CN106669706A - Preparation method of hydrotreating catalyst - Google Patents

Preparation method of hydrotreating catalyst Download PDF

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Publication number
CN106669706A
CN106669706A CN201510750630.5A CN201510750630A CN106669706A CN 106669706 A CN106669706 A CN 106669706A CN 201510750630 A CN201510750630 A CN 201510750630A CN 106669706 A CN106669706 A CN 106669706A
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catalyst
oxide
content
preparation
methods according
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Inventor
唐兆吉
杨占林
姜虹
温德荣
王平
孙立刚
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/883Molybdenum and nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/882Molybdenum and cobalt
    • B01J35/60
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining 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
    • C10G45/04Refining 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
    • C10G45/06Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P

Abstract

The invention discloses a preparation method of a hydrotreating catalyst. The preparation method comprises the following steps: (1) preparing an impregnating solution containing group-VIII metals, group-VIB metals and 2-amino-1,3 propylene glycol, wherein the molar ratio of 2-amino-1,3 propylene glycol in the impregnating solution to group-VIII metal atoms contained in a final catalyst is 0.1:1 to 2:1; (2) impregnating an aluminum oxide carrier by adopting the impregnating solution prepared in the step (1) and firstly treating for 2-60 minutes under the condition that the microwave power is 2-20 W/g after the end of impregnation; then drying to prepare the hydrotreating catalyst. The catalyst prepared by the preparation method disclosed by the invention is easy to fully vulcanize; more Class-II active centers are generated, so that the effective utilization rate of active components is increased, and the activity of the catalyst is improved.

Description

A kind of preparation method of hydrotreating catalyst
Technical field
The present invention relates to a kind of preparation method of hydrotreating catalyst, is especially suitable for heavy distillate hydrogenation de- The preparation method of nitrogen, the hydrotreating catalyst of sweetening process.
Background technology
Content containing nitrogen, sulphur, oxygen and metal impurities in crude oil is continuously increased, and crude oil degree of heaviness is constantly deepened, Pendulum is come true in face of people, and the presence of these impurity not only makes catalyst poisoning in subsequent processes, but also meeting The pernicious gases such as substantial amounts of sulfur and nitrogen oxides are given off, the health of the mankind and the protection of environment is injured.Using work Property the high, catalyst of good stability relax can not only process conditions, moreover it is possible to reduce hydrogen consumption, reach energy-saving effect.
Hydroprocessing processes be exactly with containing the VIIIth race in periodic table and group VIB it is metal oxide supported to refractory without In machine porous material, typically using aluminum oxide, silica, titanium dioxide, carborundum, boron oxide, zirconium oxide and their combinations Composite carrier together.By dipping process, catalyst precarsor is prepared, then through the drying and roasting of some steps Operation prepares finished catalyst.Finished catalyst is containing hydrogen sulfide, sulfur-bearing organic compound using presulfurization is front carried out In the presence of thing or elemental sulfur, oxidized catalyst is set to change into sulphided state catalyst.
The purpose of weighted BMO spaces is to remove the impurity such as nitrogen, sulphur, oxygen in feedstock oil, the quality and quantity of intermediate oil All increased.For example, it is hydrocracked and is required for pre-processing feedstock oil with hydroforming reaction, prevents miscellaneous in crude oil Matter makes catalyst poisoning, and catalyst is once be poisoned, and the loss for causing is inestimable.So, hydroprocessing processes are oil refining process In one of indispensable and particularly significant step.It is known in the art, without the activearm of calcined catalyst Divide dispersiveness high, weaker model ylid bloom action power is only existed between active metal and carrier, therefore it is anti-to effectively improve catalyst Should activity.High activity, the development of the catalyst of high stability are always the bottleneck of this area institute Gonna breakthrough, industrial using high living Property, high stability catalyst not only can voluminous target product, and reaction can also be made to carry out under conditions of relatively relaxing, transport Turn cycle stretch-out, reduce production cost.
This area is done a lot of work in terms of activity of hydrocatalyst is improved, and many documents have been reported, and are achieved Great success, is that later research and development are laid a good foundation.CN 85103891 describes the preparation method of hydrogenation conversion catalyst.Should Method is that phosphorus containg substances and soluble amine compound are separately added into maceration extract, and two kinds of solution is admixed together to be impregnated, And need to adjust the pH value of maceration extract and the temperature of dipping solution in dipping process.The method prepares catalyst process condition and answers Miscellaneous, ammonium hydroxide has ammonia to release in course of dissolution, and harmful to environment, denitrification effect is not obvious, is difficult industrialized production.
Chinese patent CN 101590416A describe the preparation method of molybdenum-nickel hydrogenation catalyst, the method be using kneading ~ Two steps of dipping are prepared catalyst, first under conditions of nitric acid presence, by molybdenum oxide, titanium-containing compound, containing phosphatization Compound and aluminum oxide Jing kneadings, extruded moulding, dry, roasting obtains the aluminum oxide article shaped of titaniferous, phosphorus, molybdenum, then impregnates nickeliferous Phosphoric acid solution, obtain molybdenum-nickel hydrogenation catalyst after drying, roasting.Chinese patent CN 1052501A disclose hydrogenation and urge The preparation method of agent.The method is added in the maceration extract containing the metals of Co-W-Mo tri- and helped to improve the activity of catalyst Agent P, F, B, using segmentation impregnation, after drying, roasting finished catalyst are obtained.Said method is lived in dip loading Property metal after through high-temperature roasting, active metal component is stronger with the active force of carrier, affect catalyst cure efficiency, and And also assemble can amount of activated metal component, the decentralization of active metal is affected, and then affect the activity of catalyst.
In Japan Patent JP11033412, a kind of method for preparing load type metal catalyst is disclosed.The method is by gold The aqueous solution of category salt and surfactant is added in porous media material, and room temperature lower section is put more than 1 hour, and ultrasonic wave is used afterwards Process the maceration extract 2 hours, it is ultrasonically treated after, the porous media material after this is impregnated was in 120 DEG C of dryings 12 hours Roasting 2 hours, obtains finished catalyst under 500 DEG C of air atmospheres.The method preparation catalyst process engineering is loaded down with trivial details, and activity is low, It is unsuitable for industrial mass production.
Japan Patent JP 04 ~ 166231 describes a kind of hydrogenation catalyst preparation method.The method is soaked using substep Stain, carrier first with phosphorous active metal component solution impregnation after, be dried at room temperature ~ 200 DEG C, impregnated carrier after being dried Contact with polyol solution, passing below 200 DEG C of dryings, obtain finished catalyst.United States Patent (USP) US 6281333 Disclose a kind of preparation method of hydrotreating catalyst.The carrier loaded active metal maceration extract containing volatile organic components, no Catalyst is obtained through roasting, in above-mentioned catalyst preparation process, organic additive is added in maceration extract, the catalyst Jing rooms after dipping Temperature ageing is some as a child, is dried process.There is metal precipitating, color blackening phenomena in dried catalyst surface, and And have a large amount of dust to occur in catalyst surface.So both have impact on high degree of dispersion of the active component in carrier surface, and to urging Agent brings adverse effect during later stage filling, directly affects the reactivity of catalyst.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method of hydrotreating catalyst.The method is obtained Catalyst be easy to full cure, generate more II classes activated centres, increased the effective rate of utilization of active component, improve The activity of catalyst.
A kind of preparation method of hydrotreating catalyst, comprises the steps:
(1)Prepare and contain group VIII metal, group VIB metal and 2- amino -1, the maceration extract of 3 propane diols, 2- ammonia in maceration extract The content of propylene glycol of base -1,3 is 0.1 with the mol ratio of contained group VIII metal atom in final catalyst:1~2:1, preferably 0.5:1-1:1;
(2)Using step(1)The maceration extract oxide impregnation alumina supporter of preparation, dipping terminate after first microwave power be 2 ~ 20W/ 2 ~ 60min, most preferably preferably 5 ~ 30min, 10 ~ 15min are processed under conditions of g, preferably 6 ~ 18W/g, most preferably 8-10 W/g, Wherein microwave power presses the Mass Calculation of final catalyst;Then drying is obtained hydrotreating catalyst.
The inventive method step(1)In, group VIII metal is Co and/or Ni, and group VIB metal is W and/or Mo, with most On the basis of the weight of whole catalyst, the content that group VIII metal is counted with oxide is as 1 wt % ~ 15 wt %, preferred 4wt % ~ 10 Wt %, the content that group VIB metal is counted with oxide is as 10 wt % ~ 30 wt %.It is preferred that 15wt % ~ 25 wt %.Above-mentioned tungsten master Will be from one or two in ammonium metatungstate, tetrathio ammonium tungstate, molybdenum is essentially from molybdenum oxide, ammonium molybdate, tetrathio molybdic acid One or more in ammonium, ammonium paramolybdate, nickel mostlys come from nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride, nickel acetate One or more, cobalt mostlys come from one or more of cobalt nitrate, cobalt oxalate, basic cobaltous carbonate, cobaltous chlorate.
The inventive method step(1)In, described maceration extract can as needed contain auxiliary agent, and described auxiliary agent is selected from One or more in phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, vanadium, preferred phosphorus.Auxiliary agent is in terms of oxide in catalyst In weight content be 0.01% ~ 10%, preferably 0.01% ~ 2%.
The inventive method step(2)In, described alumina support can using commercial goods or self-control, preferably after Person.Self-control process is as follows:Aluminum hydroxide solid elastomer powder and SB powder are made into catalyst load through kneading, shaping, then drying roasting Body.The routine shaping assistant such as extrusion aid, binding agent, peptizing agent can be added as needed in kneading process.Described oxidation Adjuvant component can be contained in alumina supporter.Described drying condition is as follows:Baking temperature be 50 DEG C ~ 300 DEG C, preferably 100 DEG C ~ 150 DEG C, drying time 0.5h ~ 22h, preferred 8h ~ 15h.Be dried atmosphere can be air atmosphere, vacuum atmosphere, steam atmosphere, Inert gas atmosphere etc., is dried under preferred air atmosphere.Described roasting condition is as follows:Sintering temperature is 350 DEG C ~ 650 DEG C, excellent Select 450 DEG C ~ 550 DEG C, roasting time 0.5h ~ 22h, preferred 8h ~ 15h, most preferably 6 ~ 10h.Forming method mainly has compressing tablet, mould Plate, powder spin, extrusion, forming oil column etc., the shape of carrier can be spherical, piece shape, bar shaped(Clover or bunge bedstraw herb Irregular strip)Deng.The shape of carrier can be selected according to specific needs, preferably bar shaped, and carrier dimensions may be selected on request difference.
The inventive method step(2), described baking temperature is 100 DEG C ~ 250 DEG C, preferably 120 DEG C ~ 200 DEG C, when being dried Between 0.5h ~ 5h, preferred 1h ~ 3h.
Result of study shows that 2- amino -1 in maceration extract of the present invention, 3 propane diols have with group VIII metal atom Ni or Co Stronger interaction, can form stable comple.Particularly above-mentioned complex compound 2- ammonia under suitable microwave treatment conditions Base -1, the active force of the chelate bonds that 3 propane diols are formed with group VIII metal atom Ni or Co is further strengthened, and makes Ni or Co Curing temperature significantly improve than the curing temperature of Mo or W, postpone Ni or Co sulfuration, increase molybdenum or the sulphidity of tungsten, hold Class Ni (Co)-Mo (the W)-S of high activity II activated centres are easily formed, and can at short notice make active component be dispersed in load Body surface face, specific surface area of catalyst is big, and active bit quantity increases, and substantially increases active component effective rate of utilization, reduces catalysis The cost of agent.
Specific embodiment
The present invention is further elaborated below by embodiment, but following examples do not constitute the limit to the inventive method System.In the present invention, wt% is mass fraction.
Embodiment 1(It is prepared by alumina support)
200 grams of aluminum hydroxide solid elastomer powder is weighed, 100 grams of SB powder adds sesbania powder and citric acid each 4 grams, adds after mixing acid Solution, the concentration of nitric acid is 2wt% in acid solution, and remaining is distilled water.Roll 15 ~ 25 minutes, with the three of a diameter of 1.7mm Leaf grass orifice plate carries out extrusion, 120 DEG C of Jing dryings 12 hours, 550 DEG C of roastings 3 hours, obtains alumina support, i.e. Z-1, its property It is as follows:Pore volume is 0.72ml/g, and specific surface area is 342m2/g。
Embodiment 2
Appropriate carrier Z-1 is weighed, with Mo, Ni, P, 2- amino -1 is contained, the maceration extract of 3 propane diols carries out waiting body to carrier Z-1 Product dipping, maceration extract consists of MoO3Content be 88.5g/100ml, NiO contents are 15 g/100ml, and the content of P is 2.3g/100ml, 2- amino -1, the consumption of 3 propane diols is 0.5 with the mol ratio of Ni atoms in final catalyst:1.Dipping terminates After carry out microwave treatment, the power of microwave is 8 W/g, and process time is 15min, and the sample after microwave treatment is in 180 DEG C of air Drying under atmosphere obtains catalyst C-1 in 3 hours, and catalyst consists of 23%MoO3, 3.6%NiO, 1.5% p.
Embodiment 3
Appropriate catalyst carrier Z-1 is weighed, with Mo, Ni, P, 2- amino -1 is contained, the maceration extract of 3 propane diols is to carrier Z-1 Carry out incipient impregnation, maceration extract consists of MoO3Content be 89.5g/100ml, NiO contents be 15 g/100ml, P's Content is 2.5g/100ml, and 2- amino -1, the consumption of 3 propane diols is 1 with the mol ratio of Ni contents in final catalyst:1.Leaching Sample after stain carries out microwave treatment, and the power of microwave is 10 W/g, and process time is 15min, and the sample after microwave treatment exists Drying under 150 DEG C of air atmospheres obtains catalyst C-2 in 1 hour, and catalyst consists of 23%MoO3, 3.6%NiO, 1.63% p.
Embodiment 4
Appropriate catalyst carrier Z-1 is weighed, with Mo, Ni, P, 2- amino -1 is contained, the maceration extract of 3 propane diols enters to carrier Z-1 Went volume impregnation, maceration extract consists of MoO3Content be 89.5g/100ml, NiO contents be 15 g/100ml, P's contains Measure as 2.5g/100ml, 2- amino -1, the consumption of 3 propane diols is 1 with the mol ratio of Ni contents in final catalyst:1.After filtration Sample carry out microwave treatment, the power of microwave is 10W/g, and process time is 25min, and the sample after microwave treatment is at 180 DEG C Drying under air atmosphere obtains catalyst C-3 in 1 hour, and catalyst consists of 23%MoO3, 3.6%NiO, 1.63% p.
Embodiment 5
Appropriate catalyst carrier Z-1 is weighed, with Mo, Co, P, 2- amino -1 is contained, the maceration extract of 3 propane diols enters to carrier Z-1 Went volume impregnation, maceration extract consists of MoO3Content be 89.5g/100ml, CoO contents be 13.5 g/100ml, P's Content is 2.2g/100ml, and the consumption of the propane diols of 2- amino -1,3 is 0.8 with the mol ratio of Ni contents in final catalyst:1. Sample after filtration carries out microwave treatment, and the power of microwave is 15W/g, and process time is 20min, and the sample after microwave treatment exists Drying under 130 DEG C of air atmospheres obtains catalyst C-4 in 3 hours, and catalyst consists of 23%MoO3, 3.6%CoO, 1.48% p.
Comparative example 1
It is added without 2- amino -1,3 propane diols, remaining obtains catalyst C-5 with embodiment 1.
Comparative example 2
Microwave treatment is not carried out, remaining obtains catalyst C-6 with embodiment 1.
Comparative example 3
Using citric acid replacement 2- amino -1 of same molar, 3 propane diols, remaining obtains catalyst C-7 with embodiment 1.
The catalyst of above-described embodiment and comparative example carries out active evaluation test, institute in the small-sized hydrogenation reaction devices of 50ml It is atmosphere 3rd side cut diesel oil with raw material, property is shown in Table 1.Catalyst will carry out presulfurization using before, and sulfurized oil is virgin kerosene, wherein Add the DMDS of 5wt%(DMDS), feedstock oil is introduced directly into after presulfurization carries out test reaction.Presulfurization and test bar Part is shown in Table 2, and evaluation result is shown in Table 3.
Table 1
Table 2
Table 3
From data in table 3, prepared apparently higher than comparative example method using the activity of the catalyst of the inventive method preparation Catalyst.
Table 4
Catalyst is numbered C-1 C-2 C-3 C-4 C-5 C-6 C-7
With respect to denitrification activity, % 139 155 140 142 100 118 121
It is relatively desulphurizing activated, % 132 145 128 121 98 102 110
C-1 ~ C-7 catalyst 1200h Activity evaluations are shown in Table 4, and by data in table 4 the inventive method preparation is can be seen that Catalyst stability is good, is conducive to long-term operation.

Claims (18)

1. a kind of preparation method of hydrotreating catalyst, it is characterised in that:Comprise the steps:
(1)Prepare and contain group VIII metal, group VIB metal and 2- amino -1, the maceration extract of 3 propane diols, 2- ammonia in maceration extract The content of propylene glycol of base -1,3 is 0.1 with the mol ratio of contained group VIII metal atom in final catalyst:1~2:1;
(2)Using step(1)The maceration extract oxide impregnation alumina supporter of preparation, dipping terminate after first microwave power be 2 ~ 20W/ 2 ~ 60min is processed under conditions of g, then drying is obtained hydrotreating catalyst.
2. method according to claim 1, it is characterised in that:Step(1)The content of propylene glycol of 2- amino -1,3 in maceration extract It is 0.5 with the mol ratio of contained group VIII metal atom in final catalyst:1-1:1.
3. method according to claim 1, it is characterised in that:Step(2)Dipping terminate after first microwave power be 6 ~ 5 ~ 30min is processed under conditions of 18W/g.
4. method according to claim 3, it is characterised in that:Step(2)Dipping terminate after first microwave power be 8- 10 ~ 15min is processed under conditions of 10 W/g.
5. method according to claim 1, it is characterised in that:Step(1)In, group VIII metal be Co and/or Ni, the VIth B races metal is W and/or Mo, and on the basis of the weight of final catalyst, the content that group VIII metal is counted with oxide is as 1 wt % ~ 15 wt %, the content that group VIB metal is counted with oxide is as 10 wt % ~ 30 wt %.
6. method according to claim 5, it is characterised in that:On the basis of the weight of final catalyst, group VIII metal , as 4wt % ~ 10 wt %, the content that group VIB metal is counted with oxide is as 15wt % ~ 25 wt % for the content counted with oxide.
7. method according to claim 5, it is characterised in that:The one kind of tungsten in ammonium metatungstate, tetrathio ammonium tungstate Or two kinds.
8. method according to claim 5, it is characterised in that:Molybdenum is from molybdenum oxide, ammonium molybdate, four thio ammonium molybdate, secondary One or more in ammonium molybdate.
9. method according to claim 5, it is characterised in that:Nickel comes from nickel nitrate, basic nickel carbonate, nickel oxalate, chlorine One or more of change nickel, nickel acetate.
10. method according to claim 5, it is characterised in that:Cobalt comes from cobalt nitrate, cobalt oxalate, basic cobaltous carbonate, chlorine One or more of sour cobalt.
11. methods according to claim 1, it is characterised in that:Step(1)Described in maceration extract contain auxiliary agent, it is described One or more in phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, the vanadium of auxiliary agent.
12. methods according to claim 11, it is characterised in that:Auxiliary agent is phosphorus.
13. methods according to claim 11, it is characterised in that:Weight content of the auxiliary agent in terms of oxide in the catalyst For 0.01% ~ 10%.
14. methods according to claim 1, it is characterised in that:Step(2)Middle carrying alumina production procedure is as follows:Will Aluminum hydroxide solid elastomer powder and SB powder kneadings, shaping, then make catalyst carrier after drying, roasting.
15. methods according to claim 14, it is characterised in that:Extrusion aid, binding agent and peptization are added in kneading process Agent.
16. methods according to claim 14, it is characterised in that:Described drying condition is as follows:Baking temperature be 50 DEG C ~ 300 DEG C, drying time 0.5h ~ 22h, described roasting condition is as follows:Sintering temperature is 350 DEG C ~ 650 DEG C, roasting time 0.5h ~ 22h。
17. methods according to claim 1, it is characterised in that:Step(2)Described baking temperature is 100 DEG C ~ 250 DEG C, Drying time 0.5h ~ 5h.
18. methods according to claim 17, it is characterised in that:Step(2)Described baking temperature is 120 DEG C ~ 200 DEG C, drying time 1h ~ 3h.
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CN111974406A (en) * 2019-05-22 2020-11-24 环球油品有限责任公司 Process for preparing highly reactive metal oxide and metal sulfide materials

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CN111974406A (en) * 2019-05-22 2020-11-24 环球油品有限责任公司 Process for preparing highly reactive metal oxide and metal sulfide materials
CN110280258A (en) * 2019-08-02 2019-09-27 北京高新利华科技股份有限公司 A kind of diesel oil hydrofining catalyst and preparation method thereof
CN110280258B (en) * 2019-08-02 2022-05-17 北京高新利华科技股份有限公司 Diesel oil hydrofining catalyst and preparation method thereof
CN111729689A (en) * 2020-06-19 2020-10-02 湖北中超化工科技有限公司 Regeneration method of deactivated hydrogenation catalyst

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