CN107812525A - A kind of hydrogenating catalyst composition and the method for hydrotreating - Google Patents
A kind of hydrogenating catalyst composition and the method for hydrotreating Download PDFInfo
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- CN107812525A CN107812525A CN201610818804.1A CN201610818804A CN107812525A CN 107812525 A CN107812525 A CN 107812525A CN 201610818804 A CN201610818804 A CN 201610818804A CN 107812525 A CN107812525 A CN 107812525A
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- Prior art keywords
- hydrogenation
- catalyst
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- organic
- catalyst composition
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- 239000000969 carrier Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
This disclosure relates to a kind of hydrogenating catalyst composition and the method for hydrotreating, the hydrogenating catalyst composition includes hydrogenation catalyst I and hydrogenation catalyst II;By volume and on the basis of the hydrogenating catalyst composition, the content of the hydrogenation catalyst I is 5 95%;The hydrogenation catalyst I includes carrier, hydrogenation active metals element and non-metal assistant element, and the hydrogenation active metals element contains vib metals element and group VIII metallic element;Wherein, the preparation method of the hydrogenation catalyst I includes:The carrier of the compound for being loaded with the element containing hydrogenation active metals, the first organic complexing agent and non-metal assistant element is carried out into first to dry and be calcined, obtains semi-finished product catalyst;Second organic complexing agent is loaded on the semi-finished product catalyst, and carries out second and dries and without roasting, obtain the hydrogenation catalyst I.When the hydrogenating catalyst composition that the disclosure is provided is applied to hydrotreating, active good, long lifespan.
Description
Technical field
This disclosure relates to a kind of hydrogenating catalyst composition and the method for hydrotreating.
Background technology
The environmental consciousness and increasingly stricter environmental regulation increasingly strengthened forces oil refining circle more to focus on clean fuel life
Produce technological development.Future market vehicle fuel is intended to " super-low sulfur ", it is impossible to meets that the fuel of discharge standard will be unable into entering the market
.Hydrogen addition technology plays more and more important work as a kind of effective desulfurization means in the production of fuel for cleaning vehicle
With, wherein efficient hydrogenation catalyst is then the core technology of hydrogen addition technology, therefore, exploitation with more high activity and selectivity it is new
Type hydrogenation catalyst turns into one of most urgent demand of petroleum refining industry.
Prepared by hydrogenation catalyst generally use infusion process, i.e., active component (such as Ni, Mo, Co, W) is molten needed for containing
Liquid, impregnates certain carrier, the method for being dried and being calcined afterwards.
Chinese patent CN103551162A discloses a kind of diesel hydrogenation for removal sulphur denitrification catalyst, and the composition of catalyst includes carrying
Body, auxiliary agent, active metal;Carrier is Al2O3-ZrO2-TiO2-SiO2Multivariant oxide complex carrier;Auxiliary agent is phosphorus;With nickel, cobalt,
Molybdenum and tungsten are active component;Weight percent content of each component on the basis of catalyst be:In terms of oxide, cobalt oxide 1~
6wt%;1~15wt% of nickel oxide, 2~12wt% of molybdenum oxide, 12~35wt% of tungsten oxide, auxiliary agent phosphorus pentoxide 1.5~
5wt%;Pore volume ≮ 0.2mL/g of catalyst, specific surface area are ≮ 140m2/ g, mechanical strength ≮ 15N/mm;It is each in complex carrier
Shared proportion is respectively component in the carrier:Titanium oxide accounts for 2~15wt%, and silica accounts for 2~20wt%, and zirconium oxide accounts for 5~
15wt%;Surplus is aluminum oxide.The catalyst is made by step impregnation method:Co-impregnated solution is divided into isometric two parts, point
Two step impregnated carriers, and be all calcined after the completion of each step dipping.
Chinese patent CN103657667A discloses a kind of preparation of new macroporous structure catalyst for heavy oil hydrogenation demetal
Method, specifically comprise the following steps:1) preparation of Alumina gel;2) asphaltic residue powder and Alumina gel are mixed with macroporous structure
Catalyst carrier;3) catalyst carrier after shaping is used to two step impregnations of isometric branch;Catalysis is finally made
Agent.Two step infusion processes of the preparation method are specially:The first step first impregnates Mo, and second step impregnates Ni, and not including in maceration extract has
Machine complexing agent.
Although above-mentioned preparation method can improve the Hydrogenation of catalyst to a certain extent, further research
Have been found that, the defects of it is relatively low that catalyst made from prior art still suffers from catalyst activity, or catalyst life is shorter.
The content of the invention
The purpose of the disclosure is to provide a kind of method of hydrogenating catalyst composition and hydrotreating, and the disclosure is provided
When hydrogenating catalyst composition is applied to hydrotreating, active good, long lifespan.
To achieve these goals, the disclosure provides a kind of hydrogenating catalyst composition, the hydrogenating catalyst composition bag
Include hydrogenation catalyst I and hydrogenation catalyst II;By volume and on the basis of the hydrogenating catalyst composition, the hydrogenation is urged
Agent I content is 5-95%;The hydrogenation catalyst I includes carrier, hydrogenation active metals element and non-metal assistant element,
The hydrogenation active metals element contains vib metals element and group VIII metallic element;Wherein, the hydrogenation catalyst
I preparation method includes:Compound, the first organic complexing agent and the non-metal assistant of the element containing hydrogenation active metals will be loaded with
The carrier of element carries out first and dries and be calcined, and obtains semi-finished product catalyst;Wherein, it is catalyzed in terms of butt and with the semi-finished product
On the basis of the butt weight of agent, the carbon content of the semi-finished product catalyst is 0.01-0.5 weight %;By the second organic complexing agent
Load on the semi-finished product catalyst, and carry out second and dry and without roasting, obtain the hydrogenation catalyst I.
Preferably, in hydrogenation reactor, the type of feed of the hydrogenation catalyst I and hydrogenation catalyst II fill for layering
Fill out or mixed packing;The mode of the layering filling includes:According to the flow direction of feedstock oil, the hydrogenation catalyst I is seated in institute
State hydrogenation catalyst II upstream, the hydrogenation catalyst II is seated in the upstream of the hydrogenation catalyst I or the hydrogenation is urged
Agent I loads with the hydrogenation catalyst II alternatively layereds.
Preferably, the compound for being loaded with the element containing hydrogenation active metals, the first organic complexing agent and nonmetallic help
The preparation process of the carrier of agent element includes:With compound and the first organic complex containing the element containing hydrogenation active metals
Carrier of the aqueous solution dipping containing the non-metal assistant element of agent;Or with containing the element containing hydrogenation active metals
Compound, the solution impregnating carrier of non-metal assistant element and the first organic complexing agent.
Preferably, counted and on the basis of the butt weight of the semi-finished product catalyst by butt, the semi-finished product catalyst
Carbon content be 0.04-0.4 weight %.
Preferably, the described first condition dried and the described second condition dried include independently of one another:Dry temperature
Spend for 100-250 DEG C, the dry time is 1-12 hours;The condition of the roasting includes:Under conditions of oxygen-containing gas is passed through
Carry out, on the basis of the weight of carrier, the intake of oxygen-containing gas is 0.2-20 liters/(gram hour);The temperature of roasting is
350-500 DEG C, the time of roasting is 0.5-8 hours.
Preferably, first organic complexing agent and the second organic complexing agent include organic oxygen-containing compound independently of one another
And/or nitrogen-containing organic compound;The organic oxygen-containing compound is Organic Alcohol and/or organic acid, the nitrogen-containing organic compound
For organic amine and/or organic ammonium salt.
Preferably, first organic complexing agent and the second organic complexing agent are included selected from ethylene glycol, third independently of one another
Triol, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexane diamine tetrems
At least one of acid, citric acid, tartaric acid, malic acid, ethylenediamine and ethylenediamine tetra-acetic acid.
Preferably, the mol ratio of the hydrogenation active metals element and first organic complexing agent is 1:(0.03-2).
Preferably, the mol ratio of first organic complexing agent and second organic complexing agent is 1:(0.25-4).
Preferably, counted and on the basis of the gross weight of the hydrogenation catalyst I by oxide, the hydrogenation active metals member
The content of element is 6-70 weight %;Counted by element and on the basis of the gross weight of the hydrogenation catalyst I, the non-metal assistant
The content of element is no more than 10 weight %.
Preferably, the non-metal assistant element be selected from group IVA element, V Group IIA element, V A race's elements and
At least one of group III A element, the carrier be selected from gama-alumina, silica, aluminium oxide-silicon oxide, titanium oxide,
Magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania,
Titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia
With the one or more in silica-alumina, zirconia.
Preferably, the vib metals element is molybdenum and/or tungsten, the group VIII metallic element be cobalt and/or
Nickel;The non-metal assistant element is selected from least one of fluorine element, element silicon, P elements and boron element.
Preferably, counted and on the basis of the gross weight of the hydrogenation catalyst I by oxide, the group VIII metal member
The content of element is 1-10 weight %, and the content of the vib metals element is 5-60 weight %.
Preferably, the hydrogenation catalyst II contains at least one vib metals element and at least one group VIII
Metallic element;Counted by oxide and on the basis of the gross weight of the hydrogenation catalyst II, the group VIII metallic element
Content is 1-10 weight %, and the content of the vib metals element is 5-60 weight %.
The disclosure also provides a kind of method of hydrotreating, and this method includes:Add what feedstock oil and the disclosure were provided
Hydrogen catalyst composition contacts and carries out hydrogenation reaction.
Preferably, the condition of the hydrogenation reaction includes:Temperature is 300-400 DEG C, and pressure is 1-10 MPas, feedstock oil
Volume space velocity is 0.5-3 hours during liquid-1, hydrogen to oil volume ratio 100-800.
Preferably, the feedstock oil is selected from gasoline, diesel oil, lubricating oil, kerosene, naphtha, reduced crude, decompression slag
At least one of oil, pertroleum wax and Fischer-Tropsch synthesis oil.
The disclosed invention people has found that the hydrogenation catalyst I prepared using method of disclosure is urged with hydrogenation commonly used in the art
After agent II is applied in combination, there is good hydrogenation activity and longer catalyst life, have well to various hydrocarbon oil crude materials
Hydrodesulfurization, hydrodenitrogeneration performance.
In addition, the hydrogenating catalyst composition that the disclosure provides has higher hydrodesulfurization activity concurrently and hydrodenitrogeneration is lived
Property, hence it is evident that extend the service life of catalyst.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the disclosure is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explained the disclosure, is not limited to the disclosure.
The disclosure provides a kind of hydrogenating catalyst composition, and the hydrogenating catalyst composition includes hydrogenation catalyst I and added
Hydrogen catalyst II;By volume and on the basis of the hydrogenating catalyst composition, the content of the hydrogenation catalyst I is 5-
95%;The hydrogenation catalyst I includes carrier, hydrogenation active metals element and non-metal assistant element, the hydrogenation activity gold
Category element contains vib metals element and group VIII metallic element;Wherein, the preparation method bag of the hydrogenation catalyst I
Include:The carrier of the compound for being loaded with the element containing hydrogenation active metals, the first organic complexing agent and non-metal assistant element is entered
Row first is dried and is calcined, and obtains semi-finished product catalyst;Wherein, in terms of butt and with the butt weight of the semi-finished product catalyst
On the basis of, the carbon content of the semi-finished product catalyst is 0.01-0.5 weight %, preferably 0.04-0.4 weight %;Second is had
Machine complexing agent is loaded on the semi-finished product catalyst, and is carried out second and dried and without roasting, obtain the hydrogenation catalyst
Agent I.It should be noted that the butt weight measurement method of semi-finished product catalyst described in the disclosure is:Weigh constant weight
Testing sample (such as 30 grams), the sample is calcined 3 hours for 450 DEG C in Muffle furnace, weighed after cooling, the weight is sample
The butt weight of product.
The disclosure does not have special limit to the type of feed of hydrogenation catalyst I and hydrogenation catalyst II in hydrogenation reactor
System, such as type of feed can be layering filling or mixed packing;The mode of the layering filling can include:According to feedstock oil
Flow direction, the hydrogenation catalyst I is seated in the upstream of the hydrogenation catalyst II, the hydrogenation catalyst II be seated in it is described
Hydrogenation catalyst I upstream or the hydrogenation catalyst I load with the hydrogenation catalyst II alternatively layereds.Because hydrogenation is urged
Agent I better performances, are lasted a long time, and hydrogenation catalyst I is preferably seated in downstream, with more exacting terms with raw material
Oil is reacted.
The inventor of the disclosure has found, by introducing complexing agent and complexing dry at low temperature dipping in dipping process
Technology, active component and carrier interaction can be weakened, the decentralization of hydrogenation active metals element is improved, change metal vulcanization
Sequentially, form the activity of more high activities mutually and improve activated centre number.But due to being used in dipping technique is complexed
Low temperature drying, not by the process of high-temperature roasting, hydrogenation active metals element exists still in the form of metallic salt
In carrier surface, hydrogenation active metals element and carrier function power are weaker, cause the hydrogenation in HTHP and severe raw material
Under reaction condition, metal is constantly assembled during the course of the reaction, and auxiliary agent effect weakens, and activated centre number is reduced, latent active
Decline, therefore the activity and stability of catalyst decline.And although the catalyst stability for using high-temperature roasting method to prepare is preferable,
But active component and carrier active force is stronger, the latent active in activated centre is relatively low, due to the scattered and resistance of no complexing agent
Every effect, active component platelet is larger, and activated centre number is less, and activity is very low.Compared with traditional infusion process, complexing dipping
Although technology can further lift the activity of such catalyst, exist catalytic activity reduce it is too fast, cause catalyst to make
With the life-span it is too short the defects of.
The inventor of the disclosure by research it has furthermore been found that loading (such as dipping) method by two steps prepares catalyst,
The first step loads and second step load is respectively used to introduce hydrogenation active metals element and organic complexing agent, is loaded in the first step
The first organic complexing agent is added in journey and is run through roasting and is converted into charcoal, the activity of catalyst, Er Qieneng can not only be improved
Enough high activities for effectively keeping catalyst for a long time, so as to greatly improve the service life of catalyst.Speculate that its reason may
It is because the first organic complexing agent added in first step loading process hinders hydrogenation active metals element in roasting process
Aggregation, make its scattered more uniform;Meanwhile roasting can make the compound of the element containing hydrogenation active metals after first step load
Metal oxide is converted into, the first organic complexing agent is converted into charcoal, so that the combination between metal oxide and carrier is more
Add the activity and stability for firmly, improving catalyst.And the second organic complexing agent added in second step loading process covers
Cover in catalyst surface, can effectively prevent aggregation of the metal oxide during catalyst vulcanization, improve metal dispersity,
It is more beneficial for being formed with higher active II classes activity phase and forms more activated centres, is urged so as to further increase
The activity of agent.
The disclosure to the compound of the element containing hydrogenation active metals, the first organic complexing agent and non-metal assistant element with
Which kind of form, which kind of sequentially load to it is not restricted on the carrier, only need to roasting when, the first organic complexing agent can hinder
Hinder the aggregation of hydrogenation active metals element and form charcoal:
For example, the compound for being loaded with the element containing hydrogenation active metals, the first organic complexing agent and the non-metal assistant
The preparation process of the carrier of element includes:With compound and the first organic complexing agent containing the element containing hydrogenation active metals
The aqueous solution dipping containing the non-metal assistant element carrier;Or with containing the element containing hydrogenation active metals
Dipping described in the solution impregnating carrier of compound, non-metal assistant element and the first organic complexing agent can be isometric leaching
Stain, or supersaturation dipping, be not particularly limited to the temperature of the dipping, can be that maceration extract can reach various
Temperature, the time of dipping is not particularly limited, if the desired amount of required component can be loaded, such as:The temperature of dipping
Degree can be 15-60 DEG C, and the time of dipping can be 0.5-5 hours.
According to the disclosure, hydrogenation active metals element is well-known to those skilled in the art, for example, the vib
Metallic element is preferably molybdenum and/or tungsten, and the group VIII metallic element is preferably cobalt and/or nickel;In terms of oxide and with institute
On the basis of the gross weight for stating hydrogenation catalyst I, the content of the hydrogenation active metals element can be 6-70 weight %, be preferably
15-60 weight %, preferably 20-50 weight %, more preferably 20-40 weight %;The group VIII metallic element
Content can be 1-10 weight %, and the content of the vib metals element can be 5-60 weight %.
According to the disclosure, in hydrogenation catalyst I preparation method, the compound of the element containing hydrogenation active metals is this area
Can be that various solubility meet load request or can formed in the presence of cosolvent in water molten known to personnel
Xie Du meets the water soluble compound of the desired element containing hydrogenation active metals, such as can be salt and/or oxide, preferably
For at least one of nitrate, chloride, sulfate, carbonate, more preferably nitrate.With elemental metal with the aqueous solution
On the basis of, the concentration of the water soluble salt of the element containing hydrogenation active metals can be 0.2-8mol/L, preferably 0.2-5mol/L, more
More preferably 0.2-2mol/L.Concentration herein is respective dense for the water soluble salt of the various elements containing hydrogenation active metals
Degree, rather than total concentration.
The compound and the compound of the metallic element containing group VIII that the element containing vib metals will be illustrated respectively below.
A kind of embodiment, the compound of the element containing vib metals can be selected from ammonium molybdate, ammonium paramolybdate, partially
At least one of ammonium tungstate, molybdenum oxide and tungsten oxide.
Another embodiment, the compound of the metallic element containing group VIII can be selected from the nitre of group VIII metal
Hydrochlorate, the chloride of group VIII metal, the sulfate of group VIII metal, the formates of group VIII metal, group VIII
The acetate of metal, the phosphate of group VIII metal, the citrate of group VIII metal, the oxalic acid of group VIII metal
Salt, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydroxide of group VIII metal,
The phosphate of group VIII metal, the phosphide of group VIII metal, the sulfide of group VIII metal, the aluminium of group VIII metal
Hydrochlorate, the molybdate of group VIII metal, the tungstates of group VIII metal and group VIII metal water-soluble oxide in
At least one.
A kind of preferred embodiment, the compound of the metallic element containing group VIII are selected from group VIII metal
Oxalates, the nitrate of group VIII metal, the sulfate of group VIII metal, the acetate of group VIII metal, VIII
The chloride of race's metal, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydrogen of group VIII metal
Oxide, the phosphate of group VIII metal, the molybdate of group VIII metal, the tungstates of group VIII metal and VIII
At least one of water-soluble oxide of race's metal.
A kind of further preferred embodiment, the compound of the metallic element containing group VIII can be selected from nitric acid
In nickel, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride
At least one.
According to the disclosure, the compound loaded order on carrier of the element containing hydrogenation active metals does not limit particularly
It is fixed, hydrogenation activity can be contained by all by the solution impregnating carrier of the compound containing a variety of elements containing hydrogenation active metals
The compound mutual load of metallic element can also prepare the compound containing the element containing hydrogenation active metals respectively on carrier
Solution step impregnation carrier, the compound of the element containing hydrogenation active metals is loaded on carrier successively.Soaked when using substep
When stain, preferably it is dried after each dipping.Dry mode and condition is referred to prior art and selected.
According to the disclosure, the mode that first organic complexing agent is loaded on carrier has no particular limits.First has
Machine complexing agent can with least one of the compound of the element containing hydrogenation active metals co-formulation into maceration extract impregnated carrier,
Maceration extract impregnated carrier can also be individually configured to, preferably the former.
According to the disclosure, non-metal assistant element is well-known to those skilled in the art, can be commonly used in the art
The various nonmetalloids that can improve the performance with hydrogenation catalyst action catalysts, can be according to the applicable cases of catalyst
Selected.Such as can be in group IVA element, V Group IIA element, V A race's elements and group III A element
At least, group IVA metallic element is preferably silicon and/or carbon, V Group IIA metallic element be preferably in fluorine, chlorine, bromine and iodine extremely
Few one kind, V A races metallic element is preferably at least one of phosphorus and/or arsenic, and group III A element for example can be boron, more
Preferably, the non-metal assistant element is selected from least one of fluorine element, element silicon, P elements, boron element, nonmetallic to help
The content of agent element is usually no more than 10 weight %, preferably 0.5-6 weight %.Due to equal in carrier and non-metal assistant element
Element silicon can be contained, unless otherwise noted, if silicon content more than 10 weight %, and in the form of silica exist, be included into
Carrier, otherwise element silicon belong to non-metal assistant element.
According to the disclosure, the mode that the non-metal assistant element is loaded on carrier does not limit specifically, described
The carrying method of non-metal assistant element can be by number of ways, for example, can be loaded in carrier preparation process, can also
By various modes as the mode impregnated loads after carrier preparation.
It should be noted that when loading non-metal assistant element by the method for impregnated carrier, it is necessary to introduce non-gold
It is calcined after category auxiliary element, the sintering temperature can be 250-600 DEG C, and preferably 350-500 DEG C, roasting time can be with
For 2-8 hours, preferably 3-6 hours.
According to the disclosure, the load of non-metal assistant element described in catalyst I need to load it in the second organic complexing agent
Preceding progress, to ensure that the second organic complexing agent does not suffer from roasting process.
During using infusion process, preferably non-metal assistant element and the compound of the element containing hydrogenation active metals and first are had
Machine complexing agent is loaded on carrier together.Non-metal assistant element can use the various soluble-salts of non-metal assistant to be born
Carry, such as selected from oxide, chloride, containing at least one of hydrochlorate and ammonium salt.In terms of nonmetalloid, non-gold in maceration extract
The dosage for belonging to auxiliary element can be 0.05-3mol/L, preferably 0.1-2mol/L.
The disclosure controls the carbon content of semi-finished product catalyst by the condition dried and be calcined, for example, described first is dry
Dry condition and the described second condition dried includes independently of one another:Dry temperature is 100-250 DEG C, preferably 100-
200 DEG C, the dry time is 1-12 hours, preferably 1-10 hours;The condition of the roasting includes:It is being passed through oxygen-containing gas
Under the conditions of carry out, on the basis of the weight of carrier, the intake of oxygen-containing gas be more than 0.2 liter/(gram hour), be preferably
0.2-20 liters/(gram hour), more preferably 0.3-10 liters/(gram hour);The temperature of roasting is 350-500 DEG C, excellent
Elect 360-450 DEG C as, time of roasting is 0.5-8 hours, preferably 1-6 hours, wherein, the oxygen-containing gas can be empty
Gas, oxygen and other oxygen-containing gas, preferably oxygen volume content are not less than 20 body %, and being passed through for oxygen-containing gas on the one hand can
Meet the condition of burning, make the compound of the element containing hydrogenation active metals, for example, the salt conversion of the element containing hydrogenation active metals and
For hydrogenation active metals oxide, and the first organic complex is set to be converted into charcoal, on the other hand also can be by the dioxy formed that burns
Change carbon and water and other compositions emit, to avoid being deposited on the room obstruction caused on catalyst I to active phase.
According to the disclosure, first organic complexing agent and the second organic complexing agent include organic oxygen-containing independently of one another
Compound and/or nitrogen-containing organic compound, the organic oxygen-containing compound can be Organic Alcohol and/or organic acid, the Organic Alcohol
Preferably polyalcohol, more preferably carbon number are 2-6 polyalcohol, the oligomer of polyalcohol and the poly of polyalcohol
Body, for example, in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol and butanediol at least one in, the polyethylene glycol
Molecular weight be preferably 200-1500, the organic acid is preferably C2-C7The organic acid containing one or more carboxyls, for example, choosing
From in acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid and malic acid
It is at least one.The nitrogen-containing organic compound can be organic amine and/or organic ammonium salt, and the organic amine is preferably C2-C7Contain
The compound of one or more amino groups, at least one of primary amine, secondary amine and tertiary amine, preferably ethylenediamine are selected from,
The organic ammonium salt is preferably ethylenediamine tetra-acetic acid.Specifically, first organic complexing agent and the second organic complexing agent are preferred
Include independently of one another selected from ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, ammonia
In base triacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, malic acid, ethylenediamine and ethylenediamine tetra-acetic acid extremely
Few one kind.It is further preferred that first organic complexing agent and the second organic complexing agent are organic acid, so that catalyst obtains
Get Geng Gao hydrogenation activity.The mol ratio of the hydrogenation active metals element and first organic complexing agent can be 1:
(0.03-2), preferably 1:The mol ratio of (0.08-1.5), first organic complexing agent and second organic complexing agent can
Think 1:(0.25-4), preferably 1:(0.5-2).
According to the disclosure, carrier is well-known to those skilled in the art, for example, the carrier can be selected from γ-oxygen
Change aluminium, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica-oxygen
Change thorium, silica-berylias, silica-titania, titania-zirconia, silica-alumina thoria, silica-oxygen
Change at least one of aluminium-titanium oxide, silicaalumina-magnesia and silica-alumina, zirconia, wherein aluminum oxide
The oxidation obtained after more preferably a kind of hydrated alumina (aluminium hydroxide, such as boehmite) glue compound roasting
Aluminium.
According to the disclosure, hydrogenation catalyst II can be the conventional hydrogenation catalyst in this area, generally comprise carrier and gold
Belong to component, hydrogenation catalyst II is not particularly limited the disclosure, and it can be commercially available commodity, can also use arbitrary existing
There is technology preparation.For example, the hydrogenation catalyst II can contain vib metals element and group VIII metallic element;With
Oxide meter and on the basis of the gross weight of the hydrogenation catalyst II, the content of the group VIII metallic element can be 1-
10 weight %, the content of the vib metals element can be 5-60 weight %.
The disclosure also provides a kind of method of hydrotreating, and this method includes:Add what feedstock oil and the disclosure were provided
Hydrogen catalyst composition contacts and carries out hydrogenation reaction.Compared with using conventional hydrogenation catalyst, provided using the disclosure
Hydrogenating catalyst composition has higher hydrogenation activity.
According to the disclosure, hydrogenation catalyst I and hydrogenation catalyst II can be layered and be loaded on the same of same reactor
In beds or different catalysts bed, it can also be loaded in the reactor of several series connection and use, not have to this disclosure
There is special limitation.
According to the disclosure, before hydrogenation catalyst I, afterwards and among and hydrogenation catalyst II before, afterwards and it
In, any other catalyst or filler for helping to improve hydrogenation catalyst performance can be set.If for example, hydrogenation catalyst
I is located at hydrogenation catalyst II upstreams, and such as porcelain ball, active supporter filler can be added before hydrogenation catalyst I, to improve
The distribution of feedstock oil in the reactor etc..The occupation mode of filler is known to those skilled in the art, and the disclosure does not repeat.
According to the disclosure, hydrotreating is well-known to those skilled in the art, such as can be hydrodesulfurization and hydrogenation
The unifining process such as denitrogenation, the condition of the hydrogenation reaction can include:Temperature is 300-400 DEG C, preferably 320-380
DEG C, pressure is 1-10 MPas (in terms of gauge pressure), preferably 1-8 MPas, and volume space velocity is 0.5-3 hours during the liquid of feedstock oil-1, it is excellent
Elect 0.5-2.5 hours as-1, hydrogen to oil volume ratio 100-800, preferably 100-700, the hydrogen to oil volume ratio refers to the body of hydrogen
The ratio of the volume flow rate of product flow velocity and feedstock oil.The feedstock oil is well-known to those skilled in the art, is for example, selected from
At least one in gasoline, diesel oil, lubricating oil, kerosene, naphtha, reduced crude, decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil
Kind.
According to the disclosure, conventional method of the hydrogenating catalyst composition preferably using this area before use carries out sulphur
Change.Usually, the condition of the vulcanization can include:In presence of hydrogen, at a temperature of 360-400 DEG C, with sulphur, vulcanization
At least one of hydrogen, carbon disulfide, DMDS and polysulfide carry out the presulfurization of 2-4 hours, and the presulfurization can
Carry out, can also be carried out in reactor In-situ sulphiding outside reactor.
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
Rigaku electric machine industry Co., Ltd. 3271E type X-ray fluorescence spectras are used in following examples and comparative example
Instrument, analysis measure is carried out to the content of each element in catalyst.Carbon content uses Japanese HORIBA companies in semi-finished product catalyst
The EMIA-320V carbon and sulfur analytical instruments of production carry out analysis measure.
The butt assay method of hydrated alumina or aluminium hydrate powder used is in embodiment:Weigh the to be measured of constant weight
Sample (such as 30 grams), the sample is calcined 3 hours for 600 DEG C in Muffle furnace, weighed after cooling, the weight is dry basis
The ratio of amount, the weight and testing sample is the butt of sample.
Embodiment 1
The present embodiment is used for illustrating according to hydrogenation catalyst I of the disclosure and preparation method thereof.
By 2000 grams of aluminium hydrate powders (dry glue powder of Chang Ling refinery company catalyst plant production, the weight % of butt 71) and
1039 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica are 30 weight %) are well mixed.The mixing that will be obtained
Thing is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters with banded extruder, and the wet bar of extrusion is dry 4 hours at 120 DEG C, then
It is calcined 3 hours at 600 DEG C, it is 18.0 weight % that silica content in carrier I-Z1, carrier I-Z1, which is made, and alumina content is
82.0 weight %.
Weigh respectively 54 grams of molybdenum trioxides, 19 grams of basic cobaltous carbonates, 13 grams of phosphoric acid, 30 grams of citric acids be put into 140 grams go from
In sub- water, heating stirring dissolves to obtain clarification dipping solution, and impregnating 200 grams of I-Z1 with above-mentioned solution using saturation infusion process carries
Body, dip time are 2 hours, then, dry 2 hours at 120 DEG C, are then roasted it in the state of air stream is passed through
Burn, sintering temperature be 400 DEG C, the time be 2 hours, gas agent ratio be 1 liter/(gram hour), obtain semi-finished product catalyst I-Z-S1,
Carbon content is shown in Table 1;30 grams of citric acids are added in 150 grams of deionized waters, stirring obtains settled solution, is used using saturation infusion process
Above-mentioned solution impregnates I-Z-S1, and dip time is 2 hours, then, in 150 DEG C of dry 3 hours, obtains catalyst I-1.To urge
On the basis of agent I-1 total amount, in terms of oxide, the content of hydrogenation active metal component is shown in Table 1.
Comparative example 1
Hydrogenation catalyst is prepared using method same as Example 1, unlike, by catalyst obtained by embodiment 1
I-1 is calcined 3 hours at 400 DEG C, obtains catalyst D1, on the basis of catalyst D1 total amount, in terms of oxide, and hydrogenation activity gold
The content of category component is shown in Table 1.
Embodiment 2
The present embodiment is used for illustrating according to hydrogenation catalyst I of the disclosure and preparation method thereof.
30 grams of nickel nitrates, 45 grams of ammonium metatungstates, 15 grams of oxalic acid and 21 grams of ammonium fluorides are weighed respectively is put into 140 grams of deionized waters
In, stirring and dissolving obtains settled solution, impregnates 200 grams of alumina supports, dip time with above-mentioned solution using saturation infusion process
For 2 hours, then, dry 2 hours, be then calcined it in the state of air stream is passed through, sintering temperature is at 120 DEG C
360 DEG C, the time be 6 hours, gas agent ratio be 10.0 liters/(gram hour), obtain semi-finished product catalyst I-Z-S2, carbon content is shown in Table
1;10 grams of diethylene glycol (DEG)s are put into 150 grams of deionized waters, stirring obtains settled solution, is soaked using saturation infusion process with above-mentioned solution
Stain I-Z-S2, dip time are 2 hours, then, in 150 DEG C of dry 3 hours, obtain catalyst I-2.With catalyst I-2's
On the basis of total amount, in terms of oxide, the content of hydrogenation active metal component is shown in Table 1.
Embodiment 3
The present embodiment is used for illustrating according to hydrogenation catalyst I of the disclosure and preparation method thereof.
60 grams of ammonium fluorides are weighed, add deionized water stirring and dissolving, adding deionized water, saturation impregnates 1000 to 850 milliliters
Gram Zirconia carrier 2 hours, then dried at 120 DEG C 2 hours, 400 DEG C are calcined 4 hours, obtain fluorine-containing Zirconia carrier I-Z3.
83 grams of nickel nitrates, 60 grams of ammonium metatungstates, 10 grams of ammonium molybdates, 20 grams of ammonium dihydrogen phosphates and 20 grams of citric acids are weighed respectively
It is put into 180 grams of deionized waters, stirring and dissolving obtains settled solution, and impregnating 200 grams with above-mentioned solution using saturation infusion process contains
Fluorine Zirconia carrier I-Z3, dip time are 2 hours, then, are dried 2 hours at 120 DEG C, it then is being passed through into air stream
Be calcined under state, sintering temperature is 450 DEG C, and the time is 3 hours, and gas agent ratio is 0.3 liter/(gram hour), obtain half into
Product catalyst I-Z-S3, carbon content are shown in Table 1;15 grams of ethylenediamines are put into 150 grams of deionized waters, stirring obtains settled solution,
I-Z-S3 is impregnated with above-mentioned solution using saturation infusion process, dip time is 2 hours, then, in 120 DEG C of dry 3 hours, is obtained
To catalyst I-3.On the basis of catalyst I-3 total amount, in terms of oxide, the content of hydrogenation active metal component is shown in Table 1.
Embodiment 4
Hydrogenation catalyst I is prepared using method same as Example 1, unlike, metal active constituent is impregnated into load
After body, when being calcined to carrier, sintering temperature is 480 DEG C, and the time is 6 hours.Carbon content in obtained catalyst semi-finished product
1 is shown in Table, in obtained catalyst I-4, on the basis of catalyst I-4 total amount, in terms of oxide, hydrogenation active metal component
Content is shown in Table 1.
Embodiment 5
Hydrogenation catalyst I is prepared using method same as Example 2, unlike, gas agent ratio during roasting is 1.0
Rise/(gram hour), in obtained catalyst I-5, on the basis of catalyst I-5 total amount, in terms of oxide, hydrogenation activity gold
The content of category component is shown in Table 1.
Embodiment 6
Hydrogenation catalyst I is prepared using method same as Example 1, unlike, step (1) and step (2) are organic
The amount ratio of complexing agent is by 30 grams:30 grams are changed to 50 grams:10 grams, in obtained catalyst I-6, using catalyst I-6 total amount as
Benchmark, in terms of oxide, the content of hydrogenation active metal component is shown in Table 1.
Embodiment 7-10 illustrates catalyst II preparation method.
Embodiment 7
Hydrogenation catalyst II-1 preparation methods are as follows:
Weighing the precursor of a certain amount of small porous aluminum oxide, (the first hydrated alumina, sodium metaaluminate-carbon dioxide process are made
Industrial products, name of product is dry boehmite, and Shandong Aluminum Plant produces, wherein 80 heavy % of a diaspore content, three water
5 heavy % of aluminium stone content).Separately weigh precursor (second of hydrated alumina, the sodium metaaluminate-sulfuric acid of a certain amount of macroporous aluminium oxide
Industrial products made from aluminium method, name of product are Chang Ling dry glue powder, and Chang Ling oil plant catalyst plant is produced, a diaspore content 68
Weight %, 5 heavy % of gibbsite content).By two kinds of hydrated aluminas by 75: 25 butt weight than well mixed, addition helps crowded
Agent, adhesive and water, it is extruded into the trilobal cross bar that circumscribed circle diameter is 1.4 millimeters, 120 DEG C of drying, respectively in 550~650 DEG C of roastings
Burn 4 hours, catalyst carrier is made, weighs a certain amount of alumina support respectively, with ammonium fluoride (chemistry is pure) aqueous solution dipping 1
Hour, 120 DEG C of drying, it is calcined 4 hours at 530 DEG C, obtains fluoro-containing alumina carrier.With quantitative ammonium metatungstate (chemistry pure) and
The mixed aqueous solution dipping fluoro-containing alumina carrier of nickel nitrate (chemistry is pure) 4 hours, 120 DEG C of drying, in 530 DEG C of roasting temperatures
4 hours, hydrogenation catalyst II-1 is made, it includes 4 weight % nickel (in terms of NiO), 30 weight % tungsten (in terms of tungsten oxide),
4 weight % fluorine (being calculated with element fluorine), remaining is aluminum oxide.
Embodiment 8
Hydrogenation catalyst II-2 preparation method is as follows:
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively is put into 55mL
In deionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into burning
In cup, 90 DEG C and under agitation constant temperature 8 hours are heated to, add water to 85mL, obtain clarifying dipping solution.By 2000 grams of hydroxides
Aluminium powder (dry glue powder of Chang Ling refinery company catalyst plant production, the weight % of butt 71) and 1039 grams of Ludox (Qingdao Haiyangs
Factory products, dioxide-containing silica are 30 weight %) it is well mixed.Obtained mixture is extruded into circumscribed circle diameter with banded extruder
For 1.4 millimeters of butterfly bar, and the wet bar of extrusion is dried 4 hours at 120 DEG C, be then calcined 3 hours at 600 DEG C, be made and carry
Body, silica content is 18.0 weight % in carrier, and alumina content is 82.0 weight %.The water absorption rate of carrier is 0.85.With
Dipping solution 85mL saturations 100 grams of dipping carrier 2 hours is clarified, 2 hours of 120 DEG C of dryings, 3 hours of 250 DEG C of dryings, is obtained
Hydrogenation catalyst II-2, wherein the Co (in terms of CoO) comprising 3.9 weight %, 20.1 weight % molybdenum is (with MoO3Meter), 2.1%
Weight % phosphorus is (with P2O5Meter), 5.6% citric acid, remaining is aluminum oxide.
Embodiment 9
Hydrogenation catalyst II-3 preparation method is as follows:
By containing 210 grams of aluminum oxide/liter, causticity coefficient be 1.62 high concentration NaAlO2Solution is configured to deionized water
Al2O3Concentration is 40 g/l of 5 liters of solution, then adds 16.3 grams of sodium gluconate and obtains the NaAlO containing sodium gluconate2It is molten
Liquid, it is then transferred in cumulative volume 8L plastic reactor, reactor ratio of height to diameter is 8, lower bands CO2Gas distributor.Control
Solution temperature is 25 ± 5 DEG C, and the volume % of concentration 90 CO is passed through from reactor bottom2Gas carries out plastic reaction, gelling temperature
Control adjusts CO at 20-40 DEG C2Gas flow is 15 ± 2 liters/min, reaction end pH value is reached 8.0- within 4-6 minutes
8.5, that is, stop ventilation, terminate plastic reaction.Gained slurries are heated to 70 DEG C of agings 4 hours, then use vacuum filter
Machine is filtered, it is to be filtered it is complete after, supplement adds 20 liters of deionized waters (temperature 70 C) and rinses filter cake about 30 minutes on filter cake.
Qualified filter cake will be washed it is added in 1.5 liters of deionized waters and stir into slurries, slurries is done with spray dryer is pumped into
It is dry, obtain hydrated alumina P1-2.Weighing 300 grams of boehmite P1-2 and 700 grams of boehmite P2-3, (Shandong Aluminum Co., Ltd. is public
Take charge of the business boehmite SD powder of production), after mixing, it is extruded into the cloverleaf pattern that circumscribed circle diameter is 1.6 millimeters with banded extruder
Bar, 120 DEG C of dryings 8 hours.Wherein 300 grams are taken, at 800 DEG C, calcination process 4 hours under the conditions of blowing air, carrier is made, wherein
Air mass flow is 1.5 standard cubic meters/kilogram hour.100 grams of carrier is weighed, with containing 20.6 grams of nickel nitrate, ammonium paramolybdate
85 milliliters of the aqueous solution of 34.8 grams and 1.4 grams of phosphatase 11 impregnates 1.5 hours, 120 DEG C of drying 5 hours, 380 DEG C of processing 4 hours, so
Being impregnated 2 hours with 55 milliliters of the aqueous solution containing 8.4 grams of glycerine afterwards, 140 DEG C of dryings obtain hydrogenation catalyst II-3 in 5 hours, its
In include 3.5 weight % nickel (in terms of NiO), 19.1 weight % molybdenum is (with MoO3Meter), 4.8% weight % phosphorus is (with P2O5
Meter), 5.7% organic additive, remaining is aluminum oxide.
Embodiment 10
Hydrogenation catalyst II-4 preparation method is as follows:
Weigh 2000 grams of aluminium hydrate powders (dry glue powder of Chang Ling branch company catalyst plant production, the weight % of butt 70) and
299 grams of Ludox (Haiyang Chemical Plant, Qingdao's product) containing silica 25%, circumscribed circle diameter is extruded into for 1.3 millis with banded extruder
The butterfly bar of rice, wet bar are calcined 3 hours under the conditions of being dried 4 hours, 600 DEG C in 120 DEG C, carrier are made, silica contains in carrier
Measure as 5.0 weight %.200 grams of carrier is weighed, the carrier is impregnated 2 hours with 176 milliliters of the aqueous solution containing 16.9 grams of ammonium fluoride,
120 DEG C of dryings 3 hours, 420 DEG C are calcined 3 hours, and fluorinated silicon oxide-alumina support is made.With containing 23.0 grams of ammonium paramolybdate
170 milliliters of the aqueous solution impregnates above-mentioned carrier 3 hours, 120 DEG C of dryings 4 hours, then 170 DEG C of dryings 4 hours, obtains carrier containing molybdenum.
Then with 162 milliliters of the aqueous solution containing 53.2 grams of nickel nitrate, 140.7 grams of ammonium metatungstate, 8.1 grams of phosphatase 11, to impregnate the carrier 3 small
When, 200 DEG C of dryings 4 hours, afterwards with 121 milliliters of dippings of the aqueous solution containing 77.3 grams of ethylene glycol, 120 DEG C of drying must after 6 hours
To hydrogenation catalyst II-4, wherein the nickel (in terms of NiO) comprising 3.6 weight %, 5.0 weight % molybdenum is (with MoO3Meter), 32.5
Weight % tungsten (in terms of tungsten oxide), 2.2 weight % fluorine (being calculated with element fluorine), 3.0% weight % phosphorus is (with P2O5Meter),
5.0 weight % ethylene glycol, remaining is aluminium oxide-silicon oxide.
Embodiment 11-16
In embodiment 11-16, the hydrogenation catalyst and comparative example that are prepared to the method provided using the disclosure are provided
The desulphurizing activated and denitrification activity of hydrogenation catalyst carry out hydrofinishing evaluation in accordance with the following methods, and commented according to hydrofinishing
Valency result computational method is calculated, and evaluation result is as shown in table 2 below.
Using the Middle East straight(-run) diesel distillate of 15% catalytic diesel oil of blending as raw material, its property is as shown in table 3, in 30 milliliters of diesel oil
Desulfurization, the denitrification activity of catalyst are evaluated on hydrogenation plant, Catalyst packing 30mL, raw material oil-in is located on hydrogenation plant
Side, hydrogenation catalyst II are seated in the upper bed layer of hydrogenation plant, and hydrogenation catalyst I (or D1) is seated in leaving the bed for hydrogenation plant
Layer, i.e. hydrogenation catalyst II downstream.Need to carry out presulfurization to catalyst before the reaction, its presulfurization condition is:Hydrogen dividing potential drop
6.4MPa, 320 DEG C of temperature, liquid hourly space velocity (LHSV) 4h-1, hydrogen to oil volume ratio 300, it is 8mL/h that sulfurized oil, which enters speed oil,.Reaction condition is:
Hydrogen dividing potential drop 6.4MPa, 350 DEG C of reaction temperature, hydrogen to oil volume ratio 300, liquid hourly space velocity (LHSV) 1.5h-1.Negate respectively and answer 4 hours, reaction
The sample of 500 hours, with the sulphur in gas Chromatographic Determination raw material and the product obtained, nitrogen content.
Comparative example 2-4
Catalyst D1, catalyst combination D1+II-1 and catalyst II-1 are hydrogenated with according to embodiment 11-16 method
Refined evaluation, and calculated according to hydrofinishing evaluation result computational methods, evaluation result is as shown in table 2 below.
Hydrofinishing evaluation result computational methods:
Catalysis is evaluated using the relative hydrodesulfurization activity relative to reference agent D1 (catalyst prepared in comparative example 1)
The hydrodesulfurization activity of agent, handled hydrodesulfurization reaction as 1.65 order reactions, catalyst X reaction speed is calculated by formula (1)
Rate constant k (X)HDS:
Volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction in formula (1).
The catalyst D1 prepared with comparative example 1 hydrodesulfurization activity [is designated as k (D1)HDS] on the basis of, calculated by formula (2)
Catalyst X relative hydrodesulfurization activity:
Catalysis is evaluated using the relative hydrodenitrogenationactivity activity relative to reference agent D1 (catalyst prepared in comparative example 1)
The hydrodenitrogenationactivity activity of agent, using hydrodenitrogeneration reaction as the processing of 1 order reaction, the reaction rate that catalyst X is calculated by formula (3) is normal
Number k (X)HDN:
Volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction in formula (3).
The catalyst D1 prepared with comparative example 1 hydrodenitrogenationactivity activity [is designated as k (D1)HDN] on the basis of, calculated by formula (4)
Catalyst X relative hydrodenitrogenationactivity activity:
The result explanation of table 2, the hydrogenating catalyst composition that the disclosure provides have preferably relative hydrodesulfurization activity
With relative hydrodenitrogenationactivity activity, and relative activity fall is small in the unit interval, and service life is longer.
Table 1
Table 2
Note:In table 2, "-" represents not detected.
Table 3
S contents | 12000μg/g |
N content | 220μg/g |
Density (20 DEG C) | 0.8588g/cm3 |
Refraction index (20 DEG C) | 1.4841 |
Claims (17)
1. a kind of hydrogenating catalyst composition, the hydrogenating catalyst composition includes hydrogenation catalyst I and hydrogenation catalyst II;With
Stereometer and on the basis of the hydrogenating catalyst composition, the content of the hydrogenation catalyst I is 5-95%;The hydrogenation is urged
Agent I includes carrier, hydrogenation active metals element and non-metal assistant element, and the hydrogenation active metals element contains VI B
Race's metallic element and group VIII metallic element;
Wherein, the preparation method of the hydrogenation catalyst I includes:
The carrier of the compound for being loaded with the element containing hydrogenation active metals, the first organic complexing agent and non-metal assistant element is entered
Row first is dried and is calcined, and obtains semi-finished product catalyst;Wherein, in terms of butt and with the butt weight of the semi-finished product catalyst
On the basis of, the carbon content of the semi-finished product catalyst is 0.01-0.5 weight %;
Second organic complexing agent is loaded on the semi-finished product catalyst, and carries out second and dries and without roasting, obtain
The hydrogenation catalyst I.
2. hydrogenating catalyst composition according to claim 1, wherein, in hydrogenation reactor, the hydrogenation catalyst I
Type of feed with hydrogenation catalyst II is layering filling or mixed packing;The mode of the layering filling includes:According to raw material
The flow direction of oil, the hydrogenation catalyst I is seated in the upstream of the hydrogenation catalyst II, the hydrogenation catalyst II is seated in institute
The upstream or the hydrogenation catalyst I for stating hydrogenation catalyst I are loaded with the hydrogenation catalyst II alternatively layereds.
3. hydrogenating catalyst composition according to claim 1, wherein, it is described to be loaded with the element containing hydrogenation active metals
The preparation process of the carrier of compound, the first organic complexing agent and non-metal assistant element includes:
With the aqueous solution of the compound containing the element containing hydrogenation active metals and the first organic complexing agent dipping containing described
The carrier of non-metal assistant element;
Or with the compound containing the element containing hydrogenation active metals, non-metal assistant element and the first organic complexing agent
Solution impregnating carrier.
4. hydrogenating catalyst composition according to claim 1, wherein, in terms of butt and with the semi-finished product catalyst
On the basis of butt weight, the carbon content of the semi-finished product catalyst is 0.04-0.4 weight %.
5. hydrogenating catalyst composition according to claim 1, wherein, the described first condition dried and described second dry
Dry condition includes independently of one another:Dry temperature is 100-250 DEG C, and the dry time is 1-12 hours;The roasting
Condition includes:Carried out under conditions of oxygen-containing gas is passed through, on the basis of the weight of carrier, the intake of oxygen-containing gas is 0.2-
20 liters/(gram hour);The temperature of roasting is 350-500 DEG C, and the time of roasting is 0.5-8 hours.
6. hydrogenating catalyst composition according to claim 1, wherein, first organic complexing agent and second organic network
Mixture includes organic oxygen-containing compound and/or nitrogen-containing organic compound independently of one another;The organic oxygen-containing compound is organic
Alcohol and/or organic acid, the nitrogen-containing organic compound are organic amine and/or organic ammonium salt.
7. hydrogenating catalyst composition according to claim 1, wherein, first organic complexing agent and second organic network
Mixture is included selected from ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, grass independently of one another
Acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, malic acid, ethylenediamine and ethylenediamine tetra-acetic acid
At least one of.
8. hydrogenating catalyst composition according to claim 1, wherein, the hydrogenation active metals element and described first
The mol ratio of organic complexing agent is 1:(0.03-2).
9. hydrogenating catalyst composition according to claim 1, wherein, first organic complexing agent has with described second
The mol ratio of machine complexing agent is 1:(0.25-4).
10. hydrogenating catalyst composition according to claim 1, wherein, in terms of oxide and with the hydrogenation catalyst I
Gross weight on the basis of, the content of the hydrogenation active metals element is 6-70 weight %;Urged in terms of element and with the hydrogenation
On the basis of agent I gross weight, the content of the non-metal assistant element is no more than 10 weight %.
11. hydrogenating catalyst composition according to claim 1, wherein, the non-metal assistant element is selected from IV A
At least one of race's element, V Group IIA element, V A race's elements and group III A element, the carrier are selected from γ-oxygen
Change aluminium, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica-oxygen
Change thorium, silica-berylias, silica-titania, titania-zirconia, silica-alumina thoria, silica-oxygen
Change the one or more in aluminium-titanium oxide, silicaalumina-magnesia and silica-alumina, zirconia.
12. hydrogenating catalyst composition according to claim 11, wherein, the vib metals element be molybdenum and/or
Tungsten, the group VIII metallic element are cobalt and/or nickel;The non-metal assistant element is selected from fluorine element, element silicon, phosphorus member
At least one of element and boron element.
13. hydrogenating catalyst composition according to claim 1, wherein, in terms of oxide and with the hydrogenation catalyst I
Gross weight on the basis of, the content of the group VIII metallic element is 1-10 weight %, and the vib metals element contains
Measure as 5-60 weight %.
14. hydrogenating catalyst composition according to claim 1, wherein, the hydrogenation catalyst II contains at least one
Vib metals element and at least one group VIII metallic element;In terms of oxide and with the total of the hydrogenation catalyst II
On the basis of weight, the content of the group VIII metallic element is 1-10 weight %, and the content of the vib metals element is
5-60 weight %.
15. a kind of method of hydrotreating, this method include:By adding described in any one in feedstock oil and claim 1-14
Hydrogen catalyst composition contacts and carries out hydrogenation reaction.
16. according to the method for claim 15, wherein, the condition of the hydrogenation reaction includes:Temperature is 300-400 DEG C,
Pressure is 1-10 MPas, and volume space velocity is 0.5-3 hours during the liquid of feedstock oil-1, hydrogen to oil volume ratio 100-800.
17. according to the method for claim 15, wherein, the feedstock oil is selected from gasoline, diesel oil, lubricating oil, kerosene, stone
At least one of cerebrol, reduced crude, decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil.
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RU2019106451A RU2745607C2 (en) | 2016-09-12 | 2017-04-24 | Hydration catalyst, its preparation and application |
EP17847869.9A EP3511074A4 (en) | 2016-09-12 | 2017-04-24 | Hydrogenation catalyst, manufacturing method therefor, and application thereof |
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