CN104826665A - Preparation method for hydrocracking catalyst carrier - Google Patents
Preparation method for hydrocracking catalyst carrier Download PDFInfo
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Abstract
The invention discloses a preparation method for a hydrocracking catalyst carrier. The method comprises the following steps: subjecting a small-grain Y type molecular sieve, amorphous silicon-aluminum and a binder prepared from alumina to mixing and extrusion molding and then carrying out drying and roasting so as to prepare the carrier. According to the method, a NaY type molecular sieve raw material with a high silica-alumina ratio, a high degree of crystallization and good stability is employed and successively undergoes ammonium exchange, primary hydro-thermal treatment, treatment with an alkali-containing solution, secondary hydro-thermal treatment and treatment with a mixed solution of acid and an ammonium salt; and the obtained small-grain Y type molecular sieve has a high SiO2/Al2O3 mol ratio and a high proportion of secondary pores, retains the stability of a Y type molecular sieve and has a high specific surface area and a high degree of crystallization. The hydrocracking catalyst carrier provided by the invention is applicable to a hydrocracking catalyst for high and medium oil and enables the hydrocracking catalyst to have good activity, medium oil selectivity and product properties.
Description
technical field
The present invention relates to a kind of preparation method of carrier of hydrocracking catalyst, is more particularly a kind of preparation method of the carrier of hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve.
Background technology
Along with the demand of international refined products market to intermediate oil constantly increases, need from mink cell focus, to obtain intermediate oil more, and one of the important means of hydrocracking process light materialization of heavy oil just.Due to this technique, to have adaptability to raw material strong, good product quality, adjustment flexible operation, midbarrel product yield is high, the features such as product structure is flexible, the status of hydrocracking process is made to become more and more important, being faced with petroleum resources shortage, environmental requirement increasingly stringent and oil product structure at present for China is not suitable with the problems such as market especially, the application of hydrocracking technology, by becoming the effective technology measure improving petroleum product-quality, reduce environmental pollution, increase market adaptability to changes, has become the of paramount importance process unit in modernization refinery.These factors facilitate high selectivity to middle distillates hydrocracking technology and develop rapidly just, and hydrocracking catalyst is the key of this technology.
Carrier is the important component part of catalyst, not only for metal active constituent provides dispersion place, carrier itself also participates in reaction simultaneously, whole catalytic reaction has been worked in coordination with together with other active component, hydrocracking catalyst is a kind of bifunctional catalyst, and it is simultaneously containing acidic components and hydrogenation component.Hydrogenation activity is generally selected from VI B race in the periodic table of elements and group VIII metal provides; And its acidic components are mainly provided by zeolite and inorganic oxide, major part be with aluminium oxide or amorphous aluminum silicide for carrier, be equipped with a certain amount of molecular sieve.And the key component playing cracking in this type of catalyst is generally Y molecular sieve, the quality of Y molecular sieve performance, directly affects performance and the product quality of catalyst.
Y zeolite is cracking active component the most general in residual oil cracking field at present, crystal grain is generally about 1000nm, its crystal grain is larger, duct is relatively long, diffusional resistance is large, large molecule is difficult to enter inside, duct and reacts, and afterproduct is also more difficult diffuses out, so its cracking activity and the selective of object product receive restriction in reaction.Compared with conventional Y zeolite, small crystal grain Y-shaped molecular sieve has larger external surface area and Geng Duo outer surface activated centre, is conducive to improving large molecule hydrocarbon cracking capability, thus has more superior catalytic perfomance.Meanwhile, reduce Y zeolite crystallite dimension and can also improve inner surface active sites utilization rate.In general, the diffusion of reactant molecule in molecular sieve endoporus duct is called micropore diffusion.Make molecular sieve inner surface all be used to carry out catalyzed conversion, micropore diffusion speed must be made to be greater than endoporus catalyzed conversion speed.Shortening diffusion path is the best way.The effective way overcoming micropore diffusion restriction reduces zeolite crystal size.This not only can increase the external surface area of zeolite crystal, and shortens diffusion length simultaneously.EP0204236 compares small crystal grain NaY molecular sieve and large grain size NaY molecular sieve, and result shows, the former has higher activity and selective preferably to RFCC.
Small crystal grain NaY molecular sieve does not possess acidity, needs to carry out modification, to meet the performance requirement of Cracking catalyst.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, the method uses dry gas and the fine grain NaY zeolitic contact of silicon tetrachloride, obtain after washing, due to the heat of its raw material self and hydrothermal stability just poor, the method is the mode process molecular sieve adopting gas phase dealumination complement silicon simultaneously, this make the heat of product and hydrothermal stability poorer, active low.Especially to heat endurance and the poor fine grain NaY zeolite of hydrothermal stability, sial skeleton structure less stable in zeolite, be easy to cause removing of framework aluminum in modifying process, simultaneously also some framework silicon also along with removing, part skeleton is caused to occur the phenomenon of caving in, make the crystallization reservation degree of product lower, the activity of zeolite is not high.
CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.This catalyst comprises the carrier of hydrogenation active metals component and small-grain Y molecular sieve, amorphous aluminum silicide and aluminium oxide composition, and wherein said small crystal grain Y-shaped molecular sieve is the small crystal grain Y-shaped molecular sieve after adopting hydrothermal treatment consists.Raw materials used small crystal grain NaY molecular sieve is prepared for method disclosed in CN101722023A, i.e. SiO
2/ Al
2o
3mol ratio is 4.0 ~ 6.0, and average grain diameter, at 100 ~ 700nm, successively by the mixed aqueous solution process of successive modified i.e. ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydrothermal treatment consists, aluminium salt and acid, obtains small-grain Y molecular sieve.In the method, need first to raw material with after the process of ammonium hexafluorosilicate dealumination complement silicon, then carry out the process such as hydrothermal treatment consists, could reduce caving in of the skeleton structure of molecular sieve like this, improve crystallization the reservations degree of molecular sieve, but the method is due to after first using the process of ammonium hexafluorosilicate dealumination complement silicon, due to generation sial same order elements, molecular sieve silica constructed of aluminium is more complete, carry out hydrothermal treatment consists again, the secondary pore of formation is few, and secondary pore proportion is low, divide as catalyst molecule screen banks, middle oily yield is low.
Existing method fine grain NaY type molecular sieve is in preparation process, and Silicified breccias easily runs off, and silicon utilization rate is low, and silicon, aluminium distributing inhomogeneity, easy appearance is reunited, and therefore still cannot to prepare silica alumina ratio high for existing method, and the fine grain NaY type molecular sieve that heat endurance and hydrothermal stability are good again.Through successive modified, can not obtain structural integrity, degree of crystallinity is high and have the small crystal grain Y-shaped molecular sieve of more secondary pore, and as the cracking component of catalyst, middle oily yield is low.
Summary of the invention
For weak point of the prior art, the invention provides the preparation method of the good carrier of hydrocracking catalyst of a kind of catalytic performance.This carrier of hydrocracking catalyst adopts that a kind of dealumination depth is large, degree of crystallinity keeps good, that secondary pore is flourishing small crystal grain Y-shaped molecular sieve as acidic components, is conducive to improving the active and middle distillates oil selectivity of hydrocracking catalyst and improves product property.
The preparation method of carrier of hydrocracking catalyst of the present invention, comprise: small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide and adhesive are mixed, extruded moulding, then at the temperature of 80 DEG C ~ 150 DEG C dry 3 ~ 10 hours and 500 DEG C ~ 600 DEG C roastings 3 ~ 6 hours, is prepared into carrier;
Described small crystal grain Y-shaped molecular sieve, comprises following preparation process:
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve of step (1) is become Na
2the little crystal grain NH of O content≤1.5wt%
4naY;
(3) with little crystal grain NH
4naY is raw material, carries out first time hydrothermal treatment consists;
(4) molecular sieve step (3) obtained is with containing alkaline solution treatment;
(5) molecular sieve that step (4) obtains is carried out second time hydrothermal treatment consists;
(6) molecular sieve acid step (5) obtained and the mixed solution process of ammonium salt, obtain small crystal grain Y-shaped molecular sieve through washing and drying.
Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO
2/ Al
2o
3mol ratio is greater than 6.0 and not higher than 9.0, and preferably 6.5 ~ 9.0, more preferably 7.0 ~ 8.0, average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm; Specific area is 800 ~ 1000 m
2/ g, is preferably 850 ~ 950 m
2/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, cell parameter is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%, be generally 90% ~ 110%, be preferably 90% ~ 105%.
In the inventive method, in step (1), the preparation method of fine grain NaY type molecular sieve is as follows:
I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na
2o:Al
2o
3: (6 ~ 30) SiO
2: (100 ~ 460) H
2o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;
II, employing preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon for 40wt% ~ 75wt%, is preferably 55 wt% ~ 70wt% in the content of silica; Its preparation process comprises:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO
2gas, controlling reaction temperature is 10 ~ 40 DEG C, is preferably 15 ~ 35 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into
2gas flow accounts for 60% ~ 100% of total intake, when being preferably 80% ~ 100%, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silica, is preferably 30wt% ~ 70wt%;
C, under the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel
By (0.5 ~ 6) Na
2o:Al
2o
3: (8 ~ 15) SiO
2: (100 ~ 460) H
2total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide predecessor of step (2) gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents addition accounts for 1% ~ 20% of silica-alumina gel weight,
The reactant mixture of IV, step (3) gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
In the present invention, in step I and III, silicon source, alkali source are selected from sodium metasilicate and NaOH respectively.In step I, aluminium source is selected from sodium metaaluminate.
In Step II, the concentration of the sodium aluminate solution that step a is used is for being preferably 15 ~ 55g Al
2o
3/ L, the concentration of sodium silicate solution is 50 ~ 150 gSiO
2/ L, step b CO used
2the concentration of gas is 30v% ~ 60v%.
In Step II I, control reaction temperature 0 ~ 40 DEG C, preferably 10 ~ 30 DEG C, pH value 9.5 ~ 12.0, preferable ph 10 ~ 11.
In step IV, the reactant mixture of gained carries out crystallization and adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 50 ~ 90 DEG C, and crystallization time is 0.5 ~ 18 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 140 DEG C, and crystallization time is 3 ~ 10 hours, after crystallization completes, more after filtration, washing, dry, obtained product.Two step dynamic crystallization conditions are preferably as follows: the first step: temperature controls at 60 ~ 80 DEG C, and crystallization time is 1 ~ 10 hour; Second step: temperature controls at 80 ~ 120 DEG C, crystallization time is 5 ~ 10 hours.
In step (2), with fine grain NaY type molecular sieve for raw material, with containing H
+the aqueous solution of ammonium salt at 70 ~ 120 DEG C, preferably exchange 0.5 ~ 3.0 hour at 80 ~ 100 DEG C.Wherein said ammonium salt is as one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc.H is provided in the aqueous solution
+acid can be one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid.In the aqueous solution, H
+concentration be 0.005 ~ 0.5mol/L, NH
4 +concentration be 0.5 ~ 5.0mol/L.Y zeolite is 0.05 ~ 0.5g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, washing, dry obtained Na
2o content is at below 1.5wt%.
First time hydrothermal treatment consists temperature described in step (3) is 500 DEG C ~ 700 DEG C, and water vapor pressure is 0.01 ~ 1.0MPa, and the processing time is 1.0 ~ 10.0 hours.
The molecular sieve that step (3) obtains by step (4) is pulled an oar with the aqueous solution of alkali and is mixed, and stir process 1 ~ 4h under maintaining the temperature conditions of 60 ~ 120 DEG C, filter, wash.Alkali is selected from the mixture of NaOH, KOH or NaOH and KOH.The concentration of the aqueous solution of alkali is generally 0.1 ~ 3.0 mol/L, and the concentration of slurries Middle molecule sieve is 0.05 ~ 1.0g/mL.
Second time hydrothermal treatment consists temperature described in step (5) is 500 ~ 800 DEG C, and water vapor pressure is 0.01 ~ 1.0MPa, and the processing time is 1.0 ~ 10.0 hours, and second time hydrothermal treatment consists temperature is identical greater than or equal to first time hydrothermal treatment consists temperature.
In step (6), by the molecular sieve after hydrothermal treatment consists with acid with containing NH
4 +the mixed solution contact of salt composition, exchange the Na in molecular sieve
+with the part non-framework aluminum removed in molecular sieve, acid wherein can be one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH
4 +salt be containing above acid group ammonium salt in one or more; H in mixed solution
+concentration be 0.05 ~ 0.6mol/L, NH
4 +concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step can repeat 1 ~ 4 time.Then remove mother liquor, wash with water, dry.
Adhesive therefor of the present invention is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture aluminium oxide pore volume used is 0.3 ~ 0.5 mL/g, and specific area is 200 ~ 400m
2/ g.
In catalyst carrier of the present invention, mixing amorphous aluminum silicide used can be prepared by coprecipitation or grafting copolymerization process with small-grain Y molecular sieve and adhesive, prepares by conventional method in document.SiO in obtained amorphous aluminum silicide
2weight content be 20% ~ 60%, be preferably 25% ~ 40%, the pore volume of amorphous aluminum silicide is 0.6 ~ 1.1 mL/g, be preferably 0.8 ~ 1.0 mL/g, specific area is 300 ~ 500 m
2/ g, is preferably 350 ~ 500 m
2/ g.
Catalyst of the present invention can carry out shaping according to actual needs, and shape can be cylindrical bars, clover etc.In shaping of catalyst process, shaping assistant can also be added, as peptization acid, extrusion aid etc.Catalyst carrier of the present invention adopts conventional method to carry out drying and roasting, specific as follows: at the temperature of 80 DEG C ~ 150 DEG C dry 3 ~ 10 hours and 500 DEG C ~ 600 DEG C roastings 3 ~ 6 hours.
When catalyst carrier of the present invention is for the preparation of hydrocracking catalyst, carrying method conventional in prior art can be adopted, preferred infusion process, can be saturated leaching, excessive leaching or complexing leaching, namely with the solution impregnated catalyst carrier containing required active component, carrier after dipping, after super-dry, roasting, obtains final hydrocracking catalyst.
Carrier of hydrocracking catalyst of the present invention, comprises small-grain Y molecular sieve, aluminium oxide and amorphous aluminum silicide, and wherein said small-grain Y molecular sieve, its character is as follows: SiO
2/ A1
2o
3mol ratio is 40 ~ 120, and average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm, relative crystallinity>=95%, lattice constant 2.425 ~ 2.440nm, and specific area is 900 ~ 1200m
2/ g, pore volume is the pore volume shared by secondary pore of 0.5 ~ 0.80mL/g, 1.7 ~ 10nm is total pore volume more than 60%.
Carrier of hydrocracking catalyst character of the present invention is as follows: specific area is 450 ~ 650 m
2/ g, pore volume is 0.5 ~ 0.80 mL/g, and the pore volume of bore dia 4 ~ 10nm accounts for 60% ~ 95% of total pore volume, is preferably 70% ~ 90%.
Described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, its composition comprises: the content of small-grain Y molecular sieve is 5wt% ~ 40wt%, and the content of amorphous aluminum silicide is 20wt% ~ 65wt%, and the content of aluminium oxide is 10wt% ~ 40wt%.
Due to the small-grain Y molecular sieve that carrier of the present invention adopts, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, and degree of crystallinity is high, good stability, so in follow-up modification process, the not crystal structure of saboteur's sieve, thus do not affect the stability of final molecular sieve.The present invention is by twice hydrothermal treatment consists, and coordinate the alkali treatment process between twice hydrothermal treatment consists, namely desirable dealumination depth is reached, maintain again the rock-steady structure of molecular sieve preferably, create a large amount of secondary pores simultaneously, not only facilitate the performance of hydrogenation activity, and be conducive to the diffusion of product, hold charcoal ability also greatly to strengthen, reduce the occurrence probability of excessive fragmentation and second pyrolysis, thus catalyst can be made to have the product property of good activity, middle distillates oil selectivity and excellence.
Contain little crystal grain high-crystallinity high silica alumina ratio Y molecular sieve in carrier of the present invention in addition, be applicable in cracking reaction.In the reaction, small crystal grain molecular sieve is Cracking Component, there is larger external surface area and Geng Duo outer surface activated centre, be conducive to improving large molecule hydrocarbon cracking capability, the activity that can to make by this molecular sieve be the hydrocracking catalyst of active component increases, simultaneously can the performance of promoting catalyst Hydrogenation better.
Detailed description of the invention
In order to better the present invention is described, further illustrate the present invention below in conjunction with embodiment and comparative example.But scope of the present invention is not only limited to the scope of these embodiments.Analytical method of the present invention: specific area, pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, and the grain size of molecular sieve adopts the mode of SEM (SEM) to measure.Wt% is mass fraction.
Embodiment 1
The present embodiment is raw materials fine grain NaY type molecular sieve
The preparation of NY-1
(1) preparation of directed agents: get 10 g sodium hydrate solids and be dissolved in 80g water, add sodium metaaluminate 2g (Al
2o
3content is 45wt%, Na
2o content is 41wt%), and then add 36g waterglass (SiO
2content is 28wt%, Na
2o content is 8 wt%), stir ageing 4 hours obtained directed agents at 15 DEG C after mixing.
(2) preparation of amorphous aluminum silicide predecessor
Solid sodium aluminate being mixed with concentration is 40gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO
2/ L sodium metasilicate working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.2L sodium metasilicate working solution, control reaction temperature 20 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.0
2, then add 0.4L sodium metasilicate working solution, then ventilate and stablize 20 minutes.
(3) preparation of gel
100g SiO is added in the slurries that step (2) obtains
2directed agents 120g prepared by/L sodium metasilicate working solution 1.5L and step (1), the pH value of gel is 12, and control reaction temperature 20 DEG C, uniform stirring 30 minutes, staticizes 2 hours.
(4) crystallization
The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 4 hours at 70 DEG C, be then warming up to 100 DEG C, stir crystallization 8 hours, then filter, wash, dry NaY molecular sieve product NY-1, product property is in table 1.
The preparation of NY-2
(1) preparation of directed agents: get 8 g sodium hydrate solids and be dissolved in 80g water, adds sodium metaaluminate 2.5 g (Al
2o
3content is 45wt%, Na
2o content is 41wt%).And then add 40g waterglass (SiO
2content is 28wt%, Na
2o content is 8 wt%), stir ageing 4 hours obtained directed agents at 18 DEG C after mixing.
(2) preparation of amorphous aluminum silicide predecessor
Solid sodium aluminate being mixed with concentration is 30gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to concentration be 70g SiO
2/ L sodium metasilicate working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.4L sodium metasilicate working solution, control reaction temperature 18 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.2
2, then add 0.6L sodium metasilicate working solution, then ventilate and stablize 20 minutes.
(3) preparation of gel
70g SiO is added in the slurries that step (2) obtains
2directed agents 100g prepared by/L sodium metasilicate working solution 1.5L and step (1), the pH value of gel is 11.5, and control reaction temperature 15 DEG C, uniform stirring 30 minutes, staticizes 2.5 hours.
(4) crystallization
The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, be then warming up to 110 DEG C, stir crystallization 7 hours, then filter, wash, dry NaY molecular sieve product NY-2, product property is in table 1.
Embodiment 2
First ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-1.Preparation is containing NH
4 +and H
+concentration be respectively the solution (ammonium chloride and hydrochloric acid mixed solution) 10 liters of 1.0mol/L and 0.02mol/L.Take small crystal grain NaY molecular sieve 1000 grams, be added in above-mentioned mixed solution, speed of agitator is 300rpm, and at 90 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na
2o content; Repeat aforesaid operations, until Na in molecular sieve
2o content reach 1.5wt%, obtaining dried sample number into spectrum is NNY-1.
Embodiment 3
First ammonium exchange is carried out to raw material fine grain NaY type molecular sieve NY-2.Preparation is containing NH
4 +and H
+concentration be respectively the solution (ammonium nitrate and nitric acid mixed solution) 10 liters of 0.8.0mol/L and 0.01mol/L.Take small crystal grain NaY molecular sieve 1000 grams, be added in above-mentioned mixed solution, speed of agitator is 300rpm, and at 95 DEG C, constant temperature stirs l hour, then filtering molecular sieve, and stays sample, analyzes Na
2o content; Repeat aforesaid operations, until Na in molecular sieve
2o content reach 1.5wt%, obtaining dried sample number into spectrum is NNY-2.
Embodiment 4
Get 100 grams of NNY-1 and be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, the water vapor pressure simultaneously maintaining system is 0.15MPa, processes 2 hours, and sample is taken out in cooling.Be that 1 mol/L NaOH solution is pulled an oar and mixed by the molecular sieve obtained and 500mL concentration, and stir process 2h under maintaining the temperature conditions of 80 DEG C, filter, be washed to solution close to neutral; Wet cake is placed in heat-treatment furnace, temperature is risen to 640 DEG C, control water vapor pressure is 0.2MPa, constant temperature 3 hours, cooling, takes out sample; Finally with using containing NH
4 +and H
+concentration be respectively the solution mixed solution 600mL of 2.0mol/L ammonium chloride and 0.2mol/L hydrochloric acid and sample contacts and stir, 90 DEG C of process 2 hours, filter, washing, dry, obtain modification small-grain Y-1.The physico-chemical property of Y-1 is in table 1.
Embodiment 5
Get 100 grams of NNY-1 type molecular sieves and be placed in heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 650 DEG C, maintain the steam partial pressure 0.08MPa of system simultaneously, process 2 hours, cooling, take out sample; Be that 0.5mol/L KOH solution is pulled an oar and mixed by the molecular sieve obtained and 600mL concentration, and stir process 2h under maintaining the temperature conditions of 90 DEG C, filter, be washed to solution close to neutral; Wet cake be placed in heat-treatment furnace, temperature risen to 700 DEG C, and to control water vapor pressure in stove be 0.1MPa, constant temperature 2 hours that sample is taken out in cooling; Final sample is with containing NH
4 +and H
+concentration be respectively the mixed solution 600mL of 1.0mol/L ammonium nitrate and 0.15mol/L nitric acid and sample contacts and stir, at 100 DEG C, process 3 hours, filter, washing, dry, obtain modification small-grain Y-2.The physico-chemical property of Y-2 is in table 1.
Embodiment 6
Get 100 grams of NNY-2 type molecular sieves and be placed in heat-treatment furnace, control the heating rate of 450 DEG C/h, temperature is risen to 650 DEG C, maintain the steam partial pressure 0.15MPa of system simultaneously, process 2 hours, cooling, take out sample; The molecular sieve obtained and 500mL are contained H
+kOH and the NaOH mixed solution making beating of concentration 0.8mol/L mixes, and stir process 2h under maintaining the temperature conditions of 100 DEG C, filter, be washed to solution close to neutral; Wet cake be placed in heat-treatment furnace, temperature risen to 650 DEG C, and to control water vapor pressure in stove be 0.15MPa, constant temperature 2 hours that sample is taken out in cooling; Final sample is with containing NH
4 +and H
+concentration be respectively solution (ammonium nitrate and the nitric acid mixed solution) 600mL of 1.5mol/L and 0.3mol/L and sample contacts and stir, at 95 DEG C, process 3 hours, filter, washing, dry, obtain modification small-grain Y-3.The physico-chemical property of Y-3 is in table 1.
Embodiment 7
By 25 grams of Y-1 molecular sieves (butt 90wt%), 106.5 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-1, character is in table 2.
Embodiment 8
By 30 grams of Y-2 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-2, character is in table 2.
Embodiment 9
By 40 grams of Y-3 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesives (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst CAT-3, and carrier and corresponding catalyst character are in table 2.
Comparative example 1
1, fine grain NaY is with reference to CN101722023A preparation.
Feedstock property used in this comparative example is as follows: low alkali sodium metaaluminate: Na
2o content 120g/L, Al
2o
3content 40g/L; Waterglass: SiO
2content 250g/L; Aluminum sulfate: Al
2o
3content 90g/L.
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of gel: temperature is 8 DEG C, under stirring condition, 59.4mL aluminum sulfate, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents is added successively in the waterglass of 208mL, then constant temperature constant speed stirs 1.5 hours, then by the synthesis liquid that obtains static aging 8 hours at the temperature disclosed above, gel is obtained.
(3) crystallization: under agitation, was raised to 50 DEG C by the gel in synthesis reactor in 20 minutes, and constant temperature stirs crystallization 7 hours; After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor is brought up to 120 DEG C, then constant temperature stirs 6 hours.After filtration, wash and drying, obtain the little crystal grain CNY-l of product.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-1, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-1.
3, carry out subsequent treatment to CNNY-1, processing mode and condition, with embodiment 4, obtain Reference Product CY-1.The physico-chemical property of CY-1 is in table 1.
4, by 30 grams of CY-1 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, carrier TCCAT-1 is obtained.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst CCAT-1, and carrier and corresponding catalyst character are in table 2.
Comparative example 2
1, fine grain NaY is with reference to CN1785807A preparation.
The preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
Be positioned in beaker by 14.21g water, controlling fluid temperature in beaker is 60 DEG C, adds the A1 of 12.79g50wt% under rapid stirring simultaneously
2(SO
4)
3) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, the pH value of gel is 12.5, after stirring, loaded in stainless steel cauldron, stirred crystallization 6 hours at 60 DEG C, then be warming up to 100 DEG C of static crystallizations 60 hours, then filter, wash, dry CNY-2 molecular sieve.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-1, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-2.
3, carry out subsequent treatment to CNNY-2, processing mode and condition, with embodiment 4, obtain Reference Product CY-2.The physico-chemical property of CY-2 is in table 1.
4, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-2, character is in table 2.
Comparative example 3
1, fine grain NaY preparation
(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.
(2) preparation of amorphous aluminum silicide predecessor.
Solid sodium aluminate being mixed with concentration is 40gAl
2o
3/ L sodium aluminate working solution, gets containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to concentration be 100g SiO
2/ L sodium metasilicate working solution.Get 1L sodium aluminate working solution and be placed in plastic cans, then add 0.6L sodium metasilicate working solution, control reaction temperature 20 DEG C, pass into the CO that concentration is 50v%
2gas, stops logical CO when pH value reaches 10.0
2, then ventilate and stablize 20 minutes.
(3) preparation of gel is with embodiment 1.
(4) crystallization is with embodiment 1, obtains products C NY-3, and product property is in table 1.
2, carry out ammonium exchange to raw material small crystal grain NaY molecular sieve CNY-3, treatment conditions are with embodiment 2, and obtaining dried sample number into spectrum is CNNY-3.
3, carry out subsequent treatment to CNNY-3, processing mode and condition, with embodiment 4, obtain Reference Product CY-3.The physico-chemical property of CY-3 is in table 1.
By 40 grams of CY-3 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, than
Surface area 350m
2/ g, butt 70wt%), 120 grams of adhesive (butt 20wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.25) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCCAT-3, character is in table 2.
The character of table 1 Y zeolite
| Production code member | NY-1 | NY-2 | Y-1 | Y-2 | Y-3 | CY-1 | CY-2 | CY-3 |
| Feed intake SiO 2/Al 2O 3Mol ratio | 9.1 | 10.1 | ||||||
| SiO 2/Al 2O 3Mol ratio | 7.5 | 8.4 | 72 | 115 | 89 | 50 | 25 | 28 |
| Specific area, m 2/g | 916 | 898 | 1030 | 1140 | 1090 | 940 | 801 | 815 |
| Pore volume, mL/g | 0.39 | 0.38 | 0.59 | 0.72 | 0.66 | 0.35 | 0.33 | 0.36 |
| Secondary pore (1.7-10nm), % | 69.1 | 80.4 | 66.2 | 39.1 | 27.9 | 36.2 | ||
| External surface area, m 2/g | 191 | 182 | 274 | 299 | 255 | 170 | 159 | 180 |
| Lattice constant, nm | 2.461 | 2.462 | 2.432 | 2.426 | 2.429 | 2.432 | 2.433 | 2.433 |
| Relative crystallinity, % | 101 | 110 | 115 | 108 | 112 | 89 | 82 | 83 |
| Average crystallite size, nm | 380 | 430 | 400 | 380 | 430 | 400 | 450 | 400 |
The physico-chemical property of table 2 carrier and catalyst
| Bearer number | TCAT-1 | TCAT-2 | TCAT-3 | TCCAT-1 | TCCAT-2 | TCCAT-3 |
| Small-grain Y molecular sieve, wt% | 18 | 22 | 29 | 29 | 29 | 22 |
| Amorphous aluminum silicide, wt% | 62 | 58 | 51 | 51 | 51 | 58 |
| Aluminium oxide, wt% | 20 | 20 | 20 | 20 | 20 | 20 |
| Specific area, m 2/g | 512 | 525 | 550 | 455 | 438 | 430 |
| Pore volume, ml/g | 0.59 | 0.61 | 0.66 | 0.51 | 0.47 | 0.46 |
| Pore size distribution (4-10nm), % | 72 | 76 | 68 | 49 | 46 | 43 |
| Catalyst is numbered | CAT-3 | CCAT-1 | ||||
| Specific area, m 2/g | 420 | 325 | ||||
| Pore volume, ml/g | 0.60 | 0.46 | ||||
| Pore size distribution (4-10nm), % | 63 | 45 |
The invention described above catalyst CAT-3 and comparative example catalyst CCAT-1 is carried out active evaluation test.Test is carried out on 200ml small hydrogenation device, and adopt one-stage serial technological process, raw materials used oil nature is in table 3.Operating condition is as follows: hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500:1, air speed 1.5h
-1, control cracking zone nitrogen content 5 ~ 10 μ g/g.Catalyst Activating Test the results are shown in Table 4.
Table 3 feedstock oil character
| Feedstock oil | Iran VGO |
| Density (20 DEG C), g/cm 3 | 0.9025 |
| Boiling range, DEG C | 308～560 |
| Condensation point, DEG C | 33 |
| Acid number, mgKOH/g | 0.53 |
| Carbon residue, wt% | 0.2 |
| S，wt％ | 1.5 |
| N，wt％ | 0.11 |
| C，wt％ | 84.93 |
| H，wt％ | 12.52 |
| Aromatic hydrocarbons, wt% | 39.2 |
| BMCI value | 41.5 |
| Refractive power/n D 70 | 1.48570 |
Table 4 catalyst activity evaluation result
| Catalyst is numbered | CAT-2 | CCAT-1 |
| Reaction temperature, DEG C | 376 | 380 |
| Product slates | ||
| < 370 DEG C of conversion ratios, wt% | 65.0 | 64.8 |
| Middle distillates oil selectivity, %(132 ~ 370 DEG C) | 87.4 | 81.8 |
| Major product character | ||
| Jet fuel (132 ~ 282 DEG C) | ||
| Freezing point, DEG C | <－60 | <－60 |
| Aromatic hydrocarbons, wt% | 2.9 | 4.0 |
| Smoke point, mm | 27 | 26 |
| Diesel oil (282 ~ 370 DEG C) | ||
| Cetane number | 64 | 59 |
| Condensation point, DEG C | -7 | -2 |
Can be found out by the evaluation result of table 4 catalyst, the catalyst prepared by the present invention is on the basis of greater activity, and have well selective, product property is good.
Claims (23)
1. a preparation method for carrier of hydrocracking catalyst, comprising: by small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide and the adhesive mixing made from aluminium oxide, extruded moulding, and then drying and roasting, make carrier; The preparation method of described small crystal grain Y-shaped molecular sieve, comprising:
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve of step (1) is become Na
2the little crystal grain NH of O content≤1.5wt%
4naY;
(3) with little crystal grain NH
4naY is raw material, carries out first time hydrothermal treatment consists;
(4) molecular sieve step (3) obtained is with containing alkaline solution treatment;
(5) molecular sieve that step (4) obtains is carried out second time hydrothermal treatment consists;
(6) molecular sieve acid step (5) obtained and the mixed solution process of ammonium salt, through washing and drying, obtain small crystal grain Y-shaped molecular sieve;
The small crystal grain NaY molecular sieve that wherein step (1) is used, its character is as follows: SiO
2/ Al
2o
3mol ratio is greater than 6.0 and not higher than 9.0, average grain diameter is 200 ~ 700nm, specific surface 800 ~ 1000 m
2/ g, pore volume 0.30/ ~ 0.45mL/g, relative crystallinity is 90% ~ 130%, and cell parameter is 2.460 ~ 2.470nm, through roasting in 650 DEG C of air after 3 hours relative crystallinity be more than 90%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be more than 90%.
2. in accordance with the method for claim 1, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used
2/ Al
2o
3mol ratio is 6.5 ~ 9.0.
3. in accordance with the method for claim 1, it is characterized in that: the SiO of small crystal grain NaY molecular sieve used
2/ Al
2o
3mol ratio is 7.0 ~ 8.0.
4. in accordance with the method for claim 1, it is characterized in that: the average grain diameter of small crystal grain NaY molecular sieve used is 300 ~ 500nm.
5. in accordance with the method for claim 1, it is characterized in that: small crystal grain NaY molecular sieve used through roasting in 650 DEG C of air after 3 hours relative crystallinity be 90% ~ 110%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be 90% ~ 110%.
6. in accordance with the method for claim 1, it is characterized in that: the preparation method of small crystal grain NaY molecular sieve used, comprising:
I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6 ~ 30) Na
2o:Al
2o
3: (6 ~ 30) SiO
2: (100 ~ 460) H
2o, after stirring, stirs ageing 0.5 ~ 24 hour obtained directed agents at 0 ~ 20 DEG C by mixture;
II, adopt preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon in the content of silica for 40wt% ~ 75wt%; Its preparation process comprises:
A, respectively preparation sodium aluminate solution and sodium silicate solution;
B, to step a preparation sodium aluminate solution in add step a preparation part sodium silicate solution, then pass into CO
2gas, controlling reaction temperature is 10 ~ 40 DEG C, and the pH value controlling cemented into bundles is 8 ~ 11; Wherein as the CO passed into
2when gas flow accounts for 60% ~ 100% of total intake, add remainder sodium silicate solution, wherein in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 5wt% ~ 85wt% of silica;
C, under the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes;
III, prepare silica-alumina gel: by (0.5 ~ 6) Na
2o:Al
2o
3: (8 ~ 15) SiO
2: (100 ~ 460) H
2total molar ratio of O, under the condition of 0 ~ 40 DEG C of rapid stirring, add water, silicon source, directed agents and alkali source in the amorphous aluminum silicide predecessor of Step II gained, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel; Wherein directed agents addition accounts for 1% ~ 20% of silica-alumina gel weight,
The reactant mixture of IV, Step II I gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
7. in accordance with the method for claim 6, it is characterized in that in Step II, amorphous aluminum silicide predecessor, with the weight of the butt of amorphous aluminum silicide predecessor for benchmark, silicon is 55 wt% ~ 70wt% in the content of silica.
8. in accordance with the method for claim 6, it is characterized in that: it is 15 ~ 35 DEG C that step b controls reaction temperature.
9. in accordance with the method for claim 6, it is characterized in that: in step b, as the CO passed into
2when gas flow accounts for 80% ~ 100% of total intake, add remainder sodium silicate solution.
10. in accordance with the method for claim 6, it is characterized in that: in step b, remainder sodium silicate solution accounts for step b in silica and adds sodium silicate solution total amount in the 30wt% ~ 70wt% of silica.
11. in accordance with the method for claim 6, and it is characterized in that, in step I and III, silicon source, alkali source are selected from sodium metasilicate and NaOH respectively, in step I, aluminium source is selected from sodium metaaluminate.
12. in accordance with the method for claim 6, it is characterized in that in Step II I, controls reaction temperature 10 ~ 30 DEG C, pH value 10 ~ 11.
13. in accordance with the method for claim 6, it is characterized in that step IV adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 50 ~ 90 DEG C, and crystallization time is 0.5 ~ 18 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 140 DEG C, and crystallization time is 3 ~ 10 hours.
14. in accordance with the method for claim 6, it is characterized in that step IV adopts two step dynamic crystallizations, and wherein to carry out the condition of dynamic crystallization as follows for the first step: temperature controls at 60 ~ 80 DEG C, and crystallization time is 1 ~ 10 hour; The condition that second step carries out dynamic crystallization is as follows: temperature controls at 80 ~ 120 DEG C, and crystallization time is 5 ~ 10 hours.
15. in accordance with the method for claim 1, it is characterized in that in step (2), with fine grain NaY type molecular sieve for raw material, with containing H
+the aqueous solution of ammonium salt at 70 ~ 120 DEG C, exchange 0.5 ~ 3.0 hour; Containing H
+ammonium salt the aqueous solution in, H
+concentration be 0.005 ~ 0.5mol/L, NH
4 +concentration be 0.5 ~ 5.0mol/L, molecular sieve is 0.05 ~ 0.50 g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time.
16. in accordance with the method for claim 15, it is characterized in that in step (2), and described ammonium salt is one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, provides H in the aqueous solution
+acid be one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid.
17. in accordance with the method for claim 1, and it is characterized in that the first time hydrothermal treatment consists temperature described in step (3) is 500 DEG C ~ 700 DEG C, water vapor pressure is 0.01 ~ 1.0MPa, and the processing time is 1.0 ~ 10.0 hours.
18. in accordance with the method for claim 1, it is characterized in that molecular sieve that step (3) obtains by step (4) is pulled an oar with the aqueous solution of alkali and mix, and stir process 1 ~ 4h under maintaining the temperature conditions of 60 ~ 120 DEG C, filters, washing; Described alkali is selected from the mixture of NaOH, KOH or NaOH and KOH, and the concentration of the aqueous solution of alkali is 0.1 ~ 3.0 mol/L, and the concentration of slurries Middle molecule sieve is 0.05 ~ 1.0g/mL.
19. in accordance with the method for claim 1, it is characterized in that the second time hydrothermal treatment consists temperature described in step (5) is 500 ~ 800 DEG C, water vapor pressure is 0.01 ~ 1.0MPa, processing time is 1.0 ~ 10.0 hours, and second time hydrothermal treatment consists temperature is identical greater than or equal to first time hydrothermal treatment consists temperature.
20. in accordance with the method for claim 1, it is characterized in that in step (6), and with acid and the mixed solution process of ammonium salt, acid is wherein one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH
4 +salt be containing above acid group ammonium salt in one or more; H in mixed solution
+concentration be 0.05 ~ 0.6mol/L, NH
4 +concentration be 0.5 ~ 3.0mol/L, exchange temperature is 70 ~ 120 DEG C, and the concentration exchanging slurries Middle molecule sieve is 0.1 ~ 0.5g/mL, and swap time is 0.5 ~ 3.0 hour, and exchange step can repeat 1 ~ 4 time.
21. in accordance with the method for claim 1, it is characterized in that: mix SiO in amorphous aluminum silicide used with small crystal grain Y-shaped molecular sieve and adhesive
2weight content be 20% ~ 60%, the pore volume of amorphous aluminum silicide is 0.6 ~ 1.1 mL/g, and specific area is 300 ~ 500 m
2/ g.
22. in accordance with the method for claim 1, it is characterized in that: the condition of carrier drying and roasting is as follows: at the temperature of 80 DEG C ~ 150 DEG C dry 3 ~ 10 hours and 500 DEG C ~ 600 DEG C roastings 3 ~ 6 hours.
23. in accordance with the method for claim 1, it is characterized in that: described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, its composition comprises: the content of small crystal grain Y-shaped molecular sieve is 5wt% ~ 40wt%, the content of amorphous aluminum silicide is 20wt% ~ 65wt%, and the content of aluminium oxide is 10wt% ~ 40wt%.
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| CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN102049280A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN103100403A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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|---|---|---|---|---|
| CN101618348A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN102049280A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve and preparation method thereof |
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