 6nm and less than or equal to 8nm, the pores with the diameter of 8-10nm refer to pores with the diameter of more than 8nm and less than 10nm, and the pores with the diameter of 10-20nm refer to pores with the diameter of more than or equal to 10 nm.
The hydrodesulfurization and denitrification performance of the catalyst is measured on a 20mL high-pressure micro-reaction device, and an oxidation-state catalyst is directly converted into a vulcanization-state catalyst by adopting a temperature programming vulcanization method. The vulcanization conditions are as follows: the vulcanization pressure is 6.4MPa, and the vulcanized oil contains CS22% by weight of kerosene, the volume space velocity being 2h-1And the hydrogen-oil ratio is 300v/v, the constant temperature is kept for 6h at 230 ℃/h, then the temperature is raised to 360 ℃ for vulcanization for 8h, and the temperature raising rate of each stage is 10 ℃/h. After vulcanization, reaction raw materials are switched to carry out hydrodesulfurization and denitrification activity test, and the reaction raw materials are high-nitrogen high-aromatic-hydrocarbon distillate oil with the sulfur content of 9100ppm, the nitrogen content of 532ppm and the aromatic hydrocarbon content of 55 wt%. The test conditions were: the pressure is 6.4MPa, and the volume space velocity is 1.5h-1The hydrogen-oil ratio was 300v/v, and the reaction temperature was 360 ℃. After the reaction was stabilized for 7 days, the mass fractions of sulfur and nitrogen were analyzed using a sulfur-nitrogen analyzer (model number TN/TS3000, available from Saimer Feishell).
Comparative example 1
Pseudo-boehmite (PB 90 powder produced by Changling catalyst factory with specific surface area of 345 m)2Per gram), sesbania powder according to 100 g: after 3g of the mixture was mixed uniformly, 105mL of a 1.5 wt% nitric acid aqueous solution was added and stirred uniformly again, and then the mixture was extruded into a bar. The pure alumina carrier D1 with the grain diameter of 1.6mm is prepared by the steps of drying at 120 ℃ for 3h and roasting at 600 ℃ for 4 h. The specific surface area of the carrier D1 was 283m2The pore volume was 0.72mL/g, and the pore size distribution is shown in Table 1.
Heating the vector D1 at 300 ℃ for 5h to obtain vector D1-1. The specific surface area, the pore volume and the pore size distribution of the carrier D1-1 are all equivalent to those of D1, and the variation range is less than +/-5%.
Example 1
Soaking the carrier D1 in water at 200 deg.C by pore saturation soaking methodDrying for 1h to obtain the carrier Sup 1. The specific surface area of the support Sup1 was 260m2The pore volume was 0.69mL/g, and the pore size distribution was as shown in Table 1.
Heating the vector Sup1 at 300 deg.C for 5h to obtain vector Sup 1-1. The pore size distribution of the support Sup1-1 is shown in Table 1.
Comparative example 2
Pseudo-boehmite (PB 100 powder produced by Changling catalyst factory, specific surface area is 330 m)2Per gram), sesbania powder according to 100 g: after 3.5g of the mixture was mixed uniformly, 120mL of a 1.5 wt% nitric acid aqueous solution was added and stirred uniformly again, followed by extrusion molding. The pure alumina carrier D2 with the grain diameter of 1.6mm is prepared by the steps of drying at 120 ℃ for 3h and roasting at 900 ℃ for 3 h. The specific surface area of the support D2 was 240m2The pore volume was 0.8mL/g, and the pore size distribution is shown in Table 1.
Heating the vector D2 at 400 ℃ for 1h to obtain vector D2-1. The specific surface area, the pore volume and the pore size distribution of the carrier D2-1 are all equivalent to those of D2, and the variation range is less than +/-5%.
Example 2
Soaking the carrier D2 in water by pore saturation impregnation method, and drying at 100 deg.C for 4 hr to obtain carrier Sup 2. The specific surface area of the support Sup2 was 235m2The pore volume was 0.76mL/g, and the pore size distribution was as shown in Table 1.
Heating the vector Sup2 at 400 ℃ for 1h to obtain vector Sup 2-1. The pore size distribution of the support Sup2-1 is shown in Table 1.
Comparative example 3
Pseudo-boehmite (PB 110 powder produced by Changling catalyst plant, with specific surface area of 325 m)2Per gram), sesbania powder according to 100 g: after 2.5g of the mixture was mixed uniformly, 120mL of a 2 wt% nitric acid aqueous solution was added, and the mixture was stirred uniformly again, followed by extrusion molding. The pure alumina carrier D3 with the grain diameter of 1.6mm is prepared by the steps of drying at 180 ℃ for 4h and roasting at 700 ℃ for 4 h. The specific surface area of the carrier D3 was 264m2The pore volume was 0.75mL/g, and the pore size distribution is shown in Table 1.
Heating the vector D3 at 300 ℃ for 3h to obtain vector D3-1. The specific surface area, the pore volume and the pore size distribution of the carrier D3-1 are all equivalent to those of D3, and the variation range is less than +/-5%.
Example 3
Soaking the carrier D3 in water by pore saturation impregnation method, and drying at 100 deg.C for 4 hr to obtain carrier Sup 3. The specific surface area of the support Sup3 was 257m2The pore volume was 0.71mL/g, and the pore size distribution is shown in Table 1.
Heating the carrier Sup3 at 300 deg.C for 3h to obtain carrier Sup 3-1. The pore size distribution of the support Sup3-1 is shown in Table 1.
Comparative example 4
Pseudo-boehmite (PB 86 powder produced by Changling catalyst factory, specific surface area is 375m2Per gram), sesbania powder according to 100 g: after 2.5g of the mixture was mixed uniformly, 95mL of a solution containing nitric acid (concentration: 3% by weight) was added, and the mixture was stirred again uniformly and extruded into a strand. The pure alumina carrier D4 with the grain diameter of 1.6mm is prepared by the steps of drying at 120 ℃ for 6h and roasting at 800 ℃ for 9 h. The specific surface area of the support D4 was 273m2The pore volume was 0.66mL/g, and the pore size distribution is shown in Table 1.
Heating the vector D4 at 250 ℃ for 4h to obtain vector D4-1. The specific surface area, the pore volume and the pore size distribution of the carrier D4-1 are all equivalent to those of D4, and the variation range is less than +/-5%.
Example 4
Soaking the carrier D4 in water by pore saturation impregnation method, and drying at 100 deg.C for 4 hr to obtain carrier Sup 4. The support Sup4 had a specific surface area of 268m2The pore volume was 0.63mL/g, and the pore size distribution was as shown in Table 1.
Heating the vector Sup4 at 250 deg.C for 4h to obtain vector Sup 4-1. The pore size distribution of the support Sup4-1 is shown in Table 1.
Example 5
Soaking the carrier D4 in ethanol by pore saturation soaking method, and drying at 100 deg.C for 4 hr to obtain carrier Sup 5. The specific surface area of the support Sup5 was 265m2The pore volume was 0.60mL/g, and the pore size distribution is shown in Table 1.
Heating the vector Sup5 at 250 deg.C for 4h to obtain vector Sup 5-1. The pore size distribution of the support Sup5-1 is shown in Table 1.
Comparative example 5
The carrier D4 was impregnated with ethanol by pore saturation impregnation, and after impregnation, it was dried at 300 ℃ for 5 hours to give carrier D5. The specific surface area of the support D5 was 271m2The pore volume was 0.65mL/g, and the pore size distribution is shown in Table 1.
The carrier D5 was heated at 250 ℃ for 4h to give the carrier SupD-1. The pore size distribution of this support D5-1 is shown in Table 1.
TABLE 1
Figure BDA0001134863030000141
Examples 1 to 1
The method comprises the steps of preparing an impregnation solution by using ethylenediamine, ammonia water, ammonium heptamolybdate and cobalt nitrate as precursors. The concentration of ammonia water is 20 wt%, the precursor dissolving temperature is 80 ℃, and the dissolving time is 4 h. The carrier Sup1 was impregnated with the impregnation solution by an equal volume impregnation method, followed by drying at 200 ℃ for 5 hours to obtain the catalyst. Based on the dry weight of the catalyst and calculated by oxide, the content of molybdenum in the catalyst is 20.0 percent, the content of cobalt in the catalyst is 4.0 percent, and the molar ratio of ethylene diamine to cobalt atoms is 2: 1. after the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 12.0ppm, and the nitrogen content is 1.5 ppm.
Comparative examples 1 to 1
A hydrodesulfurization catalyst was prepared by following the procedure of example 1-1, except that the support Su 1 was replaced by the support D1 to prepare an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 35ppm, and the nitrogen content of the obtained product is 7.8 ppm.
Example 2-1
Phosphoric acid, molybdenum oxide, basic nickel carbonate and ethylene glycol are used as raw materials to prepare a dipping solution. The precursor dissolving temperature is 80 ℃, and the dissolving time is 4 h. The catalyst is prepared into an oxidation state catalyst by adopting an isovolumetric impregnation method and using an impregnation liquid carrier Sup2, and then drying the catalyst for 6 hours at 100 ℃. Based on the dry weight of the catalyst and calculated by oxide, the molybdenum content in the catalyst is 45%, the nickel content is 4%, the P content is 4%, and the molar ratio of ethylene glycol to nickel is 3: 1. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 7.0ppm, and the nitrogen content is 1.1 ppm.
Comparative example 2-1
A hydrodesulfurization catalyst was prepared by following the procedure of example 2-1 except that the support Su 2 was replaced by the support D2 to prepare an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 33.5ppm, and the nitrogen content of the obtained product is 7.3 ppm.
Example 3-1
Phosphorous acid, molybdenum oxide, basic nickel carbonate and propanol are used as raw materials to prepare the dipping solution. The precursor dissolving temperature is 90 ℃, and the dissolving time is 3 h. The carrier Sup3 was impregnated with the impregnation solution by an equal volume impregnation method, and then dried at 150 ℃ for 3 hours to prepare the oxidized catalyst. Based on the dry weight of the catalyst and calculated by oxide, the molybdenum content in the catalyst is 30%, the nickel content is 5.5%, the P content is 4%, and the molar ratio of propanol to nickel is 0.5: 1. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 8.3ppm, and the nitrogen content is 1.5 ppm.
Comparative example 3-1
A hydrodesulfurization catalyst was prepared by following the procedure of example 3-1 except that the support Su 3 was replaced by the support D3 to prepare an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 37.5ppm, and the nitrogen content is 7.7 ppm.
Example 4-1
Phosphoric acid, ammonium metatungstate, molybdenum oxide, basic nickel carbonate and acetic acid are used as raw materials to prepare a dipping solution. The precursor dissolving temperature is 80 ℃, and the dissolving time is 1 h. The carrier Sup4 was impregnated with the impregnation solution by an equal volume impregnation method, and then dried at 200 ℃ for 5 hours to prepare the oxidized catalyst. Based on the dry weight of the catalyst and calculated by oxide, the tungsten content in the catalyst is 20%, the molybdenum content is 6%, the nickel content is 4.1%, the P content is 5.6%, and the molar ratio of acetic acid to nickel is 1.5: 1. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 11.6ppm, and the nitrogen content of the obtained product is 0.7 ppm.
Comparative example 4-1
A hydrodesulfurization catalyst was prepared by following the procedure of example 4-1 except that the support Su 4 was replaced by the support D4 to prepare an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 35.6ppm, and the nitrogen content is 6.9 ppm.
Example 5-1
A hydrodesulfurization catalyst was prepared by following the procedure of example 4-1, except that the support Su 4 was replaced by the support Su 5 obtained in example 5, to obtain an oxidation state catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 8.0ppm, and the nitrogen content is 1.4 ppm.
Comparative example 5-1
A hydrodesulfurization catalyst was prepared by following the procedure of example 5-1, except that the support Su 5 was replaced by the support D5 to prepare an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 35.6ppm, and the nitrogen content is 6.9 ppm.
Comparative example 6-1
A hydrodesulfurization catalyst was prepared as in example 4-1 except that the impregnation solution contained no propanol and was prepared as an oxidized catalyst. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 31.5ppm, and the nitrogen content is 8.1 ppm.
Comparative example 7-1
A hydrodesulfurization catalyst was prepared as in example 34-1, except that the acetic acid was replaced by the same weight of citric acid to prepare the oxidation state catalyst Cat-D6. After the catalyst is subjected to vulcanization and reaction tests, the sulfur content of the obtained product is 35.7ppm, and the nitrogen content is 7.6 ppm.
It can be seen from the results of the above examples and comparative examples that the preparation method adopted by the present invention can reduce the distribution of small and small size pores and increase the proportion of large size pore channels. These water molecules selectively adsorbed in the pores can be removed by heating. The method can reduce small pore canals on the basis of not introducing impurities, so that active components of the catalyst can be more distributed in the large pore canals. The catalyst has higher activity than the conventional catalyst by using inferior raw oil. Therefore, the method is beneficial to the catalyst to treat macromolecular impurities, meets the requirement of the catalyst for treating poor-quality raw materials, and has good industrial application prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (63)

1. A hydrofining catalyst comprises a modified catalyst carrier and a hydrodesulfurization catalytic active component, and is characterized in that the modified catalyst carrier comprises a porous heat-resistant inorganic oxide and an organic substance selected from water and/or organic substances with a boiling point not higher than 150 ℃, the porous heat-resistant inorganic oxide is selected and the content of each component enables the pore size distribution of small-size pores to be increased and the pore size distribution of larger-size pores to be decreased after the carrier is subjected to high-temperature treatment, the small-size pores refer to 2-8nm, the larger-size pores refer to more than 8nm, and the high-temperature treatment mode is heating at the temperature of more than 200 ℃ to less than or equal to 400 ℃ for 1-10 hours.
2. The hydrofinishing catalyst according to claim 1, wherein the modified catalyst support has a pore size distribution of small size pores which increases by no more than 50% after high temperature treatment; the pore size distribution of the larger size pores is reduced by no more than 60%.
3. The hydrorefining catalyst according to claim 2, wherein the modified catalyst support has been treated at high temperature to increase the pore size distribution of the small-sized pores by not more than 10-35%; the pore size distribution of the larger size pores decreases by an amount of 10-40%.
4. The hydrorefining catalyst as defined in any one of claims 1 to 3, wherein the modified catalyst support has a pore size distribution of small-sized pores of 25 to 65%, a pore size distribution of larger-sized pores of 35 to 75%, a pore volume of 0.6 to 1.2mL/g, a specific surface area of 180-450m2/g。
5. The hydrorefining catalyst as defined in claim 4, wherein the modified catalyst support has a pore size distribution of small-sized pores of 30-60%, a pore size distribution of larger-sized pores of 40-70%, a pore volume of 0.6-0.8mL/g, a specific surface area of 220-270m2/g。
6. The hydrorefining catalyst as defined in any one of claims 1 to 3 and 5, wherein the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 35 to 70%, a pore size distribution of larger-sized pores of 30 to 65%, a pore volume of 0.85 to 1.4mL/g, a specific surface area of 200-500m2/g。
7. The hydrorefining catalyst according to claim 6, wherein the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 40 to 66% and a pore size distribution of larger-sized pores of 34 to 60%.
8. The hydrorefining catalyst as defined in claim 4, wherein the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 35 to 70%, a pore size distribution of larger-sized pores of 30 to 65%, a pore volume of 0.85 to 1.4mL/g, and a specific surface area of 200-500m2/g。
9. The hydrofinishing catalyst according to claim 8, wherein the porous refractory inorganic oxide has a pore size distribution of small size pores of 40-66% and a pore size distribution of larger size pores of 34-60%.
10. The hydrorefining catalyst as claimed in any one of claims 1 to 3, 5, and 7 to 9, wherein the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania, and zirconia, and the boiling point of the organic substance is 50 to 120 ℃.
11. The hydrofinishing catalyst according to claim 10, wherein the organic substance is one or more of methanol, ethanol, propanol, petroleum ether.
12. The hydrorefining catalyst of claim 4, wherein the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania, and zirconia, and the organic substance has a boiling point of 50-120 ℃.
13. The hydrofinishing catalyst according to claim 12, wherein the organic substance is one or more of methanol, ethanol, propanol, petroleum ether.
14. The hydrofinishing catalyst according to claim 6, wherein the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania and zirconia, and the boiling point of the organic matter is 50-120 ℃.
15. The hydrofinishing catalyst according to claim 14, wherein the organic substance is one or more of methanol, ethanol, propanol, petroleum ether.
16. A hydrofinishing catalyst according to any one of claims 1 to 3, 5, 7 to 9 and 11 to 15 wherein the hydrodesulphurisation catalytically active components are group VIII metal elements and group VIB metal elements and the content of group VIII metal elements in the hydrofinishing catalyst is from 2 to 15% based on the dry weight of the catalyst and calculated as oxides; the content of the VIB group metal elements is 15-60%.
17. The hydrofinishing catalyst according to claim 16, wherein the hydrodesulphurisation catalytically active components are nickel and/or cobalt and tungsten and/or molybdenum, and the content of group VIII metal elements in the hydrofinishing catalyst is from 3 to 10% based on the dry weight of the catalyst and calculated as oxides; the content of VIB group metal elements is 20-45%.
18. The hydrofinishing catalyst according to claim 4, wherein the hydrodesulfurization catalytically active components are group VIII metal elements and group VIB metal elements, and the content of group VIII metal elements in the hydrofinishing catalyst is 2-15% by weight on a dry basis of the catalyst and calculated as oxides; the content of the VIB group metal elements is 15-60%.
19. The hydrofinishing catalyst according to claim 18, wherein the hydrodesulphurisation catalytically active components are nickel and/or cobalt and tungsten and/or molybdenum, and the content of group VIII metal elements in the hydrofinishing catalyst is from 3 to 10% based on the dry weight of the catalyst and calculated as oxides; the content of VIB group metal elements is 20-45%.
20. The hydrofinishing catalyst according to claim 6, wherein the hydrodesulfurization catalytically active components are group VIII metal elements and group VIB metal elements, and the content of group VIII metal elements in the hydrofinishing catalyst is 2-15% by weight on a dry basis of the catalyst and calculated as oxides; the content of the VIB group metal elements is 15-60%.
21. The hydrofinishing catalyst according to claim 20, wherein the hydrodesulphurisation catalytically active components are nickel and/or cobalt and tungsten and/or molybdenum, and the content of group VIII metal elements in the hydrofinishing catalyst is from 3 to 10% based on the dry weight of the catalyst and calculated as oxides; the content of VIB group metal elements is 20-45%.
22. The hydrofinishing catalyst according to claim 10, wherein the hydrodesulfurization catalytically active components are group VIII metal elements and group VIB metal elements and the group VIII metal elements are present in the hydrofinishing catalyst in an amount of from 2 to 15% by weight, calculated as oxides and based on the dry weight of the catalyst; the content of the VIB group metal elements is 15-60%.
23. The hydrofinishing catalyst according to claim 22, wherein the hydrodesulphurisation catalytically active components are nickel and/or cobalt and tungsten and/or molybdenum, and the content of group VIII metal elements in the hydrofinishing catalyst is from 3 to 10% based on the dry weight of the catalyst and calculated as oxides; the content of VIB group metal elements is 20-45%.
24. A preparation method of a hydrofining catalyst comprises the following steps:
(1) impregnating porous heat-resistant inorganic oxide with water and/or organic matter with the boiling point not higher than 150 ℃, and then drying to obtain a modified catalyst carrier, wherein the porous heat-resistant inorganic oxide is selected and dried under the condition that the pore size distribution of small-size pores is increased and the pore size distribution of larger-size pores is decreased after the carrier is subjected to high-temperature treatment, the small size refers to 2-8nm, the larger size refers to more than 8nm, and the high-temperature treatment is carried out by heating at the temperature of more than 200 ℃ and less than or equal to 400 ℃ for 1-10 hours;
(2) impregnating the modified catalyst carrier obtained in the step (1) with an impregnating solution, wherein the impregnating solution contains a hydrodesulfurization catalytic active component and one or more organic matters with molecular weight less than 80;
(3) and (3) drying the impregnated carrier in the step (2).
25. The production method according to claim 24, wherein the modified catalyst support has a small sizeThe pore diameter distribution of the pores is 25-65%, the pore diameter distribution of the larger-size pores is 35-75%, the pore volume is 0.6-1.2mL/g, the specific surface area is 180-450m2/g。
26. The preparation method as claimed in claim 25, wherein the modified catalyst support has a pore size distribution of small-sized pores of 30 to 60%, a pore size distribution of larger-sized pores of 40 to 70%, a pore volume of 0.6 to 0.8mL/g, a specific surface area of 220 to 270m2/g。
27. The production method as claimed in any one of claims 24 to 26, wherein the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 35 to 70%, a pore size distribution of larger-sized pores of 30 to 65%, a pore volume of 0.85 to 1.4mL/g, a specific surface area of 200-500m2/g。
28. The production method according to claim 27, wherein the porous heat-resistant inorganic oxide has a pore size distribution of small-sized pores of 40 to 66% and a pore size distribution of larger-sized pores of 34 to 60%.
29. The method according to any one of claims 24 to 26 and 28, wherein the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania and zirconia, and the organic substance has a boiling point of 50 to 100 ℃.
30. The method of claim 29, wherein the organic substance is one or more of methanol, ethanol, propanol, and petroleum ether.
31. The preparation method of claim 27, wherein the porous heat-resistant inorganic oxide is one or more of alumina, silica, titania and zirconia, and the organic matter has a boiling point of 50-100 ℃.
32. The method of claim 31, wherein the organic substance is one or more of methanol, ethanol, propanol, and petroleum ether.
33. The method according to any one of claims 24 to 26, 28 and 30 to 32, wherein the organic substance having a molecular weight of less than 80 has a molecular weight of 75 or less and contains-OH, -NH2and-COOH.
34. The method of claim 33, wherein the organic substance having a molecular weight of less than 80 is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, ethanolamine, ethylamine, propylamine, butylamine, glycine.
35. The method according to claim 27, wherein the organic substance having a molecular weight of less than 80 has a molecular weight of 75 or less and contains-OH, -NH2and-COOH.
36. The method of claim 35, wherein the organic substance having a molecular weight of less than 80 is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, ethanolamine, ethylamine, propylamine, butylamine, glycine.
37. The method according to claim 29, wherein the organic substance having a molecular weight of less than 80 has a molecular weight of 75 or less and contains-OH, -NH2and-COOH.
38. The method of claim 37, wherein the organic substance having a molecular weight of less than 80 is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, ethanolamine, ethylamine, propylamine, butylamine, glycine.
39. The production process according to any one of claims 24 to 26, 28, 30 to 32 and 34 to 38, wherein the hydrodesulfurization catalytically active components are elements of group VIII metals and elements of group VIB metals; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.2-5.
40. The method of claim 39, wherein the hydrodesulfurization catalytically active component is nickel and/or cobalt and tungsten and/or molybdenum; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.5-3.
41. The preparation process according to claim 27, wherein the hydrodesulphurization catalytically active components are elements of group VIII metals and elements of group VIB metals; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.2-5.
42. The method of claim 41, wherein the hydrodesulfurization catalytically active component is nickel and/or cobalt and tungsten and/or molybdenum; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.5-3.
43. The preparation process according to claim 29, wherein the hydrodesulphurization catalytically active components are elements of group VIII metals and elements of group VIB metals; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.2-5.
44. The method of claim 43, wherein the hydrodesulfurization catalytically active component is nickel and/or cobalt and tungsten and/or molybdenum; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.5-3.
45. The preparation method according to claim 33, wherein the hydrodesulfurization catalytically active components are group VIII metal elements and group VIB metal elements; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.2-5.
46. The method of claim 45, wherein the hydrodesulfurization catalytically active component is nickel and/or cobalt and tungsten and/or molybdenum; the molar ratio of the organic matter with the molecular weight less than 80 to the VIII group metal element is 0.5-3.
47. The process according to claim 39, wherein the hydrodesulfurization catalytically active component is used in an amount such that the catalyst obtained contains the group VIII metal element in an amount of 2 to 15% by weight, calculated as oxide, based on the dry weight of the catalyst; the content of the VIB group metal elements is 15-60%.
48. The process according to claim 47, wherein the hydrodesulfurization catalytically active component is used in an amount such that the catalyst obtained contains the group VIII metal element in an amount of 3 to 10% by weight, calculated as oxide, based on the dry weight of the catalyst; the content of VIB group metal elements is 20-45%.
49. The process according to any one of claims 40 to 46, wherein the hydrodesulphurization catalytically active component is used in an amount such that the resulting catalyst has a content of group VIII metal elements in the range of from 2 to 15% by weight, calculated as oxide and based on the dry weight of the catalyst; the content of the VIB group metal elements is 15-60%.
50. The process according to claim 49, wherein the hydrodesulfurization catalytically active component is used in an amount such that the catalyst obtained contains the group VIII metal element in an amount of 3 to 10% by weight, calculated as oxide, based on the dry weight of the catalyst; the content of VIB group metal elements is 20-45%.
51. The production method according to any one of claims 24 to 26, 28, 30 to 32, 34 to 38, 40 to 48, and 50, wherein the drying temperature in the step (3) is 50 to 350 ℃, and the drying time is 1 to 15 hours.
52. The method as claimed in claim 51, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
53. The method according to claim 27, wherein the drying temperature in the step (3) is 50 to 350 ℃ and the drying time is 1 to 15 hours.
54. The method as claimed in claim 53, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
55. The method according to claim 29, wherein the drying temperature in the step (3) is 50 to 350 ℃ and the drying time is 1 to 15 hours.
56. The method as claimed in claim 55, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
57. The method according to claim 33, wherein the drying temperature in the step (3) is 50 to 350 ℃ and the drying time is 1 to 15 hours.
58. The method as claimed in claim 57, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
59. The method according to claim 39, wherein the drying temperature in the step (3) is 50 to 350 ℃ and the drying time is 1 to 15 hours.
60. The method as claimed in claim 59, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
61. The method according to claim 49, wherein the drying temperature in the step (3) is 50 to 350 ℃ and the drying time is 1 to 15 hours.
62. The method as claimed in claim 61, wherein the drying temperature in step (3) is 100-200 ℃ and the drying time is 3-6 hours.
63. A hydrorefining catalyst produced by the production process according to any one of claims 24 to 62.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63216831A (en) * 1987-03-05 1988-09-09 Shindaikiyouwa Sekiyu Kagaku Kk Production of cycloolefin
CN102463150A (en) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 Preparation method of hydroprocessing catalyst
CN102909027A (en) * 2012-09-19 2013-02-06 中国海洋石油总公司 Preparation method of catalyst by ultralow-sulfur hydrofining

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63216831A (en) * 1987-03-05 1988-09-09 Shindaikiyouwa Sekiyu Kagaku Kk Production of cycloolefin
CN102463150A (en) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 Preparation method of hydroprocessing catalyst
CN102909027A (en) * 2012-09-19 2013-02-06 中国海洋石油总公司 Preparation method of catalyst by ultralow-sulfur hydrofining

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