CN106732496B - A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method - Google Patents
A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method Download PDFInfo
- Publication number
- CN106732496B CN106732496B CN201611156531.5A CN201611156531A CN106732496B CN 106732496 B CN106732496 B CN 106732496B CN 201611156531 A CN201611156531 A CN 201611156531A CN 106732496 B CN106732496 B CN 106732496B
- Authority
- CN
- China
- Prior art keywords
- silicon source
- catalyst
- preparation
- nickel
- source
- 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.)
- Active
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/888—Tungsten
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- 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
- C10G2300/1022—Fischer-Tropsch products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method.The preparation method of amorphous silicon alumina supporter includes the following steps: the mixed aqueous solution for preparing silicon source and silicon source, mixed aqueous solution is mixed into progress co-precipitation with the solution of precipitating reagent and obtains precipitate slurry, and be transferred in closed container and carry out aging, it is roasted after forming to obtain the final product.The present invention also provides the preparation methods of the hydrocracking catalyst using amorphous silicon aluminium as carrier, it is in the preparation method of amorphous silicon alumina supporter of the present invention, the salt that nickel salt or nickel salt and metal promoter M are added in the mixed aqueous solution of silicon source and silicon source is prepared in step (1), remaining step is identical as the preparation method of carrier as amorphous silicon aluminium.The present invention uses coprecipitation during the preparation process, and silicon source silicon source used is finally present in catalyst in the form of amorphous silica-alumina, but the activity of catalyst is significantly larger than general amorphous silicon Al catalysts.
Description
Technical field
The present invention relates to a kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their system
Preparation Method belongs to oil product manufacture field.
Background technique
FT synthetic oil without sulphur, nitrogen-free, without aromatic hydrocarbons, be mainly made of the alkane and olefine of different carbon numbers, and alkene
Hydrocarbon is largely alhpa olefin.The carbon number distribution of FT product is wider, and highest can be more than 100.FT synthesis intermediate products are suitble to processing to give birth to
Produce high-quality diesel oil, aviation kerosine, naphtha etc..By hydrocracking process by FT converting heavy hydrocarbons be diesel oil, aviation kerosine
It is one of technology more important in FT product processing technique, the performance of hydrocracking catalyst is even more to directly affect target product
Yield and quality.
Hydrocracking catalyst is the bifunctional catalyst of metal function and acid function synergistic effect.Amorphous silica-alumina is stone
Widely used a kind of catalyst carrier in oil refining and petrochemical industry has the characteristics that large specific surface area, acidity are moderate.As
The carrier of heavy oil hydrocracking catalyst, biggish specific surface area can make active metal be evenly dispersed in catalyst table
Face, and acidity appropriate then can provide acidic site and catalyst made to have cracking activity.
Industrial at present generally to use aluminum sulfate method and preparing amorphous silicon alumnium using carbonization, the nothing prepared using this method is fixed
The characteristics of shape sial is that acidity is weaker, and using it as the hydrocracking catalyst of carrier preparation, often activity is weaker, reaches appropriate
The reaction temperature that conversion ratio needs is higher.How to obtain sufficiently large specific surface area and Kong Rong, acidity appropriate and is suitable for
How silica alumina ratio improves the activity, selectivity and service life for preparing catalyst by it, is at present still petroleum refining and catalysis
Common problem in agent research preparation industry.
Chinese patent application (CN1597093A) discloses a kind of amorphous silica-alumina prepared using carbonizatin method, silicon oxide-containing
8wt%~50wt%, specific surface are 300~550m20.7~1.5ml/g of/g, Kong Rongwei, infrared acidity be 0.32~
0.50mmol/g, the disadvantage is that strong acid is more, L acid is relatively fewer, this can all cause catalyst excessive fragmentation, is unfavorable for catalyst
The raising of intermediate oil selectivity.
UK Patent Application (GB2166971) discloses a kind of preparation method of amorphous silica-alumina.Preparation method is alkali
Metal aluminum salt and silicate form mixed liquor when pH value is 12 or so, are reacted later with aluminum sulfate, and silica-alumina supports are prepared,
Its product specific surface 277m2/ g, Kong Rong 0.31ml/g contains SiO235wt%, the disadvantage is that Kong Rong and specific surface are low, as carrier
The sial of type catalyst cannot provide higher metal dispersity for active component.
Also there is the report for the carrier for using amorphous silica-alumina as hydrocracking catalyst in the prior art.US4758338
A kind of preparation method of amorphous silicon alumina supporter for hydrotreating catalyst is disclosed with US4721696.The preparation method
Using pH value swing method, five formation alumina sols are swung when pH value is 2-10 first, sodium metasilicate is then added and obtains nothing
Amorphous silicon-alumina carrier.The carrier specific surface area is little, and aperture is larger, acid low, is mainly used as not needing acid hydrotreating
The carrier of catalyst.Chinese patent application (CN200710010385.X) discloses Ni-W and is supported on amorphous silica-alumina plus hydrogen
Cracking catalyst, catalyst need to carry out active phase of the presulfurization processing to be reacted before the reaction.FT intermediate products without sulphur,
It can make occur sulfur-containing impurities in product using sulphided state catalyst, product is made to be unable to reach the content standard of national requirements.
Summary of the invention
The object of the present invention is to provide a kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and
Their preparation method, there is amorphous silica-alumina provided by the invention silica alumina ratio to be adjusted, specific surface area is larger, acid moderate
Advantage.
The preparation method of amorphous silicon alumina supporter provided by the present invention, includes the following steps:
(1) mixed aqueous solution for preparing silicon source and silicon source, mixes progress with the solution of precipitating reagent for the mixed aqueous solution
Co-precipitation obtains precipitate slurry；
(2) precipitate slurry is transferred to progress constant temperature aging in closed container；
(3) through step (2), treated that slurry carries out after forming roasts up to the amorphous silicon aluminium carrier.
In above-mentioned preparation method, the quality of the silicon source is with SiO2Meter, the quality of source of aluminium is with Al2O3Meter, the silicon
The mass ratio of source and source of aluminium can be 10.0~85.0:15.0~90.0, concretely 15.0~78.3:21.7~85.0,
15.0:85.0,20.5:79.5,27.8:72.2,30.8:69.2,42.8:57.2,58.5:41.5 or 78.3:21.7.
In above-mentioned preparation method, the silicon source can be at least one of silica solution, waterglass and white carbon black；
Source of aluminium can be at least one of aluminum nitrate, aluminum sulfate, boehmite and sodium metaaluminate；
The precipitating reagent can be at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium hydrogen carbonate.
In above-mentioned preparation method, in step (1), the temperature of the co-precipitation can be 40~85 DEG C, concretely
55~85 DEG C, 55 DEG C, 65 DEG C, 75 DEG C, 80 DEG C or 85 DEG C, settling velocity is 20ml~5L/min, concretely 20ml~3.2L/
Min, 20mL/min, 50mL/min, 200mL/min, 800mL/min or 3.2L/min；PH value can be 7.0~12.5, specifically may be used
It is 8.5~10.0,8.5,9.0 or 10.0.
In the step, the silicon source and source of aluminium are dissolved into water (deionized water) simultaneously and are made into mixed solution, into
The silicon source and above-mentioned silicon source can precipitate simultaneously when row precipitating, in the amorphous silica-alumina obtained in this way between silica and aluminium oxide
It can mix visibly homogeneous.
In above-mentioned preparation method, in step (2), the temperature of the constant temperature aging can be 95~200 DEG C, concretely 95
~180 DEG C, 95 DEG C, 120 DEG C, 150 DEG C, 160 DEG C or 180 DEG C, the time can be 3~48h, concretely 24~48h, for 24 hours, 30h
Or 48h；
Silica can be gradually from amorphous to the state transformation with certain crystal form, always in the constant temperature ageing process
The temperature and time of change determines the degree of silica conversion, but carries out XRD to amorphous silica-alumina obtained in trial stretch
Amorphous state, but (NH is still presented in detection discovery, aluminium oxide therein3- TPD) infrared acidity its acidity as the result is shown it is bright
The aobvious acidity higher than common amorphous silica-alumina.
It further include being added into the slurry acid before the forming step in step (3) in above-mentioned preparation method
And the step of being handled as follows:
It is filtered, washed and dries (such as the forced air drying at 120 DEG C)；
The acid can be citric acid or nitric acid；
The temperature of the roasting can be 420~550 DEG C, and concretely 550 DEG C, the time can be 3~8 hours, concretely 3
~8 hours, 4 hours, 6 hours or 8 hours.
The amorphous silicon alumina supporter that the above method of the present invention is prepared, SiO therein2With Al2O3Mass ratio be 10.0
~85.0:15.0~90.0, specific surface area are 260~450m2/ g, aperture integrated distribution is between 4nm~12nm, Kong Rongwei
0.6~1.3ml/g, infrared acidity are 0.25~0.65mmol/g.
The amorphous silica-alumina that the amorphous silica-alumina of the method for the present invention preparation is prepared compared with prior art has acid strong spy
Point but its acid acidity for being far below molecular sieve again, are more suitable as the carrier of hydrocracking catalyst, by it as carrier system
Standby hydrocracking catalyst can intensified response activity and improve the selection of intermediate oil in isocrackate
Property, to substantially increase the reaction efficiency of hydrocracking catalyst.
In the prior art, the preparation method of common hydrocracking catalyst is that amorphous silica-alumina and molecular sieve is sufficiently mixed
Merge extruded moulding, after drying roasting wherein by active metal dipping, and is dried and roasted herein, the catalysis being prepared
Agent active metal dispersing uniformity is poor, and finally influences its catalytic performance.
Based on this, the present invention also provides the preparation sides of the hydrocracking catalyst using the amorphous silicon aluminium as carrier
Method prepares the silicon source and described specifically in the preparation method of the above-mentioned amorphous silicon alumina supporter of the present invention in step (1)
The salt of nickel salt or nickel salt and metal promoter M, remaining step and the amorphous silicon aluminium conduct are added in the mixed aqueous solution of silicon source
The preparation method of carrier is identical.
It prepares in the method for hydrocracking catalyst, the quality of the silicon source is with SiO2Meter, the quality of source of aluminium with
Al2O3Meter, the quality of the nickel salt is in terms of NiO, and the salt of the metal promoter M is with MOxMeter, it is the silicon source, source of aluminium, described
The mass ratio of the salt of nickel salt and the metal promoter M can be 10.0~60.0:10.0~70.0:5.0~30.0:1.0~15.0；
The silicon source, source of aluminium and the nickel salt mass ratio can for 13.0~20.8:55.9~66.5:20.5~
23.5,15.0:61.5:23.5,13.0:66.5:20.5 or 20.8:55.9:23.3；
The silicon source, source of aluminium, the nickel salt and the metal promoter M the mass ratio of salt can be 10.8~58.3:
16.2~69.4:15.5~23.3:5.5~12.0,10.8:69.4:15.5:4.3,12.8:55.7:19.5:12,18.5:
50.1:23.3:8.1,16.5:51.1:22.3:10.1 or 58.3:16.2:19.5:5.5；
MOxMiddle x is the number between 0.5~3.
The nickel salt can be at least one of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate；
The metal promoter M can be at least one of Cu, Mn, Ag, Co, Zn, Zr, Mo, W and Cr.
The specific surface area of hydrocracking catalyst provided by the invention is 180~600m2/ g, active component and auxiliary agent group
Point good dispersion, the acidity of amorphous silicon alumina supporter is moderate, therefore is urged by being hydrocracked of preparing of the above method of the present invention
Agent has the characteristics that hydrogenation cracking activity is high, intermediate oil is selectively high.
Hydrocracking catalyst of the invention is suitable for the hydrocracking process of heavy hydrocarbon, is particularly suitable for F- T synthesis production
The process for being hydrocracked the intermediate oils such as production aviation kerosine, diesel oil of heavy wax in object.Catalyst of the invention is for adding
The reaction condition of hydrogen cracking are as follows: reaction pressure under hydro condition: 3.0~12.0MPa, hydrogen to oil volume ratio 200~1300, volume are empty
Speed is 0.5~5.0h-1, reaction temperature is 240 DEG C~380 DEG C.Catalyst of the present invention is in hydrocracking process to midbarrel
Oily selectivity up to 85%.
Compared with the prior art, the invention has the following features:
(1) amorphous silicon alumina supporter prepared by the present invention, due to have passed through the crystallization (constant temperature aging) of certain time, wherein
Sial have the tendency that it is a kind of to transformation of crystal, but there is no crystal as molecular sieve is formed, still presentation amorphous
State, but acidity is to be better than general amorphous silicon alumina supporter.
(2) variation of the amorphous silica-alumina prepared by the present invention due to operating condition, the acidity of obtained amorphous silica-alumina
It is adjustable, and meet very much the acidity of hydrocracking catalyst needs, hydrocracking catalyst reactivity prepared therefrom is high, in
Between distillate selectivity it is high, be a kind of excellent catalyst carrier.
(3) present invention uses coprecipitation during preparation, and silicon source silicon source used is finally with the shape of amorphous silica-alumina
Formula is present in catalyst, but the activity of catalyst is significantly larger than general amorphous silicon Al catalysts.
(4) coprecipitation, point of active metal and auxiliary agent are used during preparation due to catalyst of the present invention
Scattered property is fabulous, and for the crystallite dimension of the oxide of active metal nickel within 10nm, the crystallite dimension of auxiliary agent is also in Nano grade.
(5) it is directed to this catalyst of FT converting heavy hydrocarbons exploitation, can be efficient, environmentally friendlyly other cleanings by converting heavy hydrocarbons
Oil product has important theory significance and industrial application value to the further conversion of FT product.
Detailed description of the invention
Fig. 1 is amorphous silicon alumina supporter XRD spectra prepared by the embodiment of the present invention 7.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
One, the preparation of amorphous silicon alumina supporter
Comparative example 1,
The liquor alumini chloridi of the salic 10g/100ml of 1000ml is sunk with concentration for the ammonia spirit cocurrent of 20wt%
It forms sediment, reaction temperature is 70 DEG C, by pH stable 8.5, reaction contact time 25 minutes, then proceedes to stirring 60 minutes.Then
The sodium silicate solution 600ml of 10g/100ml is added dropwise in the slurries of stirring, keeps pH value constant, continues stirring 3 after completion of dropwise addition
Hour.Precipitating is filtered, filter cake is washed three times with 70 DEG C of deionized water, then filter cake is dried to 10 at 120 DEG C small
When, roasting 6 hours at 500 DEG C can be obtained amorphous silica-alumina product.
Embodiment 1,
Aluminum nitrate is made into the solution of 2mol/L, it is 260m that specific surface area is then added in the solution2The white carbon black of/g stirs
It mixes uniformly, and makes the mass ratio 15:85 of wherein silica and aluminium oxide.Sodium carbonate is made into the solution of 2mol/L, it is molten by two
Liquid carries out parallel-flow precipitation, settling rate 20mL/min at 55 DEG C, and precipitating pH value is 8.5, continues stirring two after precipitating
Ten minutes, mixed material is transferred in closed reactor, crystallization (constant temperature aging) 48 hours at 95 DEG C.By the good object of crystallization
Then material cooling is filtered, washed, moderate drying carries out extruded moulding.Carrier after molding is roasted at 550 DEG C
6h obtains amorphous silicon alumina supporter.
The weight percent of silica and aluminium oxide forms in carrier are as follows: SiO2:Al2O3=15.0:85.
Embodiment 2,
Catalyst is prepared by the step of embodiment 1, silicon source white carbon black is changed to waterglass, precipitating reagent is the hydrogen-oxygen of 2mol/L
Change sodium solution, changes simultaneously the proportion of silica and aluminium oxide in aluminum nitrate and sodium silicate solution, remaining behaviour does the constant system of condition
Standby carrier, carrier weight percentage of each component composition are as follows: SiO2:Al2O3=20.5:79.5.
Embodiment 3,
Catalyst is prepared by the step of embodiment 1, silicon source white carbon black is changed to silica solution, silicon source is aluminum sulfate, precipitating reagent
For the sodium hydroxide solution of 2mol/L, precipitation temperature is 80 DEG C, and precipitating pH value is 10.0, and slurries immigration reaction kettle exists after precipitating
Then amorphous silicon alumina supporter is made through filtration washing, drying and moulding in crystallization 24 hours at 180 DEG C, resulting vehicle each component
Mass ratio composition are as follows: SiO2:Al2O3=27.8:72.2.
Embodiment 4,
Aluminum sulfate is made into 2mol/L mixed solution, silica solution is then added in the solution, is mixed evenly.By carbonic acid
Hydrogen sodium is made into the solution of 1mol/L, two solution is carried out parallel-flow precipitation at 65 DEG C, settling rate 50mL/min precipitates pH value
It is 9.0, continues stirring 20 minutes after precipitating, mixed material is transferred in closed reactor, the crystallization 30 at 120 DEG C
Hour.The good material of crystallization is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.By catalysis after molding
Agent carries out roasting 8h at 550 DEG C, obtains amorphous silicon alumina supporter.Weight percentage of each component forms in carrier are as follows: SiO2:Al2O3
=30.8:69.2.
Embodiment 5,
Aluminum nitrate is made into 3mol/L mixed solution, silica solution is then added in the solution, is mixed evenly.By carbonic acid
Sodium is made into the solution of 2mol/L, two solution is carried out parallel-flow precipitation at 85 DEG C, settling rate 200mL/min precipitates pH value
It is 9.0, continues stirring 20 minutes after precipitating, mixed material is transferred in closed reactor, the crystallization 24 at 150 DEG C
Hour.The good material of crystallization is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.By catalysis after molding
Agent carries out roasting 4h at 550 DEG C, obtains amorphous silicon alumina supporter.Weight percentage of each component forms in carrier are as follows: SiO2:Al2O3
=42.8:57.2.
Embodiment 6,
Aluminum nitrate is made into the mixed solution of 2mol/L, waterglass is then added in the solution, is mixed evenly.By carbon
Sour ammonia is made into the solution of 2mol/L, two solution is carried out parallel-flow precipitation at 85 DEG C, settling rate 3.2L/min precipitates pH value
It is 9.0, continues stirring 20 minutes after precipitating, mixed material is transferred in closed reactor, the crystallization 24 at 160 DEG C
Hour.The good material of crystallization is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.Nothing after molding is determined
Shape sial carries out roasting 6h at 550 DEG C and obtains carrier.Weight percentage of each component forms in carrier are as follows: SiO2:Al2O3=58.5:
41.5。
Embodiment 7,
It is 1mol/L solution that waterglass, which is diluted to concentration, and boehmite is then added in the solution, is mixed equal
It is even.Sodium hydroxide is made into the solution of 2mol/L, two solution are subjected to parallel-flow precipitation, settling rate 800mL/ at 75 DEG C
Min, precipitating pH value are 10.0, continue stirring 20 minutes after precipitating, mixed material is transferred in closed reactor,
Crystallization 24 hours at 160 DEG C.The good material of crystallization is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.
Catalyst after molding is subjected to roasting 6h at 550 DEG C and obtains amorphous silicon alumina supporter.Weight percentage of each component group in carrier
Become: SiO2:Al2O3=78.3:21.7.
Amorphous silicon alumina supporter XRD spectra manufactured in the present embodiment as shown in Figure 1, by disperse Bao Feng known to silica and
Aluminium oxide is in amorphous state.
Two, the preparation and application of hydrocracking catalyst
Embodiment 8,
Aluminum nitrate and nickel sulfate are made into mixed solution, white carbon black is then added in the solution, is mixed evenly carbon
Sour sodium is made into the solution of 2mol/L, and two solution are carried out parallel-flow precipitation at 55 DEG C, and precipitating pH value is 8.5, after precipitating after
Continuous stirring 20 minutes, mixed material is transferred in closed reactor, crystallization 48 hours at 95 DEG C.By the good material of crystallization
It is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.Catalyst after molding is roasted at 550 DEG C,
Obtain wanted catalyst.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3: NiO=15.0:61.5:23.5,
The specific surface area of catalyst is 308m2/g。
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 10 is small at hydrogen atmosphere, 400 DEG C
When, 350 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 60% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 9,
Catalyst is prepared by the step of embodiment 8, silicon source white carbon black is changed to waterglass, precipitating reagent is the hydrogen-oxygen of 2mol/L
Change sodium solution, remaining condition is constant to prepare catalyst, and weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3:NiO
=13.0:66.5:20.5.
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 10 is small at hydrogen atmosphere, 400 DEG C
When, 350 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 56% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 10,
Catalyst is prepared by the step of embodiment 8, silicon source white carbon black is changed to silica solution, silicon source is aluminum sulfate, precipitating reagent
For the sodium hydroxide solution of 2mol/L, precipitation temperature is 80 DEG C, and precipitating pH value is 10.0, and slurries immigration reaction kettle exists after precipitating
Then catalyst, the mass ratio of gained catalyst components is made through filtration washing, drying and moulding in crystallization 24 hours at 180 DEG C
Composition are as follows: SiO2:Al2O3: NiO=20.8:55.9:23.3, the specific surface area of catalyst are 386m2/g。
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 10 is small at hydrogen atmosphere, 400 DEG C
When, 300 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 54% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 11,
Aluminum sulfate and nickel sulfate are made into mixed solution, silica solution and cobalt nitrate are then added in the solution, is mixed
Sodium bicarbonate is uniformly made into the solution of 1mol/L, two solution are subjected to parallel-flow precipitation at 65 DEG C, precipitating pH value is 9.0, is sunk
Continue stirring 20 minutes after shallow lake, mixed material is transferred in closed reactor, crystallization 30 hours at 120 DEG C.It will
The good material of crystallization is cooling, is then filtered, washed, moderate drying carries out extruded moulding.By catalyst after molding 550
It DEG C is roasted, obtains wanted catalyst.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3: NiO:CoO=
10.8:69.4:15.5:4.3。
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 8 is small at hydrogen atmosphere, 380 DEG C
When, 340 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 53% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 79%.
Embodiment 12,
Aluminum nitrate and nickel acetate are made into mixed solution, silicon zirconium colloidal sol then is added in the solution and zinc nitrate, mixing are stirred
The solution that sodium carbonate is uniformly made into 2mol/L is mixed, two solution are subjected to parallel-flow precipitation at 85 DEG C, precipitating pH value is 9.0, is sunk
Continue stirring 20 minutes after shallow lake, mixed material is transferred in closed reactor, crystallization 24 hours at 150 DEG C.It will
The good material of crystallization is cooling, is then filtered, washed, moderate drying carries out extruded moulding.By catalyst after molding 550
It DEG C is roasted, obtains wanted catalyst.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3:NiO:ZrO:
ZnO=12.8:55.7:19.5:8.1:3.9.
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 8 is small at hydrogen atmosphere, 360 DEG C
When, 320 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 56% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 13,
Aluminum nitrate and nickelous carbonate are made into mixed solution, silica solution and ammonium molybdate are then added in the solution, is mixed
Carbonic acid ammonia is uniformly made into the solution of 2mol/L, two solution are subjected to parallel-flow precipitation at 85 DEG C, precipitating pH value is 9.0, precipitating
After continue stirring 20 minutes, mixed material is transferred in closed reactor, crystallization 24 hours at 160 DEG C.It will be brilliant
The material changed is cooling, is then filtered, washed, moderate drying carries out extruded moulding.By catalyst after molding at 550 DEG C
It is roasted to obtain wanted catalyst.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3: NiO:MoO=
18.5:50.1:23.3:8.1。
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 8 is small at hydrogen atmosphere, 400 DEG C
When, 350 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 50% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 14,
Sodium metaaluminate and waterglass, nickel chloride are made into mixed solution, metatungstic acid sodium is then added in the solution, mixing is stirred
The solution that sodium carbonate is uniformly made into 2mol/L is mixed, two solution are subjected to parallel-flow precipitation at 75 DEG C, precipitating pH value is 10.0, is sunk
Continue stirring 20 minutes after shallow lake, mixed material is transferred in closed reactor, crystallization 24 hours at 180 DEG C.It will
The good material of crystallization is cooling, is then filtered, washed, moderate drying carries out extruded moulding.By catalyst after molding 550
It DEG C is roasted to obtain wanted catalyst.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3:NiO:WO2=
16.5:51.1:22.3:10.1。
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 8 is small at hydrogen atmosphere, 400 DEG C
When, 350 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 56% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
Embodiment 15,
Waterglass, basic nickel carbonate are made into mixed solution, boehmite and chromic nitrate are then added in the solution, is mixed
Conjunction stirs evenly the solution that sodium hydroxide is made into 2mol/L, two solution is carried out parallel-flow precipitation at 75 DEG C, precipitating pH value is
10.0, continue stirring 20 minutes after precipitating, mixed material is transferred in closed reactor, the crystallization 24 at 160 DEG C
Hour.The good material of crystallization is cooling, it is then filtered, washed, moderate drying carries out extruded moulding.By catalysis after molding
Agent is roasted to obtain wanted catalyst at 550 DEG C.Weight percentage of each component forms in catalyst are as follows: SiO2:Al2O3:NiO:
CrO2=58.3:16.2:19.5:5.5.
Take 10ml catalyst loaded in continuous fixed bed reactor, normal pressure reduction 10 is small at hydrogen atmosphere, 400 DEG C
When, 330 DEG C are then cooled to, starts to feed.Raw material is that (initial boiling point is 290 DEG C to Fischer-Tropsch heavy wax, and greater than 520 DEG C distillates account for
58%, most of is linear paraffin), reaction feed ratio is hydrogen to oil volume ratio 500, reaction pressure 7MPa, and volume space velocity is
1.5h-1.DEG C distillate conversion ratio is 57% to product analysis as the result is shown: greater than 520, and diesel oil distillate is selectively 80%.
The amorphous silica-alumina property obtained by comparative example and embodiment 1-7 is as shown in table 1.
The product property of 1 amorphous silica-alumina of table
As shown in Table 1, silica alumina ratio variation range is big in amorphous silicon alumina supporter prepared by the present invention, specific surface area and Kong Rong
It is larger and acid higher than general amorphous silica-alumina, it is a kind of excellent carrier for preparing catalyst.
By embodiment 8-15 it is found that hydrocracking catalyst of the invention is carried out using Fischer-Tropsch heavy wax as raw material plus hydrogen is split
Change, reaction condition is mild, and treating capacity is larger, and activated partial does not need to carry out vulcanizing treatment, and environment friendly is stronger.Hydrogen is added to split
The selectivity for the product light hydrocarbon that change obtains is low and intermediate oil selectivity is high, is hydrocracked life suitable for Fischer-Tropsch heavy wax
Produce the process of the intermediate oils such as aviation kerosine, diesel oil.
Claims (4)
1. a kind of preparation method of hydrocracking catalyst, includes the following steps:
(1) following 1) or 2 are prepared) mixed aqueous solution, the mixed aqueous solution mix to progress cocurrent with the solution of precipitating reagent
Co-precipitation, obtains precipitate slurry；
1) silicon source, silicon source and nickel salt；
The quality of the silicon source is with SiO2Meter, the quality of source of aluminium is with Al2O3Meter, the quality of the nickel salt are described in terms of NiO
The mass ratio of silicon source, source of aluminium and the nickel salt is 13.0 ~ 20.8:55.9 ~ 66.5:20.5 ~ 23.5；
2) silicon source, silicon source, nickel salt and metal promoter M salt；
The quality of the silicon source is with SiO2Meter, the quality of source of aluminium is with Al2O3Meter, the quality of the nickel salt are described in terms of NiO
The salt of metal promoter M is with MOxMeter, the silicon source, source of aluminium, the nickel salt and the salt of the metal promoter M mass ratio be
10.0 ~ 60.0:10.0 ~ 60.0:5.0 ~ 30.0:1.0 ~ 15.0；
MOxMiddle x is the number between 0.5 ~ 3；
The silicon source is at least one of silica solution, waterglass and white carbon black；
Source of aluminium is at least one of aluminum nitrate, aluminum sulfate, boehmite and sodium metaaluminate；
The nickel salt is at least one of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate；
The precipitating reagent is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium hydrogen carbonate；
The metal promoter M is at least one of Cu, Mn, Ag, Co, Zn, Zr, Mo, W and Cr；
The temperature of the co-precipitation is 40 ~ 85 DEG C, and settling velocity is 20ml ~ 5L/min, and pH value is 7.0 ~ 12.5；
(2) precipitate slurry is transferred to progress constant temperature aging in closed container；
The temperature of the constant temperature aging is 150 ~ 180 DEG C, and the time is 24 ~ 48 h；
(3) through step (2), treated that slurry carries out after forming roasts up to the hydrocracking catalyst.
2. preparation method according to claim 1, it is characterised in that: in step (3), before the forming step, also wrap
Include the step of being added into the slurry acid and being handled as follows:
It is filtered, washed and dries；
The acid is citric acid or nitric acid；
The temperature of the roasting is 420 ~ 550 DEG C, and the time is 3 ~ 8 hours.
3. the hydrocracking catalyst of method preparation as claimed in claim 1 or 2.
4. application of the hydrocracking catalyst as claimed in claim 3 in catalysis being hydrocracked of Fischer-Tropsch heavy wax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611156531.5A CN106732496B (en) | 2016-12-14 | 2016-12-14 | A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611156531.5A CN106732496B (en) | 2016-12-14 | 2016-12-14 | A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732496A CN106732496A (en) | 2017-05-31 |
| CN106732496B true CN106732496B (en) | 2019-07-16 |
Family
ID=58888916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611156531.5A Active CN106732496B (en) | 2016-12-14 | 2016-12-14 | A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732496B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626310B (en) * | 2017-09-19 | 2020-02-14 | 中科合成油技术有限公司 | Copper-based catalyst for synthesizing 2,3-dihydrofuran and preparation method and application thereof |
| CN109569622B (en) * | 2017-09-29 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst composition, synthesis method and application thereof |
| CN110038625B (en) * | 2018-01-16 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN110433819A (en) * | 2018-05-04 | 2019-11-12 | 国家能源投资集团有限责任公司 | The method that Fischer Tropsch waxes hydrocracking catalyst and preparation method thereof and Fischer Tropsch waxes are hydrocracked |
| RU2722181C1 (en) * | 2020-01-17 | 2020-05-28 | Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") | Hydrotreating catalyst carrier |
| CN111468097B (en) * | 2020-03-24 | 2023-03-03 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN116059987A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of amorphous silicon aluminum |
| CN115155552B (en) * | 2022-07-13 | 2024-03-12 | 黄骏 | Five-coordination aluminum enriched amorphous silicon-aluminum material and synthesis method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951561A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A catalyst composition and preparation method thereof |
| CN101491774A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | High-silicon amorphous silica aluminum and preparation method thereof |
| CN103861609A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Preparation method of non-supported high-activity hydrogenation catalyst |
-
2016
- 2016-12-14 CN CN201611156531.5A patent/CN106732496B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951561A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A catalyst composition and preparation method thereof |
| CN101491774A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | High-silicon amorphous silica aluminum and preparation method thereof |
| CN103861609A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Preparation method of non-supported high-activity hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732496A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732496B (en) | A kind of high activity amorphous silica-alumina, using it as the hydrocracking catalyst of carrier and their preparation method | |
| JP6134334B2 (en) | Silica-containing alumina support, catalyst produced therefrom and method of use thereof | |
| CN102039138B (en) | Heavy oil or residual oil hydrogenation catalyst and preparation method thereof | |
| RU2569682C2 (en) | Composition and method for preparation of carrier and catalyst of deep hydrofining of hydrocarbon stock | |
| CN101298043A (en) | Hydrothermal deposition preparation of load type single metal hydrogenation catalyst | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| CN101619234B (en) | Method for producing low sulfur gasoline by using light weight gasoline | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| EP2938433A1 (en) | Preparation of a hydrocarbon conversion catalyst | |
| CN109423324B (en) | Method for removing mercaptan from FCC gasoline | |
| RU2306978C1 (en) | Petroleum fractions hydrofining catalyst and a method for preparation thereof | |
| CN113083356B (en) | Mesoporous and microporous ZSM-5/alumina catalyst and preparation method and application thereof | |
| CN105126899B (en) | A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application | |
| CN109420506B (en) | Catalyst for removing mercaptan from gasoline and preparation method thereof | |
| CN104549345B (en) | Active hydrocracking proppant and preparation method thereof | |
| CN101116818B (en) | Hydrated alumina containing metallic element and method for preparing the same | |
| CN107286987B (en) | A kind of group technology handling poor ignition quality fuel | |
| CN105713657B (en) | Hydrocracking method | |
| CN113680347A (en) | Hydrofining catalyst, preparation method thereof and application thereof in oil refining and aromatic ring saturation regulation | |
| RU2607905C1 (en) | Catalyst for hydrocracking hydrocarbon material | |
| CN108212168A (en) | A kind of Hydrobon catalyst of modification and preparation method and application | |
| CN106179389B (en) | Hydrobon catalyst and preparation method thereof | |
| CN106947521B (en) | A kind of processing method of poor ignition quality fuel | |
| CN106268850B (en) | The multi-metal body catalyst and its preparation method of a kind of ultra-deep desulfurization denitrogenation and application | |
| CN113881456B (en) | Hydrocracking method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |