CN108452846A - Gasoline hydrogenation treatment catalyst and preparation method thereof - Google Patents
Gasoline hydrogenation treatment catalyst and preparation method thereof Download PDFInfo
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- CN108452846A CN108452846A CN201711032892.3A CN201711032892A CN108452846A CN 108452846 A CN108452846 A CN 108452846A CN 201711032892 A CN201711032892 A CN 201711032892A CN 108452846 A CN108452846 A CN 108452846A
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- Prior art keywords
- hydrogenation treatment
- gasoline hydrogenation
- catalyst
- treatment catalyst
- carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
Abstract
A kind of gasoline hydrogenation treatment catalyst, including carrier and active component, active component are carried on carrier, using heteropoly acid as active component, Al2O31 graphene composite oxides of TS are carrier；Specific surface area of catalyst is 250~500m20.5~0.8mL/g of/g, Kong Rongwei.The method for preparing catalyst be by molecular sieve and aluminium oxide and graphene after mixing, salpeter solution and suitable quantity of water is added, the catalyst carrier of the present invention is made after kneading, extrusion, drying, roasting.Carrier is impregnated with the solution containing heteropoly acid, and catalyst of the present invention is obtained after drying, roasting.The features such as catalyst has special pore size distribution, large hole is held, higher hydrodesulfurization activity can be used as gasoline hydrogenation treatment catalyst use.
Description
Technical field
The present invention relates to a kind of gasoline hydrogenation treatment catalyst and preparation method thereof, the gasoline suitable for petroleum refining field
Unifining process.
Background technology
Currently, hydrodesulfurization is to reduce a kind of main method of sulfur content in gasoline stocks, it can be carried out at the same time plus hydrogen is de-
Reactions, V gasoline of producing country or its blend component such as sulphur, hydrodenitrogeneration, alkene saturation.
China in 2017 carries out V motor petrol standard of state comprehensively, plans to carry out VI motor petrol standard of state in 2019.Vapour
Catalytic gasoline, coker gasoline have higher sulphur, nitrogen, olefin(e) centent, it more difficult in processing compared with direct steaming gasoline in oily raw material.
In order to meet the requirement of tightened up standard, while crude oil in poor quality trend is coped with, novel high-activity gasoline hydrogenation catalyst is ground
Send out imperative.
CN100998952A prepares the coking gasoline hydrogenation refining catalyst containing Mo, W, Ni, P, the catalyst metals
Content is high, has alkene saturation temperature low when processing coker gasoline, carries out alkene saturation, desulfurization, denitrogenation at a lower temperature
Reaction, coking speed is slow, and the regeneration period is long, but this catalyst is prepared using double-steeping method, and preparation process is cumbersome, and low temperature
The lower desulfurization of degree, denitrification effect are bad.
Invention content
It is an object of the invention to develop a kind of gasoline hydrogenation treatment catalyst, support acidity is adjusted by TS-1 contents,
It uses containing heteropoly acid as maceration extract, weakens the interaction of carrier and active component, prepare the gasoline of active component high degree of dispersion
Hydrobon catalyst significantly improves the hydrodesulfurization activity of catalyst, is suitable for direct steaming gasoline, catalytic gasoline, coker gasoline
Or the hydrofinishing of its miscella.
The present invention provides a kind of gasoline hydrogenation treatment catalyst, including carrier and active component, active component are carried on load
On body, wherein：
Using heteropoly acid as active component, Al2O3- TS-1- graphene composite oxides are carrier；
Specific surface area of catalyst is 250~500m20.5~0.8mL/g of/g, Kong Rongwei.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：In terms of oxide, it is total that active component preferably accounts for catalyst
10~40wt% of quality.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：Based on the weight percent of catalyst, TS-1 molecular sieves
Content is preferably 5~30wt%, γ-Al2O3Content is preferably 25~60wt%, and graphene content is preferably 0.01~5wt%,
Heteropoly acid content is preferably 10~40wt%.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：The heteropoly acid is preferably M6[WM3(H2O)2
(ZnW9O34)2], M is preferably one or more of Mn, Co, Ni and Cu.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：The shape of catalyst is preferably sheet, spherical shape, cylinder
Item, irregular strip, graininess or tooth are spherical.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：The diameter of catalyst is preferably 0.8mm~2.0mm's
Slice or thick item more than 2.5mm.
Gasoline hydrogenation treatment catalyst of the present invention, wherein：The diameter of catalyst is more preferably 1.0mm~1.8mm
Slice.
The present invention also provides a kind of preparation methods of gasoline hydrogenation treatment catalyst, are above-mentioned gasoline hydrofinishing catalysis
The preparation method of agent, includes the following steps：
(1) alumina powder is uniformly mixed with TS-1 molecular sieves, adds graphene, add extrusion aid after mixing and glued
Mixture is uniformly mixed again, extruded moulding, and carrier is made in freeze-drying or vacuum drying after roasting；
(2) it is made into maceration extract with the heteropoly acid containing active component, carrier obtained is subjected to incipient impregnation, freezing is dry
Dry or vacuum drying, is made gasoline hydrogenation treatment catalyst after roasting.
The preparation method of gasoline hydrogenation treatment catalyst of the present invention, wherein：The heteropoly acid is preferably M6[WM3
(H2O)2(ZnW9O34)2], M is preferably one or more of Mn, Co, Ni and Cu.
The preparation method of gasoline hydrogenation treatment catalyst of the present invention, wherein：The extrusion aid is preferably starch, field
One or more of cyanines powder, polyvinyl alcohol, methylcellulose and polyethylene glycol.
The preparation method of gasoline hydrogenation treatment catalyst of the present invention, wherein：Described adhesive is preferably nitric acid, lemon
One or more of lemon acid, ethanedioic acid and tartaric acid.
The preparation method of gasoline hydrogenation treatment catalyst of the present invention, wherein：The medium volume dip time of step (2)
Preferably 0.5~5 hour；Roasting condition is preferably in step (2)：It is roasted 2~6 hours at 400~550 DEG C.
The present invention can be with details are as follows：
Gasoline hydrogenation treatment catalyst of the present invention is using heteropoly acid solution as maceration extract, Al2O3- TS-1- graphene combined oxidations
Object is carrier.Specific surface area of catalyst is 250~500m2/ g, hole hold 0.5~0.8mL/g.
Gasoline hydrogenation treatment catalyst of the present invention, based on the weight percent of catalyst, TS-1 molecular sieve contents be 5~
30wt%, γ-Al2O3Content be 25~60wt%, graphene content be 0.01~5wt%, heteropoly acid content be 10~
40wt%.
Gasoline hydrogenation treatment catalyst of the present invention, the heteropoly acid contained in used maceration extract are M6[WM3(H2O)2
(ZnW9O34)2] (M=Mn, Co, Ni, Cu) one or more.
Gasoline hydrogenation treatment catalyst of the present invention, active metal W, Mn, Co, Ni, Cu etc., the active component in terms of oxide
Content 10~40%.
Gasoline hydrogenation treatment catalyst preparation process of the present invention is as follows：Alumina powder is uniformly mixed with TS-1 molecular sieves,
Appropriate graphene is added, appropriate extrusion aid and adhesive is added after mixing, is uniformly mixed again.Extruded moulding, shape can
To be that bar shaped, cloverleaf pattern, graininess or tooth are spherical.After freeze-drying or vacuum drying, roasts and carrier is made.With containing active
The heteropoly acid of metal is made into maceration extract.Carrier obtained is subjected to incipient impregnation, after freeze-drying or vacuum drying, roasting system
Obtain gasoline hydrogenation treatment catalyst.
Above-mentioned graphene can be or mixtures thereof graphene oxide, graphene.
Above-mentioned extrusion aid can be starch, sesbania powder, polyvinyl alcohol, methylcellulose, one kind in polyethylene glycol or several
Kind, it is subject to each component total weight, additive amount is 1%~5%, preferably 2%~4%.
Above-mentioned adhesive can be one or more of nitric acid, citric acid, ethanedioic acid, tartaric acid, with each component gross weight
Subject to amount, additive amount is 1%~10%, preferably 4%~8%.
The carrier impregnation time is 0.5~5 hour, preferably 1~3 hour in the present invention.It is dry that impregnated carrier carries out freezing
Dry, carrier roasts 2~6 hours, preferably 3~5 hours at 400~550 DEG C, and gasoline hydrogenation treatment catalyst is made.
Gasoline hydrogenation treatment catalyst of the present invention can be used for after vulcanization direct steaming gasoline, catalytic gasoline, coker gasoline or its
The hydrofinishing of miscella.Reaction condition is that reaction temperature is 220~350 DEG C, and hydrogen partial pressure is 1.0~6.0MPa, hydrogen oil volume
Than 100:1~500:1, volume space velocity is 0.5~3.0h-1。
Beneficial effects of the present invention：
The present invention provides a kind of preparation method of gasoline hydrogenation treatment catalyst, passes through TS-1 molecular sieves, graphene modulation
The acidity of alumina support weakens the interaction of carrier and active component, increases specific surface area of catalyst, improves it and adds hydrogen de-
Sulphur activity.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The gasoline hydrogenation treatment catalyst of the present invention can be used for direct steaming gasoline, catalytic gasoline, coker gasoline or its mixing
The hydrofinishing of oil.
The following examples will be further described a kind of gasoline hydrogenation treatment catalyst provided by the invention, but
It is not thereby limiting the invention.
Embodiment 1
It takes 100g boehmites, 20gTS-1 molecular sieves that graphene 1g is added, is uniformly mixed.4g sesbania powders are added, mix
Close uniform, be added dropwise the mixed solution kneading being made of 4g nitric acid, 4g citric acids and 40g deionized waters, extrusion at 1.5mm three leaves
Careless shape, freeze-drying, then 550 DEG C of roasting 4h, are made carrier.Ni is used again6[WNi3(H2O)2(ZnW9O34)2] prepare maceration extract
Catalyst A is made in incipient impregnation, freeze-drying, 400 DEG C of roasting 4h.
Embodiment 2
It takes 100g boehmites, 20gTS-1 molecular sieves that graphene 1g is added, is uniformly mixed.4g sesbania powders are added, mix
Close uniform, be added dropwise the mixed solution kneading being made of 4g nitric acid, 4g citric acids and 40g deionized waters, extrusion at 1.5mm three leaves
Careless shape, freeze-drying, then 550 DEG C of roasting 4h, are made carrier.Co is used again6[WCo3(H2O)2(ZnW9O34)2] prepare maceration extract
Catalyst B is made in incipient impregnation, freeze-drying, 400 DEG C of roasting 4h.
Embodiment 3
It takes 100g boehmites, 84gTS-1 molecular sieves that 14g graphenes are added, is uniformly mixed.14g sesbania powders are added,
It being uniformly mixed, the aqueous solution kneading of nitric acid containing 14g, 14g citric acids is added dropwise, extrusion is freeze-dried at the cylinder bar shaped of 1.5mm,
Then 550 DEG C of roasting 4h, are made carrier.Ni is used again6[WNi3(H2O)2(ZnW9O34)2] prepare maceration extract incipient impregnation, it is cold
Dry, 400 DEG C of roastings 6h, obtained catalyst C are lyophilized.
Embodiment 4
It takes 100g boehmites, 5.8gTS-1 molecular sieves that graphene 0.1g is added, is uniformly mixed.1.2g sesbanias are added
Powder is uniformly mixed, and the aqueous solution kneading of nitric acid containing 1.2g, 1.2g citric acids is added dropwise, extrusion is at the cloverleaf pattern of 1.5mm, freezing
Dry, then 550 DEG C of roasting 4h, are made carrier.Cu is used again6[WCu3(H2O)2(ZnW9O34)2] prepare maceration extract soak in equal volume
Catalyst D is made in stain, freeze-drying, 550 DEG C of roasting 2h.
Embodiment 5
It takes 100g boehmites, 35gTS-1 molecular sieves that graphene 0.1g is added, is uniformly mixed.4g sesbania powders are added,
It is uniformly mixed, the aqueous solution kneading of nitric acid containing 4g, 4g citric acids is added dropwise, extrusion is freeze-dried, so at the cloverleaf pattern of 1.5mm
550 DEG C of roasting 4h afterwards, are made carrier.Mn is used again6[WMn3(H2O)2(ZnW9O34)2] prepare maceration extract incipient impregnation, freezing
Dry, catalyst E is made in 400 DEG C of roasting 4h.
Comparative example 1
A kind of regular price gasoline Hydrobon catalyst F, hydrogenation active metals are molybdenum, nickel.This catalyst is to carry with aluminium oxide
Body, the co-impregnated solution prepared with nickel nitrate and ammonium molybdate impregnate, and 100 DEG C~120 DEG C dry 4h, 500 DEG C~600 DEG C roast 4h and make
.
The physicochemical properties of 1 catalyst of table
Embodiment 6
This example introduces the micro anti-evaluation result of above-mentioned catalyst.
The catalytic amount that micro anti-evaluation uses is 5g, is evaluation raw material with direct steaming gasoline and coker gasoline miscella, carries out
Gasoline hydrogenation catalyst is evaluated.Reaction condition is 260 DEG C, hydrogen partial pressure 2.0MPa of reaction temperature, hydrogen to oil volume ratio 500:1, body
Product air speed is 2.0h-1.The micro anti-evaluation of catalyst the results are shown in Table 2.
Table 2 is micro- instead to add hydrogen evaluation result
As can be seen from Table 2, the introducing of molecular sieve, graphene, the hydrodesulfurization for significantly improving triturate of the present invention are lived
Property.Gasoline hydrogenation treatment catalyst of the present invention has the characteristics that large specific surface area, active metal utilization rate are high, has good answer
Use foreground.
Claims (12)
1. a kind of gasoline hydrogenation treatment catalyst, including carrier and active component, active component are carried on carrier, feature
It is：
Using heteropoly acid as active component, Al2O3- TS-1- graphene composite oxides are carrier；
Specific surface area of catalyst is 250~500m20.5~0.8mL/g of/g, Kong Rongwei.
2. gasoline hydrogenation treatment catalyst according to claim 1, it is characterised in that：In terms of oxide, active component accounts for
10~40wt% of catalyst gross mass.
3. gasoline hydrogenation treatment catalyst according to claim 1, it is characterised in that：By the weight percent of catalyst
Meter, TS-1 molecular sieve contents are 5~30wt%, γ-Al2O3Content is 25~60wt%, and graphene content is 0.01~5wt%,
Heteropoly acid content is 10~40wt%.
4. gasoline hydrogenation treatment catalyst according to claim 1, it is characterised in that：The heteropoly acid is M6[WM3(H2O)2
(ZnW9O34)2], one or more of M Mn, Co, Ni and Cu.
5. gasoline hydrogenation treatment catalyst according to claim 1, it is characterised in that：The shape of catalyst is sheet, ball
Shape, cylindrical bars, irregular strip, graininess or tooth are spherical.
6. gasoline hydrogenation treatment catalyst according to claim 1, it is characterised in that：A diameter of 0.8mm of catalyst~
The slice of 2.0mm or thick item more than 2.5mm.
7. gasoline hydrogenation treatment catalyst according to claim 6, it is characterised in that：A diameter of 1.0mm of catalyst~
The slice of 1.8mm.
8. a kind of preparation method of gasoline hydrogenation treatment catalyst is claim 1~7 any one of them gasoline hydrogenation essence
The preparation method of catalyst processed, includes the following steps：
(1) alumina powder is uniformly mixed with TS-1 molecular sieves, adds graphene, add extrusion aid and bonding after mixing
Agent is uniformly mixed again, extruded moulding, and carrier is made in freeze-drying or vacuum drying after roasting；
(2) be made into maceration extract with the heteropoly acid containing active component, by carrier obtained carry out incipient impregnation, freeze-drying or
Gasoline hydrogenation treatment catalyst is made in vacuum drying after roasting.
9. the preparation method of gasoline hydrogenation treatment catalyst according to claim 8, it is characterised in that：The heteropoly acid is
M6[WM3(H2O)2(ZnW9O34)2], one or more of M Mn, Co, Ni and Cu.
10. the preparation method of gasoline hydrogenation treatment catalyst according to claim 8, it is characterised in that：The extrusion aid
For one or more of starch, sesbania powder, polyvinyl alcohol, methylcellulose and polyethylene glycol.
11. the preparation method of gasoline hydrogenation treatment catalyst according to claim 8, it is characterised in that：Described adhesive
For one or more of nitric acid, citric acid, ethanedioic acid and tartaric acid.
12. the preparation method of gasoline hydrogenation treatment catalyst according to claim 8, it is characterised in that：Step (2) is medium
The volume impregnation time is 0.5~5 hour；Roasting condition is in step (2)：It is roasted 2~6 hours at 400~550 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711032892.3A CN108452846B (en) | 2017-10-27 | 2017-10-27 | Gasoline hydrofining catalyst and preparation method thereof |
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|---|---|---|---|
| CN201711032892.3A CN108452846B (en) | 2017-10-27 | 2017-10-27 | Gasoline hydrofining catalyst and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068750A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Modified alumina carrier, preparation method thereof and hydrofining catalyst |
| CN112705250A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Ultra-deep desulfurization and denitrification hydrotreating catalyst and preparation method thereof |
| CN112973737A (en) * | 2019-12-13 | 2021-06-18 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst and preparation method thereof |
| CN113801687A (en) * | 2020-06-12 | 2021-12-17 | 中国石油化工股份有限公司 | Hydrogenation method for producing aviation kerosene |
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| CN104646009A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof |
| CN105709822A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of heteropoly acid ammonium salt catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104646009A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Inferior heavy oil hydrodesulfurization catalyst and preparation method thereof |
| CN105709822A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of heteropoly acid ammonium salt catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068750A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Modified alumina carrier, preparation method thereof and hydrofining catalyst |
| CN111068750B (en) * | 2018-10-22 | 2022-03-04 | 中国石油化工股份有限公司 | Modified alumina carrier, preparation method thereof and hydrofining catalyst |
| CN112705250A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Ultra-deep desulfurization and denitrification hydrotreating catalyst and preparation method thereof |
| CN112705250B (en) * | 2019-10-25 | 2022-03-08 | 中国石油化工股份有限公司 | Ultra-deep desulfurization and denitrification hydrotreating catalyst and preparation method thereof |
| CN112973737A (en) * | 2019-12-13 | 2021-06-18 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst and preparation method thereof |
| CN112973737B (en) * | 2019-12-13 | 2022-04-05 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst and preparation method thereof |
| CN113801687A (en) * | 2020-06-12 | 2021-12-17 | 中国石油化工股份有限公司 | Hydrogenation method for producing aviation kerosene |
| CN113801687B (en) * | 2020-06-12 | 2023-05-30 | 中国石油化工股份有限公司 | Hydrogenation method for producing aviation kerosene |
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| CN108452846B (en) | 2020-08-07 |
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