CN108654644A - A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application - Google Patents
A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108654644A CN108654644A CN201810387068.8A CN201810387068A CN108654644A CN 108654644 A CN108654644 A CN 108654644A CN 201810387068 A CN201810387068 A CN 201810387068A CN 108654644 A CN108654644 A CN 108654644A
- Authority
- CN
- China
- Prior art keywords
- micro
- core construction
- nickel
- type hollow
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- C10G47/06—Sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application, belongs to catalyst technical field, which becomes molybdenum nickel ternary sulfide, and active component is the sulfide of molybdenum and nickel, and molybdenum is 1~1.5 with nickel molar ratio：1~3, molybdenum is 25~45% with the mass fraction of nickel in the catalyst.The present invention simultaneously applies for application of the micro-nano type hollow-core construction bimetallic catalyst in hydrocracking heavy oil.The hollow-core construction of the micro-nano type hollow structure material of the present invention can utilize minimum metal active constituent, obtain more exposed edge active site, cost is saved to improve raw metal utilization rate, a kind of high activity, inexpensive catalyst are provided for mink cell focus floating bed hydrocracking.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of micro-nano type hollow-core construction bimetallic catalyst and
Preparation method and application are suitable for mink cell focus floating bed hydrocracking.
Background technology
In recent years since the exploitation of petroleum resources increasingly increases, good petroleum resources have faced the risk of shortage.Generation
The oil increased production within the scope of boundary will be mainly heavy crude and heavy synthetic oil, therefore oil refining enterprise is faced with raw material heavy
Change the pressure in poor quality.High-quality crude gradually decreases and in the case that external crude oil with poor quality gradually increases at home, it is necessary to
These mink cell focuses are carried out lighting processing, so that the heavy constituent for being difficult to directly utilize is become common light component oil product, thus
Demand of the China to the light components of oil can greatly be alleviated, therefore the especially high carbon residue of mink cell focus, high-sulfur nitrogen, high metal are bad
The working process of matter residual oil is just becoming the development trend of the following oil refining enterprise.And heavy oil lightweight common in oil refining industry
Change method mainly has catalytic cracking, thermal cracking, is hydrocracked.Suspension bed hydrogenation process is that most potential mink cell focus adds hydrogen to split
Chemical industry skill especially has broad application prospects in terms of processing residual oil inferior, is current solution inferior heavy oil depth
One of effective way of processing problems.
Suspension bed hydrogenation catalyst is the core of suspension bed residual oil hydrogenation technology.It is commonly used in hydrocracking reaction at present
The higher catalyst of activity be Co, Mo, Ni and W series catalysts.Simultaneously study find disperse type catalyzer dispersion, catalysis,
These aspects of the performances such as suppression coke have a clear superiority.Since suspension bed catalyst is generally with tail oil discharge and without recycling, institute
It is solution to improve catalyst activity, improve catalyst metals active sites utilization rate and promote dispersibility to reduce catalyst amount
The certainly effective way of the problem.Therefore, suitable equalization point is found on catalyst performance and cost, is developed and is added with high
Hydrogen activity, high metal active sites utilization rate, polymolecularity industrial catalyst be the core of suspension bed residual oil hydrogenation technological development
The route of technology and floating bed hydrogenation technology commercialization most foreground.
Micro-nano hollow structure material have specific surface is big, density is low, saves material, reduces the advantages such as cost, material
Hollow-core construction can utilize minimum metal active constituent, obtain more exposed edge active site, thus hollow-core construction
Micro-nano catalyst can be effectively increased its catalysis react in active sites points, to improve raw metal utilization rate
Save cost.
Therefore, micro-nano type hollow-core construction bimetallic suspension bed residual oil hydrogenation cracking catalysis of the exploitation with greater activity
Agent has a very important significance.
Invention content
The present invention provides a kind of micro-nano type hollow-core construction bimetallic catalysts and its preparation method and application, solve
Synthesized distributed MoS at present2The edge active site of catalyst entity exposure is few, and metal active position utilization rate is not high
The problem of.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of micro-nano type hollow-core construction bimetallic catalyst, the catalyst group become molybdenum nickel ternary sulfide, activearm
It is divided into the sulfide of molybdenum and nickel, molybdenum is 1~1.5 with nickel molar ratio：1~3, molybdenum is 25 with the mass fraction of nickel in the catalyst
~45%.
A kind of preparation method of micro-nano type hollow-core construction bimetallic catalyst, includes the following steps：
(1) molybdenum salt and ammonium hydroxide are stirred at 45 DEG C to being completely dissolved, be warming up to 60~68 DEG C be added vulcanizing agents reaction 1~
2h obtains product 1；
(2) PVP and nickel salt are dissolved in alcohols solvent, are warming up to 65~90 DEG C, are stirred at reflux 4~8h, obtains product 2；
(3) product 1 is dissolved in deionized water, and solute is 40~60mg/90~100ml with solvent ratio；Product 2 is dissolved in alcohols
Solvent, solute are 200~250mg/90~100ml with solvent ratio；When needing rapid stirring when two solution are mixed, and reacting
Between within 1h；
(4) it centrifuges after reaction, centrifugal condition is 4500~5000r/min, and centrifugation time is 8~10min, is obtained
Solid product carry out washing centrifugation 3 times, the drying of 80 DEG C of vacuum drying chamber with alcohols solvent；
(5) product is annealed after drying, and annealing temperature is 200~500 DEG C, and annealing time is 1~3h, is finally obtained
As micro-nano type hollow-core construction bimetallic catalyst.
Wherein it is preferred to which the molybdenum salt is ammonium molybdate, vulcanizing agent is ammonium sulfide solution or hydrogen sulfide gas.
Wherein it is preferred to the nickel salt is any one or a few in nickel acetate, nickel nitrate, nickel chloride, it is described
Alcohols solvent is any one or a few in ethyl alcohol, isopropanol, ethylene glycol.
Wherein it is preferred to which the ratio of molybdenum salt and ammonium hydroxide is 1g in the step (1)：2~4ml, the molybdenum salt and ammonium sulfide
Water-soluble liquid proportional is that the ratio of 1g/5~15ml or described molybdenums salt and hydrogen sulfide gas is 1g/ml.
Wherein it is preferred to which the weight ratio of PVP and nickel salt is 1 in the step (2):0.3~0.7.
Wherein it is preferred to the annealing atmosphere of the step (4) is hydrogen or nitrogen atmosphere, temperature-rise period in annealing process
For 1~4 DEG C/min, cycle annealing is carried out after being warming up to assigned temperature.
For micro-nano type hollow-core construction bimetallic catalyst in the application of hydrocracking heavy oil, the micro-nano type is hollow
The amount that structure bimetallic catalyst is added is 80~300 μ gg of raw material-1。
Beneficial effects of the present invention：
(1) hollow-core construction of the micro-nano type hollow structure material of the present invention can utilize minimum metal active constituent, obtain
More exposed edge active site is taken, cost is saved to improve raw metal utilization rate, is mink cell focus floating bed hydrogenation
Cracking provides the catalyst of a kind of high activity, low cost.
(2) process for synthetic catalyst according to the present invention is simple, mild condition, and raw material is easy to get cheaply, is suitable for big rule
Mould industrialized production.
(3) catalyst prepared by the present invention is bimetallic catalyst, and molybdenum and nickel have therebetween synergistic effect, adds
Hydrogen activity is high, and the burnt effect of suppression is good, and heavy oil conversion rate is high.
(4) catalyst according to the present invention, need not add any vulcanizing agent in the reactor, and catalyst contains itself
There are the catalytic active components such as the sulfide of molybdenum disulfide and nickel, simplify the pre-sulfiding step in hydrocracking process of suspended bed,
Improve operating efficiency.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will to embodiment or
Attached drawing needed to be used in the description of the prior art is briefly described, it should be apparent that, the accompanying drawings in the following description is only
Some embodiments of the present invention, for those of ordinary skill in the art, without creative efforts, also
It can be obtain other attached drawings according to these attached drawings.
Fig. 1 is that the TEM of 1 micro-nano type hollow-core construction bimetallic catalyst of embodiment schemes；
Fig. 2 is that the TEM of 2 micro-nano type hollow-core construction bimetallic catalyst of embodiment schemes；
Fig. 3 is that the TEM of 3 micro-nano type hollow-core construction bimetallic catalyst of embodiment schemes.
Specific implementation mode
Below in conjunction with the specific embodiment of the invention, technical scheme of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of micro-nano type hollow-core construction bimetallic catalyst Ni-MoS3, the catalyst active component
For the sulphided state substance of molybdenum and nickel, molybdenum is 1 with nickel molar ratio：1, molybdenum is summed it up with the mass fraction of nickel in the catalyst is
32.35%, preparation method is as follows：
(1) it takes 10.0g ammonium molybdates to pour into 30ml ammonium hydroxide, stirs at 45 DEG C and be completely dissolved to ammonium molybdate, be warming up to 65
After DEG C, 50ml is added and vulcanizes ammonia spirit, reaction to 100min postcoolings crystallization is product 1；
(2) take the polyvinylpyrrolidone (PVP), tetra- water nickel acetates of 1.3g and 200ml absolute ethyl alcohols of 2.8g in container
It is interior, after being stirred at reflux 6h under 85 DEG C of reaction temperatures, product 2 is centrifuged；
(3) 50mg products 2 are dissolved in 25ml isopropanols, and 220mg products 1 are dissolved in 480ml deionized waters.1 solution of product is fallen
30min is stirred energetically after entering 2 solution of product；
(4) it centrifuges after reaction, centrifugal condition 5000r/min, centrifugation time 9min, obtained solid product
Washing centrifugation 3 times, 80 DEG C of drying of vacuum drying chamber are carried out with isopropanol；
(5) product is annealed after drying, and annealing atmosphere is hydrogen or nitrogen atmosphere, and temperature-rise period is 2 in annealing process
DEG C/min, cycle annealing is carried out after being warming up to 400 DEG C, annealing time 2h is finally obtained as micro-nano type hollow-core construction
Bimetallic catalyst.
Embodiment 2
The present embodiment provides a kind of micro-nano type hollow-core construction bimetallic catalyst Ni-MoS3, the catalyst active component
For the sulphided state substance of molybdenum and nickel, molybdenum is 1 with nickel molar ratio:3, molybdenum is 34.67% with the mass fraction of nickel in the catalyst,
Preparation method is as follows：
(1) it takes 10.0g ammonium molybdates to pour into 20ml ammonium hydroxide, stirs at 45 DEG C and be completely dissolved to ammonium molybdate, be warming up to 68
After DEG C, 150ml hydrogen sulfide gas is added, reaction to 60min postcoolings crystallization is product 1；
(2) take polyvinylpyrrolidone (PVP), 1.96g nickel nitrates and the 200ml absolute ethyl alcohols of 2.8g in container, 90
After being stirred at reflux 4h under DEG C reaction temperature, product 2 is centrifuged；
(3) 50mg products 2 are dissolved in 18ml absolute ethyl alcohols, and 220mg products 1 are dissolved in 550ml deionized waters.By 1 solution of product
30min is stirred energetically after pouring into 2 solution of product；
(4) it centrifuges after reaction, centrifugal condition 4500r/min, centrifugation time 8min, obtained solid product
Washing centrifugation 3 times, 80 DEG C of drying of vacuum drying chamber are carried out with alcohols solvent；
(5) product is annealed after drying, and annealing atmosphere is hydrogen or nitrogen atmosphere, and temperature-rise period is 1 in annealing process
DEG C/min, cycle annealing is carried out after being warming up to 400 DEG C, annealing time 2h is finally obtained as micro-nano type hollow-core construction
Bimetallic catalyst.
Embodiment 3
The present embodiment provides a kind of micro-nano type hollow-core construction bimetallic catalyst Ni-MoS3, the catalyst active component
For the sulphided state substance of molybdenum and nickel, molybdenum is 1.5 with nickel molar ratio：1, molybdenum is with the mass fraction of nickel in the catalyst
40.56%, preparation method is as follows：
(1) it takes 10.0g ammonium molybdates to pour into 40ml ammonium hydroxide, stirs at 45 DEG C and be completely dissolved to ammonium molybdate, be warming up to 60
After DEG C, 150ml is added and vulcanizes ammonia spirit, reaction to 120min postcoolings crystallization is product 1；
(2) take polyvinylpyrrolidone (PVP), 0.84g nickel chlorides and the 200ml absolute ethyl alcohols of 2.8g in container, 65
After being stirred at reflux 8h under DEG C reaction temperature, product 2 is centrifuged；
(3) 50mg products 2 are dissolved in 20ml ethylene glycol, and 220mg products 1 are dissolved in 330ml deionized waters.1 solution of product is fallen
30min is stirred energetically after entering 2 solution of product；
(4) it centrifuges after reaction, centrifugal condition 5000r/min, centrifugation time 10min, obtained solid product
Spent glycol carries out washing centrifugation 3 times, 80 DEG C of drying of vacuum drying chamber；
(5) product is annealed after drying, and annealing atmosphere is hydrogen or nitrogen atmosphere, and temperature-rise period is 4 in annealing process
DEG C/min, cycle annealing is carried out after being warming up to 400 DEG C, annealing time 2h is finally obtained as micro-nano type hollow-core construction
Bimetallic catalyst.
Embodiment 4
By the micro-nano type hollow-core construction bimetallic catalyst Ni-MoS prepared by above-described embodiment 13, clear for Shandong
Source Effect of Catalysis In Petrochemistry cracking slurry oil (FCCS) is in the hydrocracking reaction of raw material, and property is shown in Table 1-1,1-2.On autoclave
Investigate different embodiment synthetic catalyst catalysis and the conversion situation for being not added with the lower feedstock oil of catalyst blank autoclave comparison.
Prepared micro-nano type hollow-core construction bimetallic catalyst needs to carry out oil in organic acid in above-described embodiment
Dissolubility modification pretreatment, 180 DEG C of reaction temperature are investigated as catalyst in autoclave afterwards.
Reaction condition is：430 DEG C of reaction temperature reacts first pressing 8MPa, reaction time 60min, 150 μ of catalyst charge
g·g-1(based on total metal content), 200 μ gg of auxiliary agent-1, experimental result is shown in Table 2-1,2-2.
Table 1-1 is radically reformed in Shandong the fundamental property of Effect of Catalysis In Petrochemistry cracking slurry oil (FCCS) raw material
Table 1-2 catalytic cracked oil pulp true boiling point distillation data
The different embodiment synthesis catalytic catalyst hydrocracking review numbers of table 2 are according to table
Unit green coke light oil yield I=(yield of gasoline+diesel yield)/coking yield
As shown in Table 2, micro-nano type hollow-core construction bimetallic catalyst Ni-MoS provided by the invention3It is imitated with dispersion
Fruit is good, and prepared catalyst need not add the sulfide that any vulcanizing agent can be with molybdenum disulfide, nickel in the reactor
Etc. catalytic active components, the advantage that hydrogenation activity is high, the burnt performance of suppression is good.The catalyst is in the floating bed hydrogenation applied to FCCS
In cracking process, in the case of addition (in terms of metal)≤150 μ g/g of catalyst, which is provided with preferably
Suppression coke performance, coking yield ＜ 0.3m% ,≤500 DEG C of liquid product yield reaches 95m% or more, unit green coke light oil
Yield can reach 219.1.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of micro-nano type hollow-core construction bimetallic catalyst, it is characterised in that：The catalyst group vulcanizes as molybdenum nickel ternary
Object, active component are the sulfide of molybdenum and nickel, and molybdenum is 1~1.5 with nickel molar ratio：1~3, molybdenum and the quality of nickel in the catalyst
Score is 25~45%.
2. a kind of preparation method of micro-nano type hollow-core construction bimetallic catalyst described in claim 1, which is characterized in that packet
Include following steps：
(1) molybdenum salt and ammonium hydroxide are stirred at 45 DEG C to being completely dissolved, and are warming up to 60~68 DEG C and vulcanizing agent 1~2h of reaction is added, obtain
To product 1；
(2) PVP and nickel salt are dissolved in alcohols solvent, are warming up to 65~90 DEG C, are stirred at reflux 4~8h, obtains product 2；
(3) product 1 is dissolved in deionized water, and solute is 40~60mg/90~100ml with solvent ratio；Product 2 is dissolved in alcohols solvent,
Solute is 200~250mg/90~100ml with solvent ratio；Rapid stirring is needed when two solution are mixed, and the reaction time is 1h
Within；
(4) it centrifuges after reaction, centrifugal condition is 4500~5000r/min, and centrifugation time is 8~10min, obtained solid
Product carries out washing centrifugation 3 times, 80 DEG C of drying of vacuum drying chamber with alcohols solvent；
(5) product is annealed after drying, and annealing temperature is 200~500 DEG C, and annealing time is 1~3h, is finally obtained as micro-
Nano type hollow-core construction bimetallic catalyst.
3. the preparation method of micro-nano type hollow-core construction bimetallic catalyst according to claim 2, it is characterised in that：Institute
The molybdenum salt stated is ammonium molybdate, and vulcanizing agent is ammonium sulfide solution or hydrogen sulfide gas.
4. the preparation method of micro-nano type hollow-core construction bimetallic catalyst according to claim 2, it is characterised in that：Institute
The nickel salt stated is any one or a few in nickel acetate, nickel nitrate, nickel chloride, and the alcohols solvent is ethyl alcohol, isopropanol, second
Any one or a few in glycol.
5. the preparation method of micro-nano type hollow-core construction bimetallic catalyst according to claim 3, it is characterised in that：Institute
It is 1g to state the ratio of molybdenum salt and ammonium hydroxide in step (1)：2~4ml, the molybdenum salt and ammonium sulfide solution ratio are 1g/5~15ml,
Or the ratio of the molybdenum salt and hydrogen sulfide gas is 1g/50ml~150ml.
6. the preparation method of micro-nano type hollow-core construction bimetallic catalyst according to claim 2, it is characterised in that：Institute
It is 1 to state the weight ratio of PVP and nickel salt in step (2):0.3~0.7.
7. the preparation method of micro-nano type hollow-core construction bimetallic catalyst according to claim 2, it is characterised in that：Institute
The annealing atmosphere of step (4) is stated as hydrogen or nitrogen atmosphere, temperature-rise period is 1~4 DEG C/min in annealing process, waits being warming up to finger
Cycle annealing is carried out after constant temperature degree.
8. the micro-nano type hollow-core construction bimetallic catalyst of claim 1 is in the application of hydrocracking heavy oil, it is characterised in that：
The amount that the micro-nano type hollow-core construction bimetallic catalyst is added is 80~300 μ gg of raw material-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810387068.8A CN108654644A (en) | 2018-04-26 | 2018-04-26 | A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810387068.8A CN108654644A (en) | 2018-04-26 | 2018-04-26 | A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108654644A true CN108654644A (en) | 2018-10-16 |
Family
ID=63780207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810387068.8A Pending CN108654644A (en) | 2018-04-26 | 2018-04-26 | A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108654644A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279296A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Sulfuration type catalyst and preparation thereof |
| CN106179414A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof |
| CN106311341A (en) * | 2015-06-30 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst for slurry bed of heavy oil as well as catalyst and application thereof |
| CN107469837A (en) * | 2017-09-07 | 2017-12-15 | 中国石油大学(华东) | Autovulcanization oil-soluble NiMo catalyst and its preparation method and application |
-
2018
- 2018-04-26 CN CN201810387068.8A patent/CN108654644A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279296A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Sulfuration type catalyst and preparation thereof |
| CN106179414A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof |
| CN106311341A (en) * | 2015-06-30 | 2017-01-11 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst for slurry bed of heavy oil as well as catalyst and application thereof |
| CN107469837A (en) * | 2017-09-07 | 2017-12-15 | 中国石油大学(华东) | Autovulcanization oil-soluble NiMo catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| LE YU等: "General Formation of M–MoS 3 (M = Co, Ni) Hollow Structures with Enhanced Electrocatalytic Activity for Hydrogen Evolution", 《ADV. MATER.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
| CN114433203B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of vulcanized hydrocracking catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108745385B (en) | Self-vulcanized oil-soluble molybdenum-based bimetallic catalyst and preparation method and application thereof | |
| CN107779225B (en) | A kind of hydro-conversion system and method | |
| US3915894A (en) | Activation of hydrotreating catalysts | |
| CN107469837A (en) | Autovulcanization oil-soluble NiMo catalyst and its preparation method and application | |
| CN101658792A (en) | Preparation method of transition metal sulfide catalytic material and catalytic application thereof | |
| CN102311766B (en) | Class II active center hydrogenation catalyst start-up vulcanization method | |
| CN1072706C (en) | Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method | |
| CN106215953A (en) | The synthesis of controlled number of plies molybdenum sulfide and the application in fragrance phenol and ethers reaction thereof | |
| CN104371758B (en) | The method of the biological coal that navigates is prepared by grease and hydrogen supply dissolvent co-activating | |
| CN102443425B (en) | Start-up activating method of hydrocracking process | |
| CN102443412B (en) | Start-up method for ex-situ prevulcanization secondary activity center hydrogenation catalysts | |
| CN108654644A (en) | A kind of micro-nano type hollow-core construction bimetallic catalyst and its preparation method and application | |
| CN114011415A (en) | Preparation method of high-load layered cobalt catalyst for preparing green diesel oil by grease hydrodeoxygenation | |
| CN112717946A (en) | Spent lubricating oil hydrogenation regeneration catalyst and preparation method thereof | |
| CN102311765B (en) | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst | |
| CN102465011B (en) | Hydrotreatment method of heavy distillate oil | |
| CN1119398C (en) | Conversion process of hydrocarbon oil | |
| CN107649182B (en) | The circulation utilization method of oil-soluble tungsten base slurry bed system hydrocracking catalyst | |
| CN105728000A (en) | Preparation method and application of oleophylic type nanoscaled molybdenum disulfide | |
| CN111420670B (en) | Hydrogenation catalyst and preparation method and application thereof | |
| CN101255356A (en) | Unsupported catalyst and preparation method thereof | |
| CN104650970A (en) | Hydrocracking technical method reducing the content of sulfur in light fraction product | |
| CN109337714B (en) | Preparation method of low-naphthalene high-boiling-point aromatic solvent for rubber resin plasticizer | |
| CN106669801A (en) | Catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and preparation method thereof | |
| CN114250079B (en) | Method for producing biodiesel by catalyzing selective hydrodeoxygenation of methyl oleate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181016 |