CN108421548B - Hydrogenation protection catalyst, preparation method thereof and heavy oil hydrotreating method - Google Patents

Hydrogenation protection catalyst, preparation method thereof and heavy oil hydrotreating method Download PDF

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CN108421548B
CN108421548B CN201710080674.0A CN201710080674A CN108421548B CN 108421548 B CN108421548 B CN 108421548B CN 201710080674 A CN201710080674 A CN 201710080674A CN 108421548 B CN108421548 B CN 108421548B
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silica
hydrogenation
alumina
active component
amount
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CN108421548A (en
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李明丰
张乐
贾燕子
曾双亲
杨清河
刘学芬
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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
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/205—Metal content
    • 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

Abstract

The invention relates to a hydrogenation protection catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst; (2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting; the hydrogenation metal active component comprises at least one group VB metal component and at least one group VIII metal component. When the catalyst provided by the invention is used for heavy oil hydrotreating, higher demetallization rate and desulfurization rate can be obtained.

Description

Hydrogenation protection catalyst, preparation method thereof and heavy oil hydrotreating method
Technical Field
The invention relates to a preparation method of a hydrogenation protection catalyst, the hydrogenation protection catalyst prepared by the method and a heavy oil hydrotreating method using the hydrogenation protection catalyst.
Background
Along with the aggravation of the trend of heavy and inferior crude oil, the processing difficulty of crude oil is increased, the yield of light oil products is reduced, the demand of the market on high-quality light oil products is continuously increased, and environmental protection regulations are more and more strict. At present, the processing and full utilization of heavy oil, especially residual oil, is becoming a main topic of global oil refining industry attention, and the residual oil hydrogenation technology is a processing technology which is widely applied in the heavy oil processing technology, and is a well-known economic and environment-friendly deep processing technology. The residual oil contains a large amount of metal impurities such as Ni, V, Fe, Ca and the like and solid impurities, and if the impurities cannot be effectively removed, the impurities can have adverse effects on a downstream hydrogenation catalyst and can easily deactivate the downstream catalyst. One of the effective ways to solve this problem is to load a protecting agent with hydrogenation activity on the top of the hydrogenation catalyst, so the development of a protecting agent with high demetallization activity and strong metal-containing ability is one of the key technologies for heavy oil hydroprocessing.
Hydrogenation catalysts are typically prepared by impregnation, i.e., by impregnating a support with a solution containing the desired active component (e.g., Ni, Mo, Co, W, etc.), followed by drying, calcination, or no calcination. For example, prior art catalysts for heavy oil processing include:
CN1054393C discloses a preparation method of a residual oil hydrodemetallization catalyst, which is characterized in that the pore structure of a residual oil hydrodemetallization agent is improved by adopting two means, namely a physical method and a chemical method.
CN1267537C discloses a preparation method of a residual oil hydrodemetallization catalyst, which is characterized in that a carrier contains halogen, the halogen accounts for 0.1-5 wt% of the carrier, the acidity of the carrier is less than 0.2 mmol/g (the carrier acid content is low), and the carbon deposit amount of the catalyst is low while the catalyst maintains high hydrodemetallization activity.
CN103551162A discloses a diesel oil hydrodesulfurization and denitrification catalyst, which comprises a carrier, an auxiliary agent and active metal; the carrier being Al2O3-ZrO2-TiO2-SiO2A multi-oxide composite support; the auxiliary agent is phosphorus; nickel, cobalt, molybdenum and tungsten are taken as active components; the catalyst comprises the following components in percentage by weight based on the weight of the catalyst: 1-6 wt% of cobalt oxide in terms of oxide; 1-15 wt% of nickel oxide, 2-12 wt% of molybdenum oxide, 12-35 wt% of tungsten oxide and 1.5-5 wt% of auxiliary agent phosphorus pentoxide(ii) a The pore volume of the catalyst is not less than 0.2mL/g, and the specific surface area is not less than 140m2(ii)/g, mechanical strength is not less than 15N/mm; the proportion of each component in the composite carrier in the carrier is respectively as follows: 2-15 wt% of titanium oxide, 2-20 wt% of silicon oxide and 5-15 wt% of zirconium oxide; the balance being alumina. The catalyst is prepared by a step impregnation method: the co-immersion liquid was divided into two equal volumes, the carrier was impregnated in two steps, and calcination was performed after completion of each step of impregnation.
CN103657667A discloses a preparation method of a novel heavy oil hydrodemetallization catalyst with a macroporous structure, which is characterized by comprising the following steps: the method specifically comprises the following steps: 1) preparing aluminum sol; 2) mixing asphalt residue powder and alumina sol to prepare a macroporous structure catalyst carrier; 3) impregnating the molded catalyst carrier by adopting an isometric fractional two-step impregnation method; finally, the catalyst is prepared. The two-step impregnation method of the preparation method comprises the following specific steps: the first step is to impregnate Mo, the second step is to impregnate Ni, and the impregnating solution does not contain organic complexing agent.
The two-step impregnation method provided by the prior art allows the activity of the hydrogenation protection catalyst to be improved, but the degree of improvement is limited.
CN100469440C, CN102909027A disclose that Ni-W-Mo ternary metal hydrogenation protection catalysts are prepared by introducing organic dispersing agents or complexing agents (such as ethylene glycol, oxalic acid, citric acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, etc.) into the carrier during the preparation process. Compared with the catalyst provided by the existing method, the obtained catalyst has better hydrofining performance.
Other prior arts show that the performance of the catalyst can be modulated and improved by selecting the hydrogenation active metal component and changing the preparation method. The preparation method provided by the prior art can improve the activity of the hydrogenation catalyst to some extent, but the improvement degree is limited. Compared with the traditional impregnation method, the complex impregnation technology can further improve the activity of the catalyst, but still has the defects of lower catalyst activity and shorter catalyst life.
Disclosure of Invention
Aiming at the defects of lower activity of the hydrogenation protection catalyst or short service life of the catalyst in the prior art, the invention provides a novel catalyst preparation method capable of further improving the performance of the catalyst, a heavy oil hydrogenation protection catalyst prepared by the method and a heavy oil hydrogenation treatment method.
The inventor of the invention finds that the complexing impregnation technology can weaken the interaction between the active component and the carrier, improve the metal dispersion degree, change the metal vulcanization sequence, form more active phases and improve the number of active centers by introducing the complexing agent in the impregnation process and drying at low temperature. However, because low-temperature drying is adopted in the complex impregnation technology, and a high-temperature roasting process is not carried out, the metal compound still exists on the surface of the carrier in the form of metal salt, and the acting force of the active component and the carrier is weaker, so that metal is continuously aggregated in the reaction process under the conditions of high temperature and high pressure and hydrogenation reaction of a severe raw material, the auxiliary effect is weakened, the number of active centers is reduced, the intrinsic activity is reduced, and the activity and the stability of the catalyst are reduced. The catalyst prepared by the high-temperature roasting method has good stability, but the acting force of the active component and the carrier is strong, the intrinsic activity of the active center is low, and the dispersion and the blocking action of the complexing agent are avoided, so that the active component has large lamella, the number of the active centers is small, and the activity is low.
The inventor of the invention further discovers through research that the catalyst is prepared through a two-step impregnation method, the first step impregnation and the second step impregnation are respectively used for introducing a hydrogenation metal active component and an organic complexing agent, the organic complexing agent is added in the first step impregnation process and is converted into carbon through roasting, the activity of the catalyst can be improved, the high activity of the catalyst can be effectively maintained for a long time, and the service life of the catalyst is greatly prolonged. Presumably, the reason for this is that the organic complexing agent added in the first impregnation step hinders the aggregation of the active metal during the calcination process and makes it more uniformly dispersed; meanwhile, the metal compound can be converted into metal oxide by roasting after the first step of impregnation, and the organic complexing agent is converted into carbon, so that the combination between the active metal and the carrier is firmer, and the activity and the stability of the catalyst are improved. The organic complexing agent added in the second step of dipping process covers the surface of the catalyst, so that the aggregation of active metal in the vulcanization process can be effectively prevented, the metal dispersity is improved, and the formation of a II-type active phase with higher activity and the formation of more active centers are facilitated, so that the activity of the catalyst is further enhanced. Therefore, the technology can effectively overcome the technical defects of the conventional impregnation method and the existing complex impregnation method.
Therefore, the invention also provides a preparation method of the hydrogenation protection catalyst, which comprises the following steps:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the hydrogenation metal active components are at least one group VB metal component and at least one group VIII metal component.
In addition, the method of the invention also provides a hydrogenation protection catalyst prepared by the method.
In addition, the invention also provides a heavy oil hydrotreating method, which comprises the step of contacting heavy oil raw oil with the hydrogenation protection catalyst under the heavy oil hydrotreating reaction condition.
The hydrogenation protection catalyst prepared by the method has high catalytic activity and activity stability. For example, when the catalyst S1 prepared by the method provided by the invention is used for hydrotreating the Iran heavy atmospheric residue, the nickel removal rate is 62%, the vanadium removal rate is 73%, the iron removal rate is 96%, the calcium removal rate is 57%, and the sulfur removal rate is 49%; under the same other conditions, the reference agent D2 obtained by the conventional impregnation method has the nickel removal rate of 55%, the vanadium removal rate of 70%, the iron removal rate of 92%, the calcium removal rate of 54% and the desulfurization rate of 43%. Therefore, the method can obviously improve the hydrogenation activity of the catalyst. And the method is simple to operate, so that the method has a good industrial application prospect.
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.
According to the preparation method of the hydrogenation protection catalyst provided by the invention, the preparation method comprises the following steps:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the hydrogenation metal active components are at least one group VB metal component and at least one group VIII metal component.
According to the present invention, it is preferable that the calcination conditions in the step (1) are such that the content of char in the semi-finished catalyst is 0.04 to 0.4% by weight based on the total amount of the semi-finished catalyst.
In the present invention, the above-mentioned carbon content can be obtained by controlling the calcination temperature in the calcination conditions and the amount of introduction of a combustible gas, which may be one or more of various gases having an oxygen content of not less than 20% by volume, such as air, oxygen, and a mixed gas thereof.
The rate of introduction of the combustible gas is preferably not less than 0.2 liter/hour per gram of the carrier. On one hand, the combustible gas is introduced to meet the combustion condition, so that the salt of the active metal component is converted into oxide, and the organic complexing agent is converted into carbon; on the other hand, carbon dioxide and water formed by combustion and other components can be discharged to avoid the deposition on the catalyst to cause vacancy obstruction of the active phase.
Preferably, the combustible gas is introduced at a rate of 0.2 to 20 liters/hour, preferably 0.3 to 10 liters/hour, per gram of the support.
According to the present invention, preferably, the temperature of the calcination in step (1) is 350-. Controlling the roasting temperature within the range can ensure that the organic complexing agent can form carbon on the carrier within the content range to obtain the semi-finished catalyst.
According to the present invention, preferably, the molar ratio of the organic complexing agent to the metal active component in step (1) is 0.03-2: 1, preferably 0.08 to 1.5:1, more preferably 0.1 to 1.4: 1, more preferably 0.5 to 1.3: 1.
according to the present invention, preferably, the molar ratio of the organic complexing agent in the step (1) to the organic complexing agent in the step (2) is 1: 0.25 to 4, preferably 1: 0.5-2.
In the present invention, the organic complexing agents in step (1) and step (2) may be the same or different, and preferably, the organic complexing agents are selected from one or more of oxygen-containing and/or nitrogen-containing organic substances.
The oxygen-containing organic matter is preferably selected from one or more of organic alcohol and organic acid.
The organic alcohol is preferably a dihydric or higher polyhydric alcohol, more preferably a polyhydric alcohol having 2 to 6 carbon atoms or an oligomer or polymer thereof, such as one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, and butanediol. The molecular weight of the polyethylene glycol is preferably 200-1500.
The organic acid is preferably a compound containing one or more COOH groups and C2-C7, and specifically can be one or more of acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid.
The nitrogen-containing organic matter is preferably selected from one or more of organic amine and organic ammonium salt.
The organic amine is preferably a compound containing one or more NH groups and having a carbon number of from 2 to 7, and can be a primary amine, a secondary amine or a tertiary amine, and particularly preferably ethylenediamine.
The organic ammonium salt is preferably EDTA.
In particular, the organic complexing agent is particularly preferably one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is preferably 200-.
Preferably, the organic complexing agent in step (1) is selected from one or more of organic acids, more preferably, the organic complexing agent in step (1) is selected from one or more of fatty acids of C2-C7. By using an organic acid as the organic complexing agent in step (1), a more active hydrogenation protection catalyst can be obtained.
In the present invention, the drying conditions are not particularly limited, and may be various drying conditions commonly used in the art, and the drying conditions in the step (1) and the step (2) may be the same or different.
Preferably, the drying temperature in the step (1) is 100-250 ℃, and the time is 1-12 h.
Preferably, the drying temperature in the step (2) is 100-200 ℃, and the time is 1-12 h.
According to the present invention, the hydrogenation metal active component is preferably used in an amount such that the content of the hydrogenation metal active component is 15 to 60 wt%, preferably 20 to 50 wt%, and more preferably 20 to 40 wt%, in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
According to the present invention, it is preferable that the concentration of the water-soluble salt of the hydrogenation metal active component is 0.2 to 8mol/L, preferably 0.2 to 5mol/L, and more preferably 0.2 to 2mol/L, in terms of the metal element. The concentrations herein are the respective concentrations of the water-soluble salts of the various hydrogenation metal active components, not the total concentration.
The water-soluble salt of the hydrogenation metal active component can be various water-soluble compounds with the solubility meeting the loading requirement or capable of forming the hydrogenation metal active component with the solubility meeting the requirement in water in the presence of a cosolvent, and can be one or more of nitrate, chloride, sulfate and carbonate, and is preferably nitrate.
According to the present invention, preferably, the hydrogenation metal active component comprises at least one selected from group VB metal elements and at least one selected from group VIII metal elements.
In the catalyst obtained by the preparation method of the present invention, the contents of the group VB metal element and the group VIII metal element may be appropriately selected according to the specific application of the catalyst. Generally, the group VIII metal component is preferably at least one of iron, cobalt or nickel, more preferably cobalt and/or nickel, and the group VB metal component is preferably vanadium and/or niobium, more preferably vanadium. The content of the group VIII metal component is preferably 0.2 to 15% by weight, more preferably 0.5 to 8% by weight, still more preferably 0.5 to 3% by weight, in terms of oxide and based on the catalyst; the content of the group VB metal component is preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight, still more preferably 1 to 8% by weight.
According to the present invention, the aqueous solution may be prepared by dissolving at least one group VB metal element-containing compound and at least one group VIII metal element-containing compound, which are commonly used in the art, in water.
For example, the group VB metal element-containing compound may be a group VB metal element-containing water-soluble compound commonly used in the art, and the group VIII metal element-containing compound may be a group VIII metal element-containing water-soluble compound commonly used in the art.
Specifically, the compound containing a group VB metal element, taking group VB vanadium as an example, may be one or more selected from vanadium pentoxide, ammonium vanadate, ammonium metavanadate, vanadium sulfate, and vanadium heteropoly acid, and preferably ammonium metavanadate and ammonium vanadate thereof.
The group VIII metal element-containing compound may be one or more selected from the group consisting of group VIII metal nitrates, group VIII metal chlorides, group VIII metal sulfates, group VIII metal formates, group VIII metal acetates, group VIII metal phosphates, group VIII metal citrates, group VIII metal oxalates, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal phosphides, group VIII metal sulfides, group VIII metal aluminates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.
Preferably, the group VIII metal element-containing compound is selected from one or more of group VIII metal oxalates, group VIII metal nitrates, group VIII metal sulfates, group VIII metal acetates, group VIII metal chlorides, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.
The group VIII metal element-containing compound may be selected from, but is not limited to, one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt hydroxycarbonate, cobalt chloride, and nickel chloride.
According to the preparation method of the present invention, the aqueous solution of step (1) may further contain various cosolvents commonly used in the art to improve the solubility of the group VB metal element-containing compound and the group VIII metal element-containing compound in water; or stabilizing the aqueous solution against precipitation. The co-solvent may be any of various materials commonly used in the art to achieve the above-described functions, and is not particularly limited. For example, the cosolvent may be one or more of phosphoric acid, citric acid and ammonia water. The concentration of the aqueous ammonia in the present invention is not particularly limited, and may be selected conventionally in the art. The amount of co-solvent may be selected as is conventional in the art, and typically the co-solvent may be present in the aqueous solution in an amount of from 1 to 10% by weight.
According to the preparation method of the present invention, the shaped porous support may be various shaped porous supports commonly used in the art, and is not particularly limited. Preferably, the shaped porous support is a shaped inorganic refractory oxide. In the present invention, the term "inorganic refractory oxide" means an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ in oxygen or an oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃). In the present invention, the shaped porous support may be formed of one kind of inorganic refractory oxide, or may be formed of two or more kinds of inorganic refractory oxides.
The inorganic heat-resistant oxide may be selected from, for example, one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
According to a preferred embodiment of the present invention, the inorganic refractory oxide is alumina.
According to a preferred embodiment of the present invention, the carrier has a radial crush strength of 20 to 40N/mm, a water absorption of 0.7 to 1.0 ml/g, a pore volume of 0.6 to 0.9ml/g, and a specific surface area of 200 to 350m2/g。
In the present invention, the method for measuring the water absorption of the catalyst carrier is: the support (in weight g) was immersed in water (in volume ml) for 2 hours, the ratio of support (by weight) to water (by volume) being 1: and 3, separating the carrier after water absorption from water, and calculating the water absorption volume of the carrier, wherein the water absorption rate of the carrier is the water absorption volume of the carrier/weight of the carrier.
In the present invention, the pore diameter, pore volume and specific surface area of the carrier are measured by a low-temperature nitrogen adsorption method (see the eds of analytical methods of petrochemical industry (RIPP test method), Yangcui et al, ed. science publishers, 1990).
The radial crushing strength of the carrier is determined according to the standard method of GB 3635-1983.
According to the preparation method of the present invention, the shaped porous support may be prepared using a method commonly used in the art. For example: the heat-resistant inorganic oxide may be obtained by molding at least one inorganic heat-resistant oxide and/or at least one precursor capable of forming an inorganic heat-resistant oxide under firing conditions, and firing the molded article. The method of shaping may be a routine choice in the art, for example: at least one inorganic refractory oxide and/or at least one precursor capable of forming an inorganic refractory oxide under calcination conditions may be extruded in an extruder.
In the present invention, the precursor capable of forming the inorganic refractory oxide under the firing conditions may be appropriately selected depending on the kind of the desired inorganic refractory oxide, and the precursor is preferably capable of forming the inorganic refractory oxide by firing.
For example, when the inorganic refractory oxide is alumina, the precursor capable of forming the inorganic refractory oxide under the calcination conditions may be various substances capable of forming alumina under the calcination conditions, which are commonly used in the art, such as: hydrated alumina (such as pseudo-boehmite).
In a preferred embodiment of the present invention, a precursor capable of forming alumina under calcination conditions is extrusion-molded, and then the extruded molded body is dried and calcined to obtain the molded porous support.
According to the present invention, when the molding is carried out by extrusion, an extrusion aid and/or a binder may be added to the inorganic refractory oxide and/or the precursor capable of forming the inorganic refractory oxide under the firing condition. The kind and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art and will not be described herein.
The conditions under which the extruded shaped bodies are subjected to firing according to the invention may be a matter of routine choice in the art. For example, the temperature of the roasting may be 350-650 ℃, preferably 400-600 ℃; the calcination time may be 2 to 6 hours, preferably 3 to 5 hours.
According to the invention, the porous support may have various shapes depending on the specific application, for example: spherical, tablet or strip.
According to the present invention, the supporting manner of the hydrogenation metal active component is not particularly limited.
According to the present invention, preferably, the loading of the hydrogenation metal active component is to load the hydrogenation metal active component on the carrier by an impregnation method.
According to the present invention, the order of loading the hydrogenation metal active components on the carrier is not particularly limited, and all the hydrogenation metal active components may be loaded on the carrier in common by impregnating the carrier with a solution containing a plurality of water-soluble salts, or the hydrogenation metal active components may be sequentially loaded on the carrier by preparing the water-soluble salt-containing solutions to impregnate the carrier stepwise, respectively. When stepwise impregnation is used, it is preferred to dry and preferably to calcine further after each impregnation. The manner and conditions of drying and firing may be selected with reference to the prior art.
According to the present invention, the supporting method of the organic complexing agent is not particularly limited. The organic complexing agent can be prepared into an impregnation liquid impregnation carrier together with one or more of water-soluble salts of the hydrogenation metal active component, or can be prepared into the impregnation liquid impregnation carrier separately, preferably the former.
According to the present invention, the impregnation method may be an equal volume impregnation or a supersaturation impregnation, the temperature of the impregnation is not particularly limited, and may be various temperatures that can be attained by the impregnation solution, and the time of the impregnation is not particularly limited as long as the required amount of the desired components can be supported, for example: the impregnation temperature may be 15-60 deg.C and the impregnation time may be 0.5-5 hours.
The invention also provides a heavy oil hydrogenation protection catalyst prepared by the preparation method.
Compared with the catalyst prepared by the conventional method, the catalyst prepared by the method provided by the invention has higher heavy oil hydrogenation activity.
Therefore, the invention provides an application of the hydrogenation protection catalyst in heavy oil hydrodemetallization.
In addition, the invention also provides a heavy oil hydrotreating method, which comprises the step of contacting heavy oil raw oil with the hydrogenation protection catalyst under the heavy oil hydrotreating reaction condition.
When the catalyst provided by the present invention is used for heavy oil hydrodemetallation, the reaction conditions for heavy oil hydroprocessing are not particularly limited, and in a preferred embodiment, the hydroprocessing reaction conditions are as follows: the reaction temperature is 300-550 ℃, the further optimization is 330-480 ℃, the hydrogen partial pressure is 4-20MPa, the further optimization is 6-18 MPa, and the volume space velocity is 0.1-3.0 hours-1More preferably 0.15 to 2 hours-1The hydrogen-oil volume ratio is 200-. Under such conditions, heavy oil is contacted with the catalyst provided by the present invention.
The hydrogenation apparatus may be any reactor sufficient to contact and react the feedstock oil with the catalyst under hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or ebullating bed reactor.
The hydroprocessing catalyst may be presulfided prior to use with one or more of sulfur, hydrogen sulfide, carbon disulfide, DMDS, polysulfides or sulfur-containing feedstock, either ex situ or in situ, in the presence of hydrogen, typically at a temperature of 140 ℃ and 370 ℃, to convert the active metal component carried thereby to a metal sulfide component, according to methods conventional in the art.
The catalyst provided by the invention can be used independently or combined with other catalysts, and is particularly suitable for hydrotreating heavy oil, particularly inferior residual oil, so as to provide qualified raw oil for subsequent processes (such as a catalytic cracking process).
Preferably, the density of the heavy oil raw oil is 0.9-1.2g/cm3The S content is 2-5 wt%, the N content is 0.1-1.0 wt%, the Ni content is 20-100 wt ppm, the V content is 100-200 wt ppm, the Fe content is 5-15 wt ppm, and the Ca content is 20-50 wt ppm.
Compared with the hydrogenation protective agent provided by the prior art, the hydrogenation protective agent provided by the invention has the functions of a conventional protective agent and has better hydrogenation demetalization activity.
In the present invention, the dry weight means the weight measured by baking a sample at 600 ℃ for 4 hours.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples, the contents of the respective elements in the catalyst were analyzed and measured by a 3271E type X-ray fluorescence spectrometer, manufactured by japan food and electronics industries co. The carbon content in the catalyst semi-finished product was analyzed and measured using an EMIA-320V carbon sulfur analyzer manufactured by HORIBA, Japan.
Preparation example 1
2000 g of aluminum hydroxide powder (dry rubber powder produced by catalyst factory of Changling division, 72 wt% of dry base) is weighed, extruded into butterfly-shaped strips with the circumscribed circle diameter of 1.3 mm by a strip extruder, the wet strips are dried for 4 hours at 120 ℃, and are roasted for 3 hours at 600 ℃ to obtain the carrier Z1. The Z1 carrier had a radial crush strength of 29.5N/mm, a water absorption of 0.85 ml/g, a pore volume of 0.67ml/g, and a specific surface area of 275m2/g。
Preparation example 2
Weighing 2000 g of aluminum hydroxide powder (70 wt% dry basis of dry rubber powder produced by catalyst factory of Changling division), extruding into butterfly-shaped strips with circumscribed circle diameter of 1.3 mm by a strip extruder, drying wet strips at 120 deg.C for 3 hr, and calcining at 600 deg.C for 3 hrTo obtain the carrier Z2. The Z2 carrier had a radial crush strength of 28.1N/mm, a water absorption of 0.75ml/g, a pore volume of 0.62ml/g, and a specific surface area of 280m2/g。
Preparation example 3
2000 g of aluminum hydroxide powder (dry rubber powder produced by catalyst factory of Changling division, 71 wt% on dry basis) was weighed, extruded into butterfly-shaped strips with a circumscribed circle diameter of 1.3 mm by a strip extruder, the wet strips were dried at 120 ℃ for 3 hours, and calcined at 600 ℃ for 3 hours to obtain a carrier Z3. The Z3 carrier had a radial crush strength of 24.5N/mm, a water absorption of 0.95 ml/g, a pore volume of 0.75ml/g, and a specific surface area of 330m2/g。
Example 1
Respectively weighing 13.8 g of ammonium metavanadate, 7.2 g of cobalt nitrate and 3 g of citric acid, putting the ammonium metavanadate, 7.2 g of cobalt nitrate and 3 g of citric acid into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of carrier Z1 by adopting a saturated impregnation method for 2 hours, then drying at 120 ℃ for 2 hours, roasting the carrier at 400 ℃ for 2 hours in an air flow-in state, wherein the air flow-in rate is 2 liters/hour relative to each gram of carrier to obtain a semi-finished catalyst Z1-S1, and the carbon content of Z1-S1 is shown in Table 1; adding 2g of ethanol into 150 g of deionized water, stirring to obtain a clear solution, soaking the Z1-S1 in the solution for 2 hours by adopting a saturated soaking method, and then drying the solution for 3 hours at 110 ℃ to obtain the catalyst S1. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S1 is shown in Table 1.
Comparative example 1
A hydrogenation protection catalyst was prepared in the same manner as in example 1, except that the hydrogenation protection catalyst S1 obtained in example 1 was calcined at 400 ℃ for 3 hours to obtain catalyst D1, and the content of the hydrogenation metal active component in the catalyst D1, in terms of oxide based on the total amount of D1, is shown in Table 1.
Comparative example 2
Respectively weighing 13.8 g of ammonium metavanadate, 7.2 g of cobalt nitrate and 10 g of citric acid, putting the ammonium metavanadate, the cobalt nitrate and the citric acid into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of carrier Z1 with the solution by adopting a saturated impregnation method for 2 hours, then drying the carrier Z1 for 2 hours at 120 ℃, and roasting the carrier Z for 3 hours at 400 ℃ to obtain the catalyst D2. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D2, is shown in table 1.
Example 2
Respectively weighing 13.8 g of ammonium metavanadate, 8.4 g of nickel nitrate and 4 g of citric acid, putting the ammonium metavanadate, the nickel nitrate and the citric acid into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of carrier Z2 by adopting a saturated impregnation method for 2 hours, then drying the carrier Z2 at 150 ℃ for 2 hours, roasting the carrier Z at 360 ℃ for 3 hours in an air flow-in state, wherein the air flow-in rate is 10 liters/hour relative to each gram of carrier to obtain a semi-finished catalyst Z2-S2, and the carbon content of Z2-S2 is shown in Table 1; adding 8 g of citric acid into 150 g of deionized water, stirring to obtain a clear solution, soaking Z2-S2 in the solution for 2 hours by adopting a saturated soaking method, and then drying at 150 ℃ for 3 hours to obtain the hydrogenation protection catalyst S2. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S2 is shown in Table 1.
Example 3
Respectively weighing 22.4 g of ammonium metavanadate, 4.2 g of nickel nitrate and 3 g of oxalic acid, putting the ammonium metavanadate, the nickel nitrate and the oxalic acid into 140 g of deionized water, stirring and dissolving to obtain a clear solution, soaking 200 g of the carrier Z3 in a saturated soaking method for 2 hours, then drying the carrier at 120 ℃ for 2 hours, and then roasting the carrier in a state of introducing air flow, wherein the roasting temperature is 450 ℃, the time is 4 hours, and the introduction rate of air is 0.3 liter/hour relative to each gram of the carrier, so that a semi-finished catalyst Z3-S3 is obtained, wherein the carbon content of Z3-S3 is shown in Table 1; putting 4 g of diethylene glycol into 150 g of deionized water, stirring to obtain a clear solution, soaking Z3-S3 in the solution for 2 hours by adopting a saturated soaking method, and then drying at 120 ℃ for 6 hours to obtain a catalyst S3. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S3 is shown in Table 1.
Comparative example 3
A hydrocatalytic catalyst was prepared according to the procedure of example 3 except that 22.4 grams of ammonium metavanadate was replaced by 22 grams of ammonium molybdate to provide catalyst D3. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D3, is shown in table 1.
Example 4
A hydrogenation protection catalyst was prepared in the same manner as in example 3, except that the metal active component was impregnated into the carrier and then calcined at 480 ℃ for 6 hours. The content of carbon in the obtained catalyst semi-finished product is shown in table 1, and the content of the hydrogenation metal active component in the obtained catalyst S4 is shown in table 1 in terms of oxide based on the total amount of S4.
Example 5
A hydrogenation protection catalyst was prepared in the same manner as in example 3, except that the air feed rate was 1.0 liter/hr per gram of the carrier upon calcination, and the content of the hydrogenation metal active component in the catalyst S5 based on the total amount of S5 in terms of oxide was as shown in Table 1.
Example 6
A hydrogenation protection catalyst was prepared in the same manner as in example 3, except that the amount ratio of the organic complexing agent in step (1) to the organic complexing agent in step (2) was changed from 3 g: the weight of 4 g is changed into 1.5 g: 5.5 g, the content of the hydrogenation metal active component in the catalyst S6 obtained is shown in Table 1 in terms of oxide based on the total amount of S6.
TABLE 1
Figure BDA0001225785720000161
Figure BDA0001225785720000171
Test example 1
In this test example, the catalytic activity and selectivity of the hydrogenation protection catalyst prepared by the method of the present invention and the hydrogenation protection catalyst provided by the comparative example were evaluated in accordance with the following methods, and the evaluation results are shown in table 3 below.
The protecting agent was evaluated on a 100 ml small fixed bed reactor using Iran heavy atmospheric residue as the feedstock (the properties of the feedstock are shown in Table 2).
The catalyst S1, S2, S3, S4, S5, S6, D1, D2 or D3 is crushed into particles with the diameter of 2-3 mm, and the loading of the catalyst is 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.7 h-1The hydrogen-oil volume ratio was 1000, and a sample was taken after 200 hours of reaction.
The specific calculation method of the demetallization rate and the desulfurization rate is as follows:
Figure BDA0001225785720000172
Figure BDA0001225785720000173
TABLE 2
Figure BDA0001225785720000174
Figure BDA0001225785720000181
TABLE 3
Figure BDA0001225785720000182
The results in table 3 show that the catalyst prepared according to the method of the present invention shows higher demetallization and desulfurization rates during the heavy oil hydrotreating process. Has the advantages which are not compared with other methods in the prior art.
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 (76)

1. A preparation method of a hydrogenation protection catalyst comprises the following steps:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the hydrogenation metal active component comprises at least one VB group metal element and at least one VIII group metal element.
2. The production process according to claim 1, wherein the calcination conditions in the step (1) are such that the amount of the char in the semi-finished catalyst is 0.04 to 0.4% by weight based on the total amount of the semi-finished catalyst.
3. The preparation method as claimed in claim 1, wherein the calcination in step (1) is carried out under the condition of gas introduction, the calcination temperature is 350-500 ℃, and the calcination time is 0.5-8 h; the gas is introduced at a rate of 0.2 to 20 liters per hour per gram of the carrier.
4. The preparation method as claimed in claim 3, wherein the calcination in step (1) is carried out under the condition of gas introduction, the calcination temperature is 360-450 ℃, and the calcination time is 1-6 h; the gas is introduced at a rate of 0.3 to 10 liters per hour per gram of the carrier.
5. The production method according to any one of claims 1 to 4, wherein in the step (1), the molar ratio of the organic complexing agent to the metal active component is from 0.03 to 2: 1.
6. the preparation method according to claim 5, wherein in the step (1), the molar ratio of the organic complexing agent to the metal active component is 0.08-1.5: 1.
7. the preparation method according to any one of claims 1 to 4 and 6, wherein the molar ratio of the organic complexing agent in the step (1) to the organic complexing agent in the step (2) is 1: 0.25-4.
8. The preparation method according to claim 5, wherein the molar ratio of the organic complexing agent in the step (1) to the organic complexing agent in the step (2) is 1: 0.25-4.
9. The production method according to any one of claims 1 to 4, 6 and 8, wherein the organic complexing agent in step (1) is the same as or different from the organic complexing agent in step (2), and the organic complexing agent in step (1) and step (2) is selected from one or more of oxygen-containing organic substances and/or nitrogen-containing organic substances.
10. The preparation method according to claim 9, wherein the oxygen-containing organic substance is selected from one or more of organic alcohol and organic acid, and the nitrogen-containing organic substance is selected from one or more of organic amine and organic ammonium salt.
11. The preparation method according to claim 5, wherein the organic complexing agent in the step (1) is the same as or different from the organic complexing agent in the step (2), and the organic complexing agent in the step (1) and the organic complexing agent in the step (2) are selected from one or more of oxygen-containing organic substances and/or nitrogen-containing organic substances.
12. The preparation method according to claim 11, wherein the oxygen-containing organic substance is selected from one or more of organic alcohol and organic acid, and the nitrogen-containing organic substance is selected from one or more of organic amine and organic ammonium salt.
13. The preparation method according to claim 7, wherein the organic complexing agent in the step (1) is the same as or different from the organic complexing agent in the step (2), and the organic complexing agent in the step (1) and the organic complexing agent in the step (2) are selected from one or more of oxygen-containing organic substances and/or nitrogen-containing organic substances.
14. The preparation method according to claim 13, wherein the oxygen-containing organic substance is selected from one or more of organic alcohol and organic acid, and the nitrogen-containing organic substance is selected from one or more of organic amine and organic ammonium salt.
15. The preparation method according to claim 9, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms.
16. The preparation method according to any one of claims 10 to 14, wherein the organic complexing agent in step (1) is one or more of organic acids having 2 to 7 carbon atoms.
17. The production method according to any one of claims 1 to 4, 6, 8 and 10 to 15, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 0.4 to 30% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
18. The production process according to claim 17, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1 to 18% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
19. The production process according to claim 17, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1.5 to 11% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
20. The production process according to claim 5, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 0.4 to 30% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
21. The production process according to claim 20, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1 to 18% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
22. The production process according to claim 20, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1.5 to 11% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
23. The production process according to claim 7, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 0.4 to 30% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
24. The production process according to claim 23, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1 to 18% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
25. The production process according to claim 23, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1.5 to 11% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
26. The production process according to claim 9, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 0.4 to 30% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
27. The production process according to claim 26, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1 to 18% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
28. The production process according to claim 26, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1.5 to 11% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
29. The production process according to claim 16, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 0.4 to 30% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
30. The production process according to claim 29, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1 to 18% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
31. The production process according to claim 29, wherein the hydrogenation metal active component is used in an amount such that the hydrogenation metal active component is contained in an amount of 1.5 to 11% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
32. The production method according to any one of claims 1 to 4, 6, 8, 10 to 15 and 18 to 31, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.2 to 15% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
33. The production method according to claim 32, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.5 to 10% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
34. The production method according to claim 32, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 1 to 8% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
35. The production method according to claim 5, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.2 to 15% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
36. The production method according to claim 35, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.5 to 10% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
37. The production method according to claim 35, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 1 to 8% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
38. The production method according to claim 7, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.2 to 15% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
39. The production method according to claim 38, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.5 to 10% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
40. The production method according to claim 38, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 1 to 8% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
41. The production method according to claim 9, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.2 to 15% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
42. The production method according to claim 41, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.5 to 10% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
43. The production method according to claim 41, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 1 to 8% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
44. The production method according to claim 16, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.2 to 15% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
45. The production method according to claim 44, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.5 to 10% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
46. The production method according to claim 44, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 1 to 8% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
47. The production method according to claim 17, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is 0.2 to 15% by weight in terms of oxide based on the total amount of the hydrogenation protection catalyst.
48. The production method according to claim 47, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.5 to 10% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
49. The production method according to claim 47, wherein the hydrogenation metal active component is used in an amount such that the content of the group VB metal element is from 0.5 to 10% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.
50. The production method according to any one of claims 1 to 4, 6, 8, 10 to 15, 18 to 31 and 33 to 49, wherein the group VB metal element is vanadium and/or niobium.
51. The production method according to claim 5, wherein the group VB metal element is vanadium and/or niobium.
52. The production method according to claim 7, wherein the group VB metal element is vanadium and/or niobium.
53. The production method according to claim 9, wherein the group VB metal element is vanadium and/or niobium.
54. The production method according to claim 16, wherein the group VB metal element is vanadium and/or niobium.
55. The production method according to claim 17, wherein the group VB metal element is vanadium and/or niobium.
56. The production method according to claim 32, wherein the group VB metal element is vanadium and/or niobium.
57. The production method according to any one of claims 1 to 4, 6, 8, 10 to 15, 18 to 31, 33 to 49 and 51 to 56, wherein the group VIII metal element is one or more of iron, cobalt and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
58. The production method according to claim 5, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
59. The production method according to claim 7, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
60. The production method according to claim 9, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
61. The production method according to claim 16, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
62. The production method according to claim 17, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
63. The method according to claim 32, wherein the group VIII metal element is one or more of iron, cobalt, and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
64. The preparation method according to claim 50, wherein the group VIII metal element is one or more of iron, cobalt and nickel; the support is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
65. The production method according to any one of claims 1 to 4, 6, 8, 10 to 15, 18 to 31, 33 to 49, 51 to 56, and 58 to 64, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
66. The production method according to claim 5, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the carrier is alumina.
67. The production method according to claim 7, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
68. The production method according to claim 9, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
69. The production method according to claim 16, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
70. The production method according to claim 17, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
71. The production method according to claim 32, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the support is alumina.
72. The production method according to claim 50, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the carrier is alumina.
73. The method according to claim 57, wherein the group VIII metal element is selected from cobalt and/or nickel, the group VB metal element is vanadium, and the carrier is alumina.
74. A hydrogenation protection catalyst prepared by the method of any one of claims 1-73.
75. A process for hydroprocessing heavy oil, comprising contacting a heavy oil feedstock with the hydroprotecting catalyst of claim 74 under heavy oil hydroprocessing reaction conditions.
76. The method of claim 75, wherein the heavy oil hydroprocessing reaction conditions include a temperature of 30 deg.C0-550 ℃, 4-20MPa of hydrogen partial pressure and 0.1-3 hours of liquid hourly space velocity-1The volume ratio of hydrogen to oil is 200-.
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