CN104826651A - Preparation method for hydrocracking catalyst - Google Patents
Preparation method for hydrocracking catalyst Download PDFInfo
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- CN104826651A CN104826651A CN201410045472.9A CN201410045472A CN104826651A CN 104826651 A CN104826651 A CN 104826651A CN 201410045472 A CN201410045472 A CN 201410045472A CN 104826651 A CN104826651 A CN 104826651A
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Abstract
The invention discloses a preparation method for a hydrocracking catalyst. The method comprises the following steps: subjecting a small-grain Y type molecular sieve, amorphous silicon-aluminum and a binder prepared from alumina to mechanical mixing and molding and then carrying out drying and roasting so as to prepare a catalyst carrier; then loading a hydrogenation active metal component; and carrying out drying and roasting so as to obtain the catalyst. 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 alkali washing, ammonium exchange, aluminum removal and silicon supplement, 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 provided by the invention is applicable as a hydrocracking catalyst for high and medium oil and has good activity, medium oil selectivity and product properties.
Description
technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, is more particularly a kind of preparation method of the 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 hydrocracking catalyst of a kind of catalytic performance.This hydrocracking catalyst adopts that a kind of high silica alumina ratio, high-crystallinity, secondary pore are many, the small crystal grain Y-shaped molecular sieve of bigger serface as acidic components, prepared hydrocracking catalyst has higher activity, middle distillates oil selectivity and excellent product property.
Hydrocracking catalyst of the present invention, described hydrogenation active metals is the metal of group vib and/or the VIIIth race, and group vib metal is preferably molybdenum and/or tungsten, and the metal of the VIIIth race is preferably cobalt and/or nickel.With the weight of catalyst for benchmark, the content of group vib metal (with oxide basis) is the content of 10wt% ~ 30wt% and group VIII metal (with oxide basis) is 4wt% ~ 10wt%, and the content of carrier is 61.0% ~ 87.0%.
The preparation method of hydrocracking catalyst of the present invention, comprises the steps:
By small-grain Y molecular sieve, amorphous aluminum silicide and the adhesive mechanical mixture made with aluminium oxide, shaping, then dry and roasting, makes catalyst carrier; Supported active metals component in the catalyst carrier of gained, drying and roasting, make catalyst;
Wherein said small-grain Y molecular sieve, comprises following preparation process:
(1) preparation of fine grain NaY type molecular sieve;
(2) fine grain NaY is used containing alkaline solution treatment;
(3) the fine grain NaY type molecular sieve that step (2) obtains is become Na
2the little crystal grain NH of O content≤2.5wt%
4naY;
(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and separation of by-products;
(5) little crystal grain NH is obtained to step (4)
4naY molecular sieve carries out hydrothermal treatment consists;
(6) molecular sieve step (5) obtained is with containing NH
4 +and H
+mixed solution process, through washing and dry, obtain small crystal grain Y-shaped molecular sieve.
The preparation method of the middle fine grain NaY type molecular sieve of step (1) in the inventive method, comprising:
A, 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;
B, employing acid-base precipitation legal system are for amorphous aluminum silicide predecessor, and 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 acid-base neutralization plastic, aging, wherein silicon introduces the method for reaction system is in aluminiferous material and introducing portion is containing silicon materials before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and introduces before ageing after plastic;
C, prepare silica-alumina gel
By (0.5 ~ 6) Na
2o:Al
2o
3: (7 ~ 11) 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 D, step C gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
In the present invention, in steps A and C, silicon source, alkali source can adopt routine to prepare silicon source and the alkali source of molecular sieve, and in the present invention, preferred silicon source adopts sodium metasilicate, and alkali source adopts NaOH.In steps A, aluminium source can adopt routine to prepare the aluminium source of molecular sieve, preferably adopts sodium metaaluminate in the present invention.
In the present invention, step B preferably in aluminiferous material and plastic after and the silicon introduced before ageing accounts for the silicon in amorphous aluminum silicide predecessor in the 5wt% ~ 85wt% of silica in silica, be preferably 30wt% ~ 70wt%.
In the present invention, the preparation method of the amorphous aluminum silicide predecessor of step B adopts conventional acid-base precipitation method, and comprising acid-base neutralization plastic, aging, wherein acid-base neutralization plastic process is generally the neutralization reaction process of acid material and alkaline material.In and plastic process can adopt the mode of acid material or the continuous acid-base titration of alkaline material, also can adopt acid material and alkaline material and the mode of stream neutralization.Wherein the method introduced in reaction system of silicon is as follows: introducing portion is containing silicon materials in aluminiferous material and before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and introduces before ageing after plastic.Silicon in aluminiferous material and before plastic and/or in plastic process can be in carrying out again after mix with acid material or alkaline material according to the different character containing silicon materials with plastic (such as contain silicon materials adopt sodium metasilicate time, sodium metasilicate can mix with alkaline material; During containing silicon materials employing Ludox, add acid aluminiferous material), also can add containing silicon materials separately in reaction system in aluminiferous material He in plastic process, also can be the combination of said method.Plastic material generally comprises aluminiferous material (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3and NaAlO
2deng in one or more), containing silicon materials (one or more in waterglass, Ludox and organic silicon-containing compound etc., wherein organic silicon-containing compound is one or more in silanol, silicon ether and siloxanes, precipitating reagent is divided into acidic precipitation agent and alkaline precipitating agent, wherein alkaline precipitating agent is one or more in NaOH, ammoniacal liquor, sodium carbonate, sodium acid carbonate, and acidic precipitation agent is CO
2or nitric acid, the different choice according to plastic process uses, and conventional mode of operation mainly contains: (1) acid aluminium salt (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3) and basic aluminium salt (NaAlO
2) or alkaline precipitating agent (NaOH, NH
4oH) in and plastic, (2) basic aluminium salt (NaAlO
2) and acidic precipitation agent (CO
2) in and plastic.Described plastic process is generally carried out at room temperature ~ 85 DEG C, is comparatively suitably for 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C.The pH value of described plastic process control system is 7.0 ~ 10.0, is preferably 7.5 ~ 9.0.When adopting continuous acid-base titration, the pH value controlling final plastic system is 7.0 ~ 10.0, is preferably 7.5 ~ 9.0, when to adopt and the pH value making colloid system in flow with plastic time control remains 7.0 ~ 10.0, and preferably 7.5 ~ 9.0.Carry out aging after plastic, aging condition is as follows: pH is 7.0 ~ 10.0, and be preferably 7.0 ~ 9.5, ageing time 0.2 ~ 8.0 hour, is comparatively adapted at 0.5 ~ 5 hour, and be preferably 1 ~ 3 hour, aging temperature is room temperature ~ 85 DEG C, is preferably 40 ~ 80 DEG C.Temperature time aging and pH with in time temperature preferably identical with pH.
In step C, control reaction temperature 0 ~ 40 DEG C, preferably 10 ~ 30 DEG C, pH value 9.5 ~ 12.0, preferable ph 10 ~ 11.
The reactant mixture of step D 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.
Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO
2/ Al
2o
3mol ratio is 5.0 ~ 9.0, preferably 6.0 ~ 9.0, more preferably 7.0 ~ 8.0, and average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm; Specific surface 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 generally more than 85%, be preferably 90% ~ 110%, through 700 DEG C of water vapour hydrothermal treatment consists after 2 hours relative crystallinity be generally more than 85%, be preferably 90% ~ 110%.
In step (2), small crystal grain NaY molecular sieve is pulled an oar with the aqueous solution of alkali and mixes, and stir process 1 ~ 4h under maintaining the temperature conditions of 60 ~ 120 DEG C, filter, wash.Alkali wherein used is the mixture of NaOH, KOH or NaOH and KOH.The concentration of the aqueous solution of alkali is generally 0.1 ~ 3 mol/L, and the concentration of slurries Middle molecule sieve is 0.05 ~ 1.0g/mL.
In step (4), in aqueous medium, add little crystal grain NH
4naY(solid-liquid weight ratio 1:4 ~ 1:8), stir and be warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, after dropwising, constant temperature stirs 1 ~ 2 hour, isolated molecule sieve and accessory substance, and filter, dry.The concentration 10 wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little crystal grain NH
410wt% ~ the 50wt% of NaY molecular sieve.
In step (5), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500 ~ 750 DEG C, preferably controls at 600 ~ 700 DEG C, and pressure is 0.01 ~ 0.50MPa, and be preferably 0.05 ~ 0.30MPa, the processing time is 1.0 ~ 4.0 hours.
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.
Other operating procedure in modified Y molecular sieve preparation method of the present invention, as ammonium salt exchanges method of operating and the condition that can adopt this area routine.The method that step (3) adopts ammonium salt to exchange, specific as follows: to take NaY molecular sieve as raw material, with the aqueous solution of solubility ammonium salt at 70 ~ 120 DEG C, preferably exchange 0.5 ~ 3.0 hour at 80 ~ 100 DEG C, Y molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, washing, dry.Ammonium salt is as one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., and the concentration of ammonium salt solution is 0.5 ~ 5.0mol/L.
Detailed process prepared by carrier of hydrocracking catalyst of the present invention is: 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, carrier is prepared into.
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.
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%, and the content of amorphous aluminum silicide is 20wt% ~ 65wt%, and the content of aluminium oxide is 10wt% ~ 40wt%.
The load of catalyst activity metal of the present invention, 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, 100 DEG C ~ 150 DEG C dry l ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 3 ~ 6 hours, obtains final catalyst.
Hydrocracking catalyst of the present invention, the carrier comprising hydrogenation active metals component and be made up of small-grain Y molecular sieve, aluminium oxide and amorphous aluminum silicide, wherein said small-grain Y molecular sieve, its character is as follows: SiO
2/ A1
2o
3mol ratio is 30 ~ 120, and average grain diameter is 200 ~ 700nm, preferably 300 ~ 500nm, and relative crystallinity is more than 100%, and be preferably 100% ~ 120%, lattice constant 2.425 ~ 2.450nm, specific area is 850 ~ 1000m
2/ g, pore volume is the pore volume shared by secondary pore of 0.40 ~ 0.60mL/g, 1.7 ~ 10nm is more than 50% of total pore volume, is preferably 50% ~ 80%, Na
2o content≤0.15wt%.
Hydrocracking catalyst character of the present invention is as follows: specific area is 300 ~ 500 m
2/ g, pore volume is 0.35 ~ 0.60 mL/g, and the pore volume of aperture 4 ~ 10nm accounts for 55% ~ 90% of total pore volume, is preferably 65% ~ 80%.
Hydrocracking catalyst of the present invention is used for hydrocracking process, be suitable for treatment of heavy hydrocarbon material, the heavy charge scope being applicable to this law is very wide, and they comprise vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon-type oil of catalytic cracking circulation wet goods, also can be used in combination, raw material is generally the hydro carbons containing boiling point 300 ~ 600 DEG C, and nitrogen content can at 50 ~ 2500 μ g/g.
Hydrocracking catalyst of the present invention is specially adapted to single hop once by method for hydrogen cracking, operating condition is as follows: reaction temperature 350 ~ 420 DEG C, be more preferably 360 ~ 390 DEG C, hydrogen dividing potential drop 6 ~ 20MPa, be more preferably 9 ~ 15MPa, hydrogen to oil volume ratio 500 ~ 2000:1, is more preferably 800 ~ 1500:1, volume space velocity 0.5 ~ 1.8 h during liquid
-1, be more preferably 0.8 ~ 1.5h
-1.
Due to the small-grain Y molecular sieve that catalyst 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, and do not affect the stability of final molecular sieve.Molecular sieve of the present invention has carried out alkali treatment before ammonium exchanges, match with chemical dealuminization afterwards and hydrothermal treatment consists, namely desirable dealumination depth is reached, maintain molecular sieve structure preferably again, create by 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.
Small crystal grain molecular sieve is adopted to be Cracking Component in addition in carrier of the present invention, 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 small crystal grain NaY molecular sieve
The preparation of NY-1
(1) preparation of directed agents: get 8g sodium hydrate solid 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 0.3L concentration is 100g A1
2o
3/ L sodium aluminate working solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Get containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to 0.5L concentration be 140g SiO
2/ L sodium metasilicate working solution (c).Get the steel retort of one 5 liters, 0.5 liter of distilled water is added and after being heated with stirring to 70 DEG C in tank, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) to make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 60 DEG C.After reacting aluminum sulfate completes, stop adding (b), the addition of (c) is 0.17L, after the silicon-aluminum sol of generation stablizes 20 minutes, continue to add (c) 0.33L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.
(3) preparation of gel
1L H is added in the slurries that step (2) obtains
2o, 140g SiO
2directed agents 100g prepared by/L sodium metasilicate working solution 0.6L 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-1, character lists in table l.
The preparation of NY-2
(1) preparation of directed agents: get 10 g sodium hydrate solids and be dissolved in 90g water, adds sodium metaaluminate 3 g (Al
2o
3content is 45wt%, Na
2o content is 41wt%), and then add 50g waterglass (SiO
2content is 28wt%, Na
2o content is 8wt%), stir ageing 4 hours obtained directed agents at 20 DEG C after mixing.
(2) preparation of amorphous aluminum silicide predecessor
Solid aluminum sulfate being mixed with 0.5L concentration is 80g A1
2o
3/ L aluminum sulfate working solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Get containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to 0.4L concentration be 150g SiO
2/ L sodium metasilicate working solution (c).Get the steel retort of one 5 liters, 0.5 liter of distilled water is added and after being heated with stirring to 70 DEG C in tank, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) to make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 60 DEG C.After reacting aluminum sulfate completes, stop adding (b), the addition of (c) is 0.2L, after the silicon-aluminum sol of generation stablizes 20 minutes, continue to add (c) 0.2L, add in 10 minutes, start the ageing process of system, keep pH value 8.0, temperature 60 C, aging 30 minutes.
(3) preparation of gel
1.2L H is added in the slurries that step (2) obtains
2o, 150g SiO
2directed agents 120g prepared by/L sodium metasilicate working solution 0.8L and step (1), the pH value of gel is 12, and control reaction temperature 30 DEG C, uniform stirring 30 minutes, staticizes 3 hours.
(4) crystallization
The gel that step (2) obtains is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, be then warming up to 120 DEG C, stir crystallization 5 hours, then filter, wash, dry NaY molecular sieve product NY-2, character lists in table l.
Embodiment 2
First carrying out alkali treatment to raw material small crystal grain NaY molecular sieve, is that the NaOH solution making beating of 1 mol/L mixes by 1000 grams of NY-1 and 5L concentration, and stir process 2h under maintaining the temperature conditions of 80 DEG C, filter, be washed to solution close to neutral; Contacted by the 0.5mol/L aqueous ammonium nitrate solution of filter cake with 10 liters, 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 2.5wt%, obtaining dried sample number into spectrum is NNY-1.
Embodiment 3
First carrying out alkali treatment to raw material small crystal grain NaY molecular sieve, is that the KOH solution making beating of 0.8 mol/L mixes by 1000 grams of NY-2 and 5L concentration, and stir process 2h under maintaining the temperature conditions of 80 DEG C, filter, be washed to solution close to neutral; Contacted by the 0.5mol/L aqueous ammonium nitrate solution of filter cake with 10 liters, 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
2the content of O reaches 2.5wt%, and obtaining dried sample number into spectrum is NNY-2.
Embodiment 4
Get 100 grams of NNY-1 deionized waters to pull an oar, and stir condition under rapid temperature increases to 90 DEG C, then in 2 hours, the aqueous solution configured by 30 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 90 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings and drying after filtering, sample after drying is 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, takes out sample; Filter cake 400mL is contained NH
4 +and H
+the concentration mixed solution (ammonium nitrate and nitric acid) that is respectively 0.8mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is process 3 hours at 70 DEG C, filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain modification small-grain Y-1.The physico-chemical property of Y-1 is in table 1.
Embodiment 5
Get 100 grams of NNY-2 deionized waters to pull an oar, and stir condition under rapid temperature increases to 100 DEG C, then in 2 hours, the aqueous solution configured by 20 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 100 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings and drying after filtering, sample after drying is placed in hydrothermal treatment consists stove, control the heating rate of 400 DEG C/h, temperature is risen to 700 DEG C, maintain the steam partial pressure 0.1MPa of system simultaneously, process 2 hours, cooling, takes out sample; Filter cake 400mL is contained NH
4 +and H
+the concentration mixed solution (ammonium chloride and hydrochloric acid) that is respectively 1.0mol/L and 0.2mol/L process, remove the non-framework aluminum in sample, dealuminzation condition is at 75 DEG C, process 3 hours filter, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 6 hours in an oven of washing, filter cake after 7, obtain modification small-grain Y-2.The physico-chemical property of Y-2 is in table 1.
Embodiment 6
By 30 grams of Y-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 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-1.
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-1, and carrier and corresponding catalyst character are in table 2.
Embodiment 7
By 40 grams of Y-1 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-2.
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-2, 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, 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, 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, specific 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-2 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-2, and carrier and corresponding catalyst character are 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 0.3L concentration is 100g A1
2o
3/ L sodium aluminate working solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting into about 10wt% weak aqua ammonia (b).Get containing SiO
2the sodium silicate solution of 28wt%, then to be diluted to 0.5L concentration be 140g SiO
2/ L sodium metasilicate working solution (c).Get the steel retort of one 5 liters, 0.5 liter of distilled water is added and after being heated with stirring to 70 DEG C in tank, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) to make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the pH value of system remain on 7 ~ 8, and the temperature of the hierarchy of control is at about 60 DEG C.After reacting aluminum sulfate completes, stop adding (b), the silicon-aluminum sol of generation stablizes 40 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, 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.
4, 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, carrier TCCAT-3 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-3, and carrier and corresponding catalyst character are in table 2.
Comparative example 4
1, the CNNY-1 adopting comparative example 1 to prepare is raw material, then the method modification of CN200910165116.X is adopted, specific as follows: to get 100 grams of CNNY-1 100mL deionized water making beating, and stir condition under rapid temperature increases to 95 DEG C, then in 2 hours, the aqueous solution configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water is dripped with uniform speed, add rear slurry constant temperature 2 hours under 95 DEG C of stirring conditions, leave standstill 10 minutes, through 3 washings, filter, dry; Sample after above-mentioned drying is placed in heat-treatment furnace, and 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; Final sample 400mL contains Al
3+and H
+the concentration mixed solution (aluminum nitrate and nitric acid) that is respectively 1.0mol/L and 0.5mol/L remove non-framework aluminum in sample, dealuminzation condition is 80 DEG C of process 2 hours, and use hot deionized water washing leaching cake, with the pH value of cleaning solution close to stopping the 120 DEG C of dryings 5 hours in an oven of washing, filter cake after 7, obtain CY-4.The physico-chemical property of CY-4 is in table 1.
2, by 40 grams of CY-4 molecular sieves (butt 90wt%), 90 grams of amorphous aluminum silicides (pore volume 0.9ml/g, specific 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-4 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-4, and carrier and corresponding catalyst character are in table 2.
The character of table 1 Y zeolite
| Production code member | NY-1 | NY-2 | Y-1 | Y-2 | CY-1 | CY-2 | CY-3 | CY-4 |
| Feed intake SiO 2/Al 2O 3Mol ratio | 8.8 | 8.0 | ||||||
| SiO 2/Al 2O 3Mol ratio | 6.8 | 6.3 | 81 | 103 | 54 | 25 | 28 | 63 |
| Specific area, m 2/g | 898 | 884 | 990 | 1020 | 926 | 788 | 865 | 921 |
| Pore volume, mL/g | 0.38 | 0.37 | 0.56 | 0.60 | 0.49 | 0.32 | 0.34 | 0.48 |
| Secondary pore (1.7-10nm), % | 64.4 | 69.2 | 45.1 | 27.5 | 35.2 | 42.1 | ||
| External surface area, m 2/g | 189 | 180 | 249 | 240 | 196 | 164 | 195 | 189 |
| Lattice constant, nm | 2.461 | 2.461 | 2.432 | 2.430 | 2.437 | 2.450 | 2.443 | 2.436 |
| Relative crystallinity, % | 100 | 105 | 118 | 116 | 114 | 80 | 85 | 116 |
| Average crystallite size, nm | 400 | 430 | 400 | 430 | 400 | 450 | 400 | 400 |
The physico-chemical property of table 2 carrier and catalyst
| Bearer number | TCAT-1 | TCAT-2 | TCCAT-1 | TCCAT-2 | TCCAT-3 | TCCAT-4 |
| Small-grain Y molecular sieve, wt% | 22 | 29 | 29 | 29 | 22 | 22 |
| Amorphous aluminum silicide, wt% | 58 | 51 | 51 | 51 | 58 | 58 |
| Aluminium oxide, wt% | 20 | 20 | 20 | 20 | 20 | 20 |
| Specific area, m 2/g | 517 | 536 | 455 | 438 | 430 | 490 |
| Pore volume, ml/g | 0.60 | 0.63 | 0.51 | 0.47 | 0.46 | 0.55 |
| Pore size distribution (4-10nm), % | 64 | 72 | 47 | 45 | 42 | 53 |
| Catalyst is numbered | CAT-1 | CAT-2 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 |
| Specific area, m 2/g | 401 | 422 | 321 | 306 | 300 | 360 |
| Pore volume, ml/g | 0.52 | 0.56 | 0.46 | 0.43 | 0.42 | 0.49 |
| Pore size distribution (4-10nm), % | 62 | 68 | 43 | 40 | 39 | 50 |
The invention described above catalyst CAT-1, CAT-2 and comparative example catalyst CCAT-1, CCAT-2, CCAT-3 and CCAT-4 are 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-1 | CAT-2 | CCAT-1 | CCAT-2 | CCAT-3 | CCAT-4 |
| Reaction temperature, DEG C | 380 | 378 | 380 | 381 | 384 | 382 |
| < 370 DEG C of conversion ratios, wt% | 64.8 | 65.0 | 64.8 | 64.9 | 64.9 | 64.5 |
| Middle distillates oil selectivity, %(132 ~ 370 DEG C) | 86.2 | 87.0 | 81.8 | 81.9 | 82.0 | 84.1 |
| Major product character | ||||||
| Jet fuel (132 ~ 282 DEG C) | ||||||
| Freezing point, DEG C | <－60 | <－60 | <－60 | <－60 | <－60 | <－60 |
| Aromatic hydrocarbons, wt% | 3.2 | 3.1 | 4.0 | 4.6 | 4.5 | 4.0 |
| Smoke point, mm | 28 | 27 | 26 | 25 | 26 | 26 |
| Diesel oil (282 ~ 370 DEG C) | ||||||
| Cetane number | 62 | 63 | 59 | 58 | 57 | 60 |
| Condensation point, DEG C | -4 | -6 | -2 | -1 | 0 | -3 |
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 hydrocracking catalyst, comprising: by small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide and the adhesive mechanical mixture made with aluminium oxide, shaping, and then dry and roasting, makes catalyst carrier; Load hydrogenation active metals component in the catalyst carrier of gained, drying and roasting, make catalyst; The preparation method of described small crystal grain Y-shaped molecular sieve, comprising:
(1) preparation of fine grain NaY type molecular sieve;
(2) fine grain NaY is used containing alkaline solution treatment;
(3) the fine grain NaY type molecular sieve that step (2) obtains is become Na
2the little crystal grain NH of O content≤2.5wt%
4naY;
(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtained and separation of by-products;
(5) little crystal grain NH is obtained to step (4)
4naY molecular sieve carries out hydrothermal treatment consists;
(6) molecular sieve step (5) obtained is with containing NH
4 +and H
+mixed solution process, through washing and dry, obtain small crystal grain Y-shaped molecular sieve;
The wherein preparation method of the middle fine grain NaY type molecular sieve of step (1), comprising:
A, 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;
B, adopt acid-base precipitation legal system for amorphous aluminum silicide 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 acid-base neutralization plastic, aging, wherein silicon introduces the method for reaction system is in aluminiferous material and introducing portion is containing silicon materials before plastic and/or in plastic process, and remainder is in aluminiferous material containing silicon materials and introduces before ageing after plastic;
C, prepare silica-alumina gel: by (0.5 ~ 6) Na
2o:Al
2o
3: (7 ~ 11) 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 B 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 D, step C gained is through two step dynamic crystallizations, more after filtration, washing, drying, obtains small crystal grain NaY molecular sieve.
2. in accordance with the method for claim 1, it is characterized in that in step B, 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.
3. in accordance with the method for claim 1, it is characterized in that in step B, in the preparation process of amorphous aluminum silicide predecessor, in aluminiferous material and plastic after and the silicon introduced before ageing accounts for the silicon in amorphous aluminum silicide predecessor in the 5wt% ~ 85wt% of silica in silica.
4. in accordance with the method for claim 1, it is characterized in that in step B, in the preparation process of amorphous aluminum silicide predecessor, in aluminiferous material and plastic after and the silicon introduced before ageing accounts for the silicon in amorphous aluminum silicide predecessor in the 30wt% ~ 70wt% of silica in silica.
5. in accordance with the method for claim 1, it is characterized in that, in steps A and C, silicon source, alkali source are respectively sodium metasilicate and NaOH; In steps A, aluminium source is selected from sodium metaaluminate.
6. in accordance with the method for claim 1, it is characterized in that in step B, aluminiferous material is Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3and NaAlO
2in one or more, be one or more in waterglass, Ludox and organic silicon-containing compound containing silicon materials, wherein organic silicon-containing compound is one or more in silanol, silicon ether and siloxanes, precipitating reagent is acidic precipitation agent or alkaline precipitating agent, wherein alkaline precipitating agent is one or more in NaOH, ammoniacal liquor, sodium carbonate, sodium acid carbonate, acidic precipitation agent carbon dioxide or nitric acid.
7. in accordance with the method for claim 1, it is characterized in that in the acid-base precipitation method that step B adopts, acid-base neutralization plastic process is the neutralization reaction process of acid material and alkaline material, in and plastic process adopt the mode of acid material or the continuous acid-base titration of alkaline material, or adopt acid material and alkaline material and the mode of stream neutralization.
8. in accordance with the method for claim 7, it is characterized in that in step B, containing silicon materials in aluminiferous material and plastic before and/or introduce in plastic process, it is in carrying out again after mixing with acid material or alkaline material according to the different character containing silicon materials and plastic, or will add in reaction system separately in aluminiferous material He in plastic process containing silicon materials, or the combination of said method.
9. in accordance with the method for claim 1, it is characterized in that in step B, described plastic process is carried out at room temperature ~ 85 DEG C, and the pH value of the hierarchy of control is 7.0 ~ 10.0; Carry out aging after plastic, aging condition is as follows: aging pH is 7.0 ~ 10.0, ageing time 0.2 ~ 8.0 hour, and aging temperature is room temperature ~ 85 DEG C.
10. in accordance with the method for claim 1, it is characterized in that in step C, control reaction temperature 10 ~ 30 DEG C, pH value 10 ~ 11.
11. in accordance with the method for claim 1, it is characterized in that step D 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.
12. in accordance with the method for claim 1, it is characterized in that step D 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.
13. in accordance with the method for claim 1, it is characterized in that in step (2), and being pulled an oar with the aqueous solution of alkali by small crystal grain NaY molecular sieve mixes, and stir process 1 ~ 4h under maintaining the temperature conditions of 60 ~ 120 DEG C; Alkali wherein used is the mixture of NaOH, KOH or NaOH and KOH; The concentration of the aqueous solution of alkali is 0.1 ~ 3 mol/L, and the concentration of slurries Middle molecule sieve is 0.05 ~ 1.0g/mL.
14. in accordance with the method for claim 1, it is characterized in that, in step (4), in aqueous medium, adding little crystal grain NH by solid-liquid weight ratio 1:4 ~ 1:8
4naY molecular sieve, stirs and is warmed up to 90 ~ 120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, and after dropwising, constant temperature stirs 1 ~ 2 hour, isolated molecule sieve and accessory substance, and filter, dry; The concentration 10 wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little crystal grain NH
410 wt% ~ 50wt% of NaY molecular sieve.
15. in accordance with the method for claim 1, and it is characterized in that in step (5), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 500 ~ 750 DEG C, pressure is 0.01 ~ 0.50MPa, and the processing time is 1.0 ~ 4.0 hours.
16. in accordance with the method for claim 1, and it is characterized in that in step (5), the condition of described hydrothermal treatment consists is as follows: treatment temperature controls at 600 ~ 700 DEG C, pressure is 0.05 ~ 0.30MPa, and the processing time is 1.0 ~ 4.0 hours.
17. in accordance with the method for claim 1, it is characterized in that in step (6), by the molecular sieve after hydrothermal treatment consists with acid with containing NH
4 +the mixed solution contact of salt composition, 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 repeats 1 ~ 4 time.
18. in accordance with the method for claim 1, it is characterized in that: the method that step (3) adopts ammonium salt to exchange, process is as follows: take NaY molecular sieve as raw material, at 70 ~ 120 DEG C, 0.5 ~ 3.0 hour is exchanged with the aqueous solution of solubility ammonium salt, molecular sieve is 0.05 ~ 0.50g/mL exchanging the concentration in slurries, repeated exchanged l ~ 5 time, elimination mother liquor, washing, dry; Ammonium salt is one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, and the concentration of ammonium salt solution is 0.5 ~ 5.0mol/L.
19. 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.
20. 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; Drying and the roasting condition of catalyst are as follows: 100 DEG C ~ 150 DEG C dry l ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 3 ~ 6 hours.
21. 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%.
22. in accordance with the method for claim 1, it is characterized in that: described hydrogenation active metals is the metal of group vib and/or the VIIIth race, and group vib metal is molybdenum and/or tungsten, and the metal of the VIIIth race is cobalt and/or nickel.
23. in accordance with the method for claim 22, it is characterized in that: with the weight of catalyst for benchmark, group vib metal with the content of oxide basis for 10wt% ~ 30wt% and group VIII metal with the content of oxide basis for 4wt% ~ 10wt%, the content of carrier is 61wt% ~ 86wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107303493A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
| CN110078093A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of NaY molecular sieve and its preparation method and application |
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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 |
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| CN107303493B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
| CN110078093A (en) * | 2018-01-25 | 2019-08-02 | 中国石油天然气集团有限公司 | A kind of NaY molecular sieve and its preparation method and application |
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