CN104826667B - The method for preparing carrier of hydrocracking catalyst - Google Patents
The method for preparing carrier of hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of carrier of hydrocracking catalyst.This method includes：, then through drying and being calcined, carrier is made in the adhesive mixing being made by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and with aluminum oxide, extruded moulding.This method is by silica alumina ratio is higher, crystallinity is high, stability is good NaY type Molecular sieve raw materials, sequentially pass through alkali cleaning, ammonium exchange, dealumination complement silicon, hydro-thermal process and with acid with after the processing of the mixed solution of ammonium salt, resulting small crystal grain Y-shaped molecular sieve is obtaining higher SiO2/A12O3While mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of Y type molecular sieve, and molecular sieve has higher specific surface area and higher crystallinity.Carrier of hydrocracking catalyst of the present invention suitably as the oily hydrocracking catalyst of senior middle school, can make catalyst have activity, middle distillates oil selectivity and excellent product property well.
Description
Technical field
It is more specifically a kind of to contain small-grain Y the present invention relates to a kind of preparation method of carrier of hydrocracking catalyst
The preparation method of the hydrogenation catalyst cracking carrier of type molecular sieve.
Background technology
In being continuously increased with international refined products market to the demand of intermediate oil, it is necessary to more be obtained from mink cell focus
Between distillate, and one of important means of hydrocracking process exactly light materialization of heavy oil.Because the technique has raw material adaptation
Property strong, good product quality, adjustment operation is flexible, and midbarrel product yield is high, the features such as product structure is flexible so that hydrogenation splits
The status of chemical industry skill becomes more and more important, be faced with present particular for China petroleum resources shortage, environmental requirement it is increasingly tight
The problems such as lattice and oil product structure have been not suitable with market, the application of hydrocracking technology will turn into improve petroleum product-quality,
Reduce environmental pollution, increase the effective technology measure of market adaptability to changes, it has also become the mostly important technique dress in modernization refinery
Put.Exactly these factors promote high selectivity to middle distillates hydrocracking technology and rapidly developed, and hydrocracking catalyst is
The key of the technology.
Carrier is the important component of catalyst, not only scattered place is provided for metal active constituent, while carrier sheet
Body also assists in reaction, the whole catalytic reaction of completion is cooperateed with together with other active components, hydrocracking catalyst is a kind of pair of work(
Energy catalyst, it contains acidic components and hydrogenation component simultaneously.Hydrogenation activity is selected generally from VI B races and in the periodic table of elements
VIII race's metal is provided；It is largely with aluminum oxide or without fixed and its acidic components is mainly provided by zeolite and inorganic oxide
Shape sial is carrier, is equipped with a certain amount of molecular sieve.And the key component that cracking is played in such catalyst is usually Y molecules
Sieve, the quality of Y molecular sieve performance directly affects the performance and product quality of catalyst.
Y type molecular sieve is cracking active component the most universal in residual oil cracking field at present, and crystal grain is generally
1000nm or so, its crystal grain is larger, and duct is relatively long, and diffusional resistance is big, and macromolecular is difficult to enter is reacted inside duct,
Product is also more difficult after reaction diffuses out, so the selectivity of its cracking activity and purpose product receives restriction.With conventional Y types
Molecular sieve is compared, and small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface activated centres, is conducive to improving big point
Sub- hydrocarbon cracking capability, thus with more superior catalytic perfomance.Meanwhile, reducing Y type molecular sieve crystallite dimension can be with
Improve inner surface active sites utilization rate.In general, diffusion of the reactant molecule in molecular sieve endoporus duct is referred to as transgranular expansion
Dissipate.Molecular sieve inner surface is set all to be used for catalyzed conversion, it is necessary to micropore diffusion speed is more than endoporus catalyzed conversion
Speed.It is the best way to shorten diffusion path.An effective way for overcoming micropore diffusion to limit is to reduce zeolite crystal
Size.This can not only increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously.EP0204236 is to small
Crystal NaY molecular sieve and big crystal grain NaY molecular sieve are compared, and are as a result shown, the former has higher to RFCC
Active and preferable selectivity.
Small crystal grain NaY molecular sieve is that do not possess acidity, it is necessary to processing is modified, to meet the performance of Cracking catalyst
It is required that.CN1382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and this method is the drying gas with silicon tetrachloride
Body and fine grain NaY zeolitic contact, are obtained after washing, because the heat and hydrothermal stability of its raw material itself are just poor, simultaneously
This method is to handle molecular sieve by the way of gas phase dealumination complement silicon, and this make it that the heat and hydrothermal stability of product are worse, activity
It is low.Sial skeleton structure stability in fine grain NaY zeolite especially poor to heat endurance and hydrothermal stability, zeolite
It is poor, the removing of framework aluminum is easily caused in modifying process, while also some framework silicon causes portion also with removing
Skeleton is divided the phenomenon caved in occur so that the crystallization reservation degree of product is relatively low, the activity of zeolite is not high.
CN200910188140.5 discloses a kind of hydrocracking catalyst and preparation method thereof.The catalyst includes hydrogenation
The carrier of active metal component and small-grain Y molecular sieve, amorphous silica-alumina and aluminum oxide composition, wherein the small-grain Y-type point
Son sieve is using the small crystal grain Y-shaped molecular sieve after hydro-thermal process.Raw materials used small crystal grain NaY molecular sieve is in CN101722023A
Prepared by disclosed method, i.e. SiO2/Al2O3Mol ratio is 4.0~6.0, and average grain diameter is in 100~700nm, after passing sequentially through
Continuous modification is the mixed aqueous solution processing of ammonium exchange, ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal process, aluminium salt and acid, obtains small crystalline substance
Grain Y molecular sieve.In this method, need first to raw material with ammonium hexafluorosilicate dealumination complement silicon handle after, then carry out hydro-thermal process etc. processing,
The skeleton structure that molecular sieve could so be reduced is caved in, and improves the crystallization reservation degree of molecular sieve, but this method is due to first with six
After the processing of ammonium fluosilicate dealumination complement silicon, due to occurring sial same order elements, molecular sieve silica constructed of aluminium is than more complete, then enters water-filling
Heat treatment, the secondary pore of formation is few, and secondary pore proportion is low, and as catalyst molecule screen banks point, middle oil yield is low.
Existing method fine grain NaY type molecular sieve is in preparation process, and silicon and aluminium are easy to run off, and silicon utilization rate is low, and silicon,
Aluminium distributing inhomogeneity, easily reunites, therefore existing method still can not prepare silica alumina ratio height, and heat endurance and hydro-thermal are steady
Qualitative and good fine grain NaY type molecular sieve.By successive modified, it is impossible to obtain structural integrity, crystallinity is high and with more
The small crystal grain Y-shaped molecular sieve of secondary pore, as the cracking component of catalyst, middle oil yield is low.
The content of the invention
For weak point of the prior art, the invention provides a kind of good hydrocracking catalyst load of catalytic performance
The preparation method of body.The carrier of hydrocracking catalyst is using a kind of high silica alumina ratio, high-crystallinity, secondary pore be more, Large ratio surface
Long-pending small crystal grain Y-shaped molecular sieve as acidic components, be conducive to improve hydrocracking catalyst activity and middle distillates oil selectivity and
Improve product property.
The preparation method of carrier of hydrocracking catalyst of the present invention, by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and bonding
Agent is mixed, extruded moulding, and through drying and being calcined, carrier is made；
Described small crystal grain Y-shaped molecular sieve, including following preparation process：
（1）The preparation of fine grain NaY type molecular sieve；
（2）Fine grain NaY is used and contains alkaline solution treatment；
（3）By step（2）Obtained fine grain NaY type molecular sieve is prepared into Na2O content≤2.5wt% little crystal grain
NH4NaY；
（4）Step（3）The molecular sieve of gained carries out dealumination complement silicon with hexafluorosilicic acid aqueous ammonium, obtained molecular sieve and pair
Product is separated；
（5）To step（4）Obtain little crystal grain NH4NaY molecular sieve carries out hydro-thermal process；
（6）By step（5）Obtained molecular sieve, which is used, contains NH4 +And H+Mixed solution processing, it is scrubbed and dry, obtain small
Grain Y-molecular sieve.
Step（1）Described in small crystal grain NaY molecular sieve, its property is as follows： SiO2/Al2O3Mol ratio is more than 6.0 and not
Higher than 9.0, preferably 6.5~9.0, more preferably 7.0~8.0, average grain diameter be 200~700nm, preferably 300~
500nm；Specific surface area is 800~1000 m2/ g, preferably 850~950 m2/ g, 0.30/~0.45mL/g of pore volume, relative knot
Brilliant degree is 90%~130%, and cell parameter is 2.460~2.470nm, the relative crystallinity after being calcined 3 hours in 650 DEG C of air
For more than 90%, generally 90%~110%, preferably 90% ~ 105%, through relative after 700 DEG C of water vapour hydro-thermal process 2 hours
Crystallinity is more than 90%, generally 90%~110%, preferably 90% ~ 105%.
In the inventive method in step (1) fine grain NaY type molecular sieve preparation method, including：
I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6~30) Na2O：Al2O3：(6
~30) SiO2：(100~460) H2O, after stirring, stirs ageing at 0~20 DEG C by mixture and is made for 0.5~24 hour
Directed agents；
II, using preparing amorphous silicon alumnium using carbonization predecessor, using the weight of the butt of amorphous silica-alumina predecessor as base
Standard, the content that silicon is counted using silica is 40wt%~75wt%, preferably 55 wt%~70wt%；Its preparation process includes：
A, respectively preparation sodium aluminate solution and sodium silicate solution；
The part sodium silicate solution that step a is prepared is added in b, the sodium aluminate solution prepared to step a, CO is then passed to2
Gas, controlling reaction temperature is 10 ~ 40 DEG C, and preferably 15~35 DEG C, the pH value for controlling cemented into bundles is 8 ~ 11；Wherein when being passed through
CO2Gas flow accounts for the 60% ~ 100% of total intake, when preferably 80% ~ 100%, adds remainder sodium silicate solution, wherein
Remainder sodium silicate solution is accounted for step b in terms of silica and adds sodium silicate solution total amount in terms of silica in step b
5wt% ~ 85wt%, preferably 30wt% ~ 70wt%；
C, at step b control temperature and pH value, said mixture ventilation stablizes 10 ~ 30 minutes；
III, prepare silica-alumina gel
By (0.5~6) Na2O：Al2O3：(8~15) SiO2：(100~460) H2O total molar ratio, at 0~40 DEG C
To step under conditions of quick stirring（2）Water, silicon source, directed agents and alkali source are added in the amorphous silica-alumina predecessor of gained, and
Control ph is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for the 1% of silica-alumina gel weight
~20%,
IV, step（3）The reactant mixture of gained is washed through two step dynamic crystallizations, then through filtering, is dried, is obtained small crystalline substance
Grain NaY molecular sieve.
In the present invention, in step I and III, silicon source, alkali source are respectively selected from sodium metasilicate and sodium hydroxide.In step I, silicon source
Selected from sodium metaaluminate.
In step II, the concentration of the sodium aluminate solution used in step a is preferably 15~55g Al2O3/ L, sodium silicate solution
Concentration be 50~150 gSiO2/ L, CO used in step b2The concentration of gas is 30v% ~ 60v%.
In step III, 0~40 DEG C of controlling reaction temperature, 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 uses two step dynamic crystallizations, and the wherein first step enters Mobile state
The condition of crystallization is as follows：Temperature control is at 50~90 DEG C, and crystallization time is 0.5~18 hour；Second step carries out dynamic crystallization
Condition is as follows：Temperature control is at 80~140 DEG C, and crystallization time is 3~10 hours, after the completion of crystallization, then through filtering, washing, do
It is dry, product is made.Two step dynamic crystallization conditions are preferably as follows：The first step：Temperature control at 60~80 DEG C, crystallization time is 1~
10 hours；Second step：Temperature control is at 80~120 DEG C, and crystallization time is 5~10 hours.
Step（2）In, small crystal grain NaY molecular sieve is well mixed with the aqueous solution mashing of alkali, and maintain 60~120 DEG C
1~4h of stir process under temperature conditionss, filtering, washing.Alkali wherein used is NaOH, KOH or NaOH and KOH mixture.
The concentration that the concentration of the aqueous solution of alkali is generally molecular sieve in 0.1~3 mol/L, slurries is 0.05~1.0g/mL.
Step（4）In, little crystal grain NH is added in aqueous medium4NaY（Solid-liquid weight compares 1：4~1：8）, stir and be warming up to
90~120 DEG C, hexafluorosilicic acid aqueous ammonium is then added dropwise to, constant temperature is stirred 1~2 hour after completion of dropping, separates molecular sieve
And accessory substance, and filter, dry.10 wt% of concentration ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is small
Crystal grain NH410 wt% of NaY molecular sieve ~ 50wt%.
Step（5）In, the condition of described hydro-thermal process is as follows：Treatment temperature is controlled at 500~750 DEG C, is preferably controlled
At 600~700 DEG C, pressure is 0.01~0.50MPa, and preferably 0.05~0.30MPa, processing time is 1.0~4.0 hours.
Step（6）In, by the molecular sieve after hydro-thermal process with acid and containing NH4 +Salt composition mixed solution contact, exchange
Na in molecular sieve+With the part non-framework aluminum in removing molecular sieve, during acid therein can be hydrochloric acid, carbonic acid, nitric acid, sulfuric acid
One or more, containing NH4 +Salt be one or more in the ammonium salt of the acid group containing the above；H in mixed solution+Concentration be
0.05~0.6mol/L, NH4 +Concentration be 0.5~3.0mol/L, exchange temperature be 70~120 DEG C, exchange slurries in molecular sieve
Concentration be 0.1~0.5g/mL, swap time be 0.5~3.0 hour, exchange step may be repeated 1~4 time.Then remove
Mother liquor, is washed with water, and dries.
Other operating procedures in the modified Y molecular sieve preparation method of the present invention, such as ammonium salt are exchanged can be normal using this area
The operating method and condition of rule.Step（3）The method exchanged using ammonium salt, it is specific as follows：Using NaY molecular sieve as raw material, with can
The aqueous solution of undissolved ammonium salt is exchanged 0.5~3.0 hour at 70~120 DEG C at preferably 80~100 DEG C, and Y molecular sieve is exchanging slurry
Concentration in liquid is 0.05~0.50g/mL, and repeated exchanged l~5 time filter off mother liquor, washed, dry.Ammonium salt such as ammonium chloride, carbon
One or more in sour ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5
~5.0mol/L.
Step（2）In, small crystal grain NaY molecular sieve is well mixed with the aqueous solution mashing of alkali, and maintain 60~120 DEG C
1~4h of stir process under temperature conditionss, filtering, washing.Alkali wherein used is NaOH, KOH or NaOH and KOH mixture.
The concentration that the concentration of the aqueous solution of alkali is generally molecular sieve in 0.1~3mol/L, slurries is 0.05~1.0g/mL.
Step（4）In, little crystal grain NH is added in aqueous medium4NaY（Solid-liquid weight compares 1：4~1：8）, stir and be warming up to
90~120 DEG C, hexafluorosilicic acid aqueous ammonium is then added dropwise to, constant temperature is stirred 1~2 hour after completion of dropping, separates molecular sieve
And accessory substance, and filter, dry.10 wt% of concentration ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is small
Crystal grain NH410 wt% of NaY molecular sieve ~ 50wt%.
Step（5）In, the condition of described hydro-thermal process is as follows：Treatment temperature is controlled at 500~750 DEG C, is preferably controlled
At 600~700 DEG C, pressure is 0.01~0.50MPa, and preferably 0.05~0.30MPa, processing time is 1.0~4.0 hours.
Step（6）In, by the molecular sieve after hydro-thermal process with acid and containing NH4 +Salt composition mixed solution contact, exchange
Na in molecular sieve+With the part non-framework aluminum in removing molecular sieve, during acid therein can be hydrochloric acid, carbonic acid, nitric acid, sulfuric acid
One or more, containing NH4 +Salt be one or more in the ammonium salt of the acid group containing the above；H in mixed solution+Concentration be
0.05~0.6mol/L, NH4 +Concentration be 0.5~3.0mol/L, exchange temperature be 70~120 DEG C, exchange slurries in molecular sieve
Concentration be 0.1~0.5g/mL, swap time be 0.5~3.0 hour, exchange step may be repeated 1~4 time.Then remove
Mother liquor, is washed with water, and dries.
Other operating procedures in the modified Y molecular sieve preparation method of the present invention, such as ammonium salt are exchanged can be normal using this area
The operating method and condition of rule.Step（3）The method exchanged using ammonium salt, it is specific as follows：Using NaY molecular sieve as raw material, with can
The aqueous solution of undissolved ammonium salt is exchanged 0.5~3.0 hour at 70~120 DEG C at preferably 80~100 DEG C, and Y molecular sieve is exchanging slurry
Concentration in liquid is 0.05~0.50g/mL, and repeated exchanged l~5 time filter off mother liquor, washed, dry.Ammonium salt such as ammonium chloride, carbon
One or more in sour ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5
~5.0mol/L.
Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used
Aluminium pore volume is 0.3~0.5mL/g, and specific surface area is 200~400m2/g。
In catalyst carrier of the present invention, amorphous silica-alumina used is mixed with small-grain Y molecular sieve and adhesive can be by altogether
Prepared by the precipitation method or grafting copolymerization process, prepared by conventional method in document.SiO in obtained amorphous silica-alumina2Weight
Content is 20%~60%, preferably 25%~40%, and the pore volume of amorphous silica-alumina is 0.6~1.1mL/g, preferably 0.8~
1.0mL/g, specific surface area is 300~500m2/ g, preferably 350~500 m2/g。
Catalyst of the present invention can be molded according to actual needs, and shape can be cylindrical bars, clover etc..Catalyst into
During type, shaping assistant, such as peptization acid, extrusion aid can also be added.Catalyst carrier of the present invention is using conventional method
It is dried and is calcined, it is specific as follows：Dried 3~10 hours at a temperature of 80 DEG C~150 DEG C and in 500 DEG C~600 DEG C roastings
Burn 3~6 hours.
Carrier of hydrocracking catalyst of the present invention, including small-grain Y molecular sieve, aluminum oxide and amorphous silica-alumina, wherein institute
The small-grain Y molecular sieve stated, its property is as follows：SiO2/ A12O3Mol ratio be 30~120, average grain diameter be 200~
700nm, preferably 300~500nm, relative crystallinity is more than 100%, and preferably 100% ~ 120%, lattice constant 2.425~
2.450nm, specific surface area is 850~1000m2/ g, pore volume is 0.40~0.60mL/g, shared by 1.7~10nm secondary pore
Pore volume is more than the 50% of total pore volume, preferably 50% ~ 80%, Na2O content≤0.15wt%.
Carrier of hydrocracking catalyst property of the present invention is as follows：Specific surface area is 450~650 m2/ g, pore volume is 0.5~
0.80 mL/g, 4 ~ 10nm of aperture pore volume accounts for the 55%~90% of total pore volume, preferably 65%~80%.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, its composition includes：Small-grain Y molecular sieve
Content be 5wt%~40wt%, the content of amorphous silica-alumina is 20wt%~65wt%, the content of aluminum oxide for 10wt%~
40wt%.
, can be using load side conventional in the prior art when catalyst carrier of the present invention is used to prepare hydrocracking catalyst
Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component
Final hydrocracking catalyst is made after drying, roasting in carrier after agent carrier, dipping.
Due to the small-grain Y molecular sieve that carrier of the present invention is used, the silica alumina ratio of its NaY type Molecular sieve raw material is higher, crystallization
Degree is high, and stability is good, so in the crystal structure of follow-up modification process, not saboteur's sieve, without influenceing final point
The stability of son sieve.Molecular sieve of the present invention has carried out alkali process before ammonium exchange, with chemical dealuminization afterwards and hydro-thermal process phase
Coordinate, that is, reached preferable dealumination depth, and preferably maintain molecular sieve structure, while generating by substantial amounts of secondary
Hole, not only promotes the performance of hydrogenation activity, and is conducive to the diffusion of reaction product, holds charcoal ability and also greatly enhances, reduces
The occurrence probability of excessive fragmentation and second pyrolysis, so as to make catalyst that there is activity, middle distillates oil selectivity and excellent well
Product property.
Use small crystal grain molecular sieve in other carrier of the present invention for Cracking Component, with bigger external surface area and it is more outside
Active sites, are conducive to improving macromolecular hydrocarbon cracking capability, can make being hydrocracked for active component by this molecular sieve
The activity increase of catalyst, while the performance of catalyst hydrogenation performance can be advantageously promoted.
Embodiment
In order to which the present invention is better described, the present invention is further illustrated with reference to embodiment and comparative example.But this hair
Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention：Specific surface area, pore volume use low temperature liquid nitrogen physics
Absorption method, relative crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses chemical method, and the crystal grain of molecular sieve is big
It is small to be determined by the way of SEM (SEM).Wt% is mass fraction.
Embodiment 1
The present embodiment is preparing raw material fine grain NaY type molecular sieve
NY-1 preparation
（1）The preparation of directed agents：Take 10 g sodium hydrate solids to be dissolved in 80g water, add sodium metaaluminate 2g (Al2O3Contain
Measure as 45wt%, Na2O content is 41wt%), then add 36g waterglass (SiO2Content is 28wt%, Na2O content is
8wt%), in 15 DEG C of stirring 4 hours obtained directed agents of ageing after being well mixed.
（2）The preparation of amorphous silica-alumina predecessor
Solid sodium aluminate is configured to concentration for 40gAl2O3/ L sodium aluminate working solutions, take containing SiO228wt% silicic acid
Sodium solution, then concentration is diluted to for 100g SiO2/ L sodium metasilicate working solutions.1L sodium aluminate working solutions are taken to be placed in plastic cans
In, 0.2L sodium metasilicate working solutions are then added, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, works as pH value
Stop logical CO when reaching 10.02, 0.4L sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes.
（3）The preparation of gel
In step（2）100g SiO are added in resulting slurries2/ L sodium metasilicate working solution 1.5L and step（1）Prepare
Directed agents 120g, the pH value of gel is 12, and 20 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticizes 2 hours.
（4）Crystallization
By step（3）Resulting gel is poured into stainless steel cauldron, is stirred crystallization 4 hours at 70 DEG C, is then heated up
To 100 DEG C, then stirring crystallization 8 hours filters, washs, dry NaY molecular sieve product NY-1, and product property is shown in Table 1.
NY-2 preparation
（1）The preparation of directed agents：Take 8 g sodium hydrate solids to be dissolved in 80g water, add the g (Al of sodium metaaluminate 2.52O3
Content is 45wt%, Na2O content is 41wt%).Then 40g waterglass (SiO is added2Content is 28wt%, Na2O content is
8wt%), in 18 DEG C of stirring 4 hours obtained directed agents of ageing after being well mixed.
（2）The preparation of amorphous silica-alumina predecessor
Solid sodium aluminate is configured to concentration for 30gAl2O3/ L sodium aluminate working solutions, take containing SiO228wt% silicic acid
Sodium solution, then concentration is diluted to for 70g SiO2/ L sodium metasilicate working solutions.1L sodium aluminate working solutions are taken to be placed in plastic cans,
Then 0.4L sodium metasilicate working solutions are added, 18 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, when pH value reaches
To the logical CO of stopping when 10.22, 0.6L sodium metasilicate working solutions are added, then ventilation is stablized 20 minutes.
（3）The preparation of gel
In step（2）70g SiO are added in resulting slurries2/ L sodium metasilicate working solution 1.5L and step（1）Prepare
Directed agents 100g, the pH value of gel is 11.5, and 15 DEG C of controlling reaction temperature, uniform stirring 30 minutes staticizes 2.5 hours.
（4）Crystallization
By step（3）Resulting gel is poured into stainless steel cauldron, is stirred crystallization 5 hours at 75 DEG C, is then heated up
To 110 DEG C, then stirring crystallization 7 hours filters, washs, dry NaY molecular sieve product NY-2, and product property is shown in Table 1.
Embodiment 2
Alkali process is carried out to raw material small crystal grain NaY molecular sieve first, is 1mol/L's by 1000 grams of NY-1 and 5L concentration
NaOH solution mashing is well mixed, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, is washed to solution in
Property；Filter cake is in contact with 10 liters of 0.5mol/L aqueous ammonium nitrate solutions, speed of agitator is 300rpm, constant temperature is stirred at 90 DEG C
L hours, then filtering molecular was sieved, and stays sample, analyzes Na2O content；Aforesaid operations are repeated, until Na in molecular sieve2O content
2.5wt% is reached, dried sample number into spectrum is obtained for NNY-1.
Embodiment 3
Alkali process is carried out to raw material small crystal grain NaY molecular sieve first, is 0.8 mol/L's by 1000 grams of NY-2 and 5L concentration
KOH solution mashing is well mixed, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, is washed to solution close to neutrality；
Filter cake is in contact with 10 liters of 0.5mol/L aqueous ammonium nitrate solutions, speed of agitator is 300rpm, constant temperature stirring l is small at 95 DEG C
When, then filtering molecular is sieved, and stays sample, analyzes Na2O content；Aforesaid operations are repeated, until Na in molecular sieve2O content reaches
To 2.5wt%, dried sample number into spectrum is obtained for NNY-2.
Embodiment 4
Take 100 grams of NNY-1 to be beaten with deionized water, and be brought rapidly up under conditions of stirring to 95 DEG C, then with uniform
Speed be added dropwise within 2 hours by 25 grams of ammonium hexafluorosilicates and 150m1 deionized waters configuration the aqueous solution, add rear slurry and exist
2 hours of constant temperature under 95 DEG C of stirring conditions, 10 minutes are stood, dried after 3 washings and filtering, sample after drying is placed in
In heat-treatment furnace, 500 DEG C/h heating rate is controlled, temperature is risen to 600 DEG C, while the water vapor pressure of the system of maintenance is
0.15MPa, is handled 2 hours, and sample is taken out in cooling；Filter cake is contained into NH with 500mL4 +And H+Concentration be respectively 0.6mol/L and
Non-framework aluminum in 0.1mol/L mixed solution (ammonium chloride and hydrochloric acid) processing, removing sample, dealuminzation condition is at 80 DEG C
Reason 2 hours, and wash filter cake with hot deionized water, stops close to after 7 washing with the pH value of cleaning solution, filter cake in an oven 120
DEG C dry 5 hours, the physico-chemical property for obtaining being modified small-grain Y -1, Y-1 is shown in Table 1.
Embodiment 5
Take 100 grams of NNY-1 to be beaten with deionized water, and be brought rapidly up under conditions of stirring to 90 DEG C, then with uniform
Speed be added dropwise within 2 hours by 30 grams of ammonium hexafluorosilicates and 150m1 deionized waters configuration the aqueous solution, add rear slurry and exist
2 hours of constant temperature under 90 DEG C of stirring conditions, 10 minutes are stood, dried after 3 washings and filtering, sample after drying is placed in
In heat-treatment furnace, temperature is risen to 650 DEG C by the heating rate of 400 DEG C/h of control, while the steam partial pressure of the system of maintenance
0.08MPa, is handled 2 hours, and sample is taken out in cooling；Filter cake is contained into NH with 400mL4 +And H+Concentration be respectively 0.8mol/L and
Non-framework aluminum in 0.2mol/L mixed solution (ammonium nitrate and nitric acid) processing, removing sample, dealuminzation condition is at 70 DEG C
Processing 3 hours, filtering, and filter cake is washed with hot deionized water, stopping washing, filter cake close to after 7 with the pH value of cleaning solution is drying
120 DEG C of dryings 5 hours in case, the physico-chemical property for obtaining being modified small-grain Y -2, Y-2 is shown in Table 1.
Embodiment 6
Take 100 grams of NNY-2 to be beaten with deionized water, and be brought rapidly up under conditions of stirring to 100 DEG C, then with uniform
Speed be added dropwise within 2 hours by 20 grams of ammonium hexafluorosilicates and 150m1 deionized waters configuration the aqueous solution, add rear slurry and exist
2 hours of constant temperature under 100 DEG C of stirring conditions, 10 minutes are stood, dried after 3 washings and filtering, sample after drying is put
In hydro-thermal process stove, temperature is risen to 700 DEG C by the heating rate of 400 DEG C/h of control, while the water vapour of the system of maintenance
Partial pressure 0.1MPa, is handled 2 hours, and sample is taken out in cooling；Filter cake is contained into NH with 400mL4 +And H+Concentration be respectively 1.0mol/L
Handled with 0.2mol/L mixed solution (ammonium chloride and hydrochloric acid), the non-framework aluminum in removing sample, dealuminzation condition is at 75 DEG C
Lower processing is filtered for 3 hours, and washs filter cake with hot deionized water, and stopping washing, filter cake close to after 7 with the pH value of cleaning solution is drying
120 DEG C of dryings 6 hours, obtain being modified small-grain Y -3 in case.Y-3 physico-chemical property is shown in Table 1.
Embodiment 7
By 25 grams of Y-1 molecular sieves (butt 90wt%), 106.5 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with small porous aluminum oxide
You are than 0.25) to be put into mixed grind in roller, adding water, being rolled into paste, extrusion, and extrusion bar is dry 4 hours at 110 DEG C, then
It is calcined 4 hours at 550 DEG C, obtains carrier TCAT-1, property is shown in Table 2.
Embodiment 8
By 30 grams of Y-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with small porous aluminum oxide
You are than 0.25) to be put into mixed grind in roller, adding water, being rolled into paste, extrusion, and extrusion bar is dry 4 hours at 110 DEG C, then
It is calcined 4 hours at 550 DEG C, obtains carrier TCAT-2, property is shown in Table 2.
Embodiment 9
By 40 grams of Y-3 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with small porous aluminum oxide
You are than 0.25) to be put into mixed grind in roller, adding water, being rolled into paste, extrusion, and extrusion bar is dry 4 hours at 110 DEG C, then
It is calcined 4 hours at 550 DEG C, obtains carrier TCAT-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CAT-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 1
1st, fine grain NaY is prepared with reference to CN101722023A.
Feedstock property used is as follows in this comparative example：Low alkali sodium metaaluminate：Na2O content 120g/L, Al2O3Content
40g/L；Waterglass：SiO2Content 250g/L；Aluminum sulfate：Al2O3Content 90g/L.
(1) preparation of directed agents：NY-1 in the preparation be the same as Example 1 of directed agents.
(2) preparation of gel：Temperature is 8 DEG C, under stirring condition, and 59.4mL sulphur is sequentially added into 208mL waterglass
Sour aluminium, 62.7mL low sodium metaaluminate and 42.2mL directed agents, then constant temperature constant speed stirring 1.5 hours, then by obtained conjunction
Into liquid static aging 8 hours at the temperature disclosed above, gel is obtained.
(3) crystallization：Under agitation, the gel in synthesis reactor is raised to 50 DEG C, constant temperature stirring crystallization 7 in 20 minutes
Hour；After low temperature crystallized end, the temperature in synthesis reactor is brought up to 120 DEG C in 20 minutes, then constant temperature is stirred 6 hours.
Through being filtered, washed and dried drying, product little crystal grain CNY-l is obtained.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions be the same as Example 2 obtains dried sample
Numbering is CNNY-1.
3rd, subsequent treatment, processing mode and condition be the same as Example 4 are carried out to CNNY-1, obtains Reference Product CY-1.CY-1
Physico-chemical property be shown in Table 1.
4th, by 30 grams of CY-1 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with small porous aluminum oxide
You are than 0.25) to be put into mixed grind in roller, adding water, being rolled into paste, extrusion, and extrusion bar is dry 4 hours at 110 DEG C, then
It is calcined 4 hours at 550 DEG C, obtains carrier TCCAT-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 2
1st, fine grain NaY is prepared with reference to CN1785807A.
The preparation of directed agents：NY-1 in the preparation be the same as Example 1 of directed agents.
14.21g water is positioned in beaker, it is 60 DEG C to control fluid temperature in beaker, quick stirring is lower to be added simultaneously
12.79g50wt% A12(SO4)3) solution and 31.91g waterglass.After stirring, above-mentioned directed agents 1.90g, gel are added
PH value be 12.5, after stirring, be loaded into stainless steel cauldron, stir crystallization 6 hours at 60 DEG C, then heat to
100 DEG C of static crystallizations 60 hours, then filter, wash, dry CNY-2 molecular sieves.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions be the same as Example 2 obtains dried sample
Numbering is CNNY-2.
3rd, subsequent treatment, processing mode and condition be the same as Example 4 are carried out to CNNY-2, obtains Reference Product CY-2.CY-2
Physico-chemical property be shown in Table 1.
4th, by 30 grams of CY-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface area
350m2/ g, butt 70wt%), (0.25) mol ratio of butt 20wt%, nitric acid and small porous aluminum oxide is puts for 120 grams of adhesives
Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier TCCAT-2 is obtained, property is shown in Table 2.
Comparative example 3
1st, prepared by fine grain NaY
（1）The preparation of directed agents：NY-1 in the preparation be the same as Example 1 of directed agents.
（2）The preparation of amorphous silica-alumina predecessor.
Solid sodium aluminate is configured to concentration for 40gAl2O3/ L sodium aluminate working solutions, take containing SiO228wt% silicic acid
Sodium solution, then concentration is diluted to for 100g SiO2/ L sodium metasilicate working solutions.1L sodium aluminate working solutions are taken to be placed in plastic cans
In, 0.6L sodium metasilicate working solutions are then added, 20 DEG C of controlling reaction temperature is passed through the CO that concentration is 50v%2Gas, works as pH value
Stop logical CO when reaching 10.02, then divulge information and stablize 20 minutes.
（3）The preparation be the same as Example 1 of gel.
（4）Crystallization be the same as Example 1, obtains products C NY-3, and product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material small crystal grain NaY molecular sieve, treatment conditions be the same as Example 2 obtains dried sample
Numbering is CNNY-3.
3rd, subsequent treatment, processing mode and condition be the same as Example 4 are carried out to CNNY-3, obtains Reference Product CY-3.CY-3
Physico-chemical property be shown in Table 1.
4th, by 40 grams of CY-3 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than
Surface area 350m2/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with small porous aluminum oxide
You are than 0.25) to be put into mixed grind in roller, adding water, being rolled into paste, extrusion, and extrusion bar is dry 4 hours at 110 DEG C, then
It is calcined 4 hours at 550 DEG C, obtains carrier TCCAT-3, property is shown in Table 2.
Comparative example 4
1st, CNNY-1 prepared by comparative example 1 is used for raw material, is then modified using CN200910165116.X method, tool
Body is as follows：Take 100 grams of CNNY-1 to be beaten with 100mL deionized waters, and be brought rapidly up under conditions of stirring to 95 DEG C, then with
The aqueous solution by 25 grams of ammonium hexafluorosilicates and the configuration of 150m1 deionized waters is added dropwise in uniform speed within 2 hours, is starched after adding
Liquid 2 hours of constant temperature under 95 DEG C of stirring conditions, 10 minutes are stood, by 3 washings, filtering, dried；By sample after above-mentioned drying
Product are placed in heat-treatment furnace, control 500 DEG C/h heating rate, temperature is risen into 600 DEG C, while the water vapor pressure of the system of maintenance
Power is 0.15MPa, is handled 2 hours, and sample is taken out in cooling；Final sample contains Al with 400mL3+And H+Concentration be respectively
1.0mol/L and 0.5mol/L mixed solution (aluminum nitrate and nitric acid) removing sample in non-framework aluminum, dealuminzation condition be
80 DEG C are handled 2 hours, and wash filter cake with hot deionized water, and washing, filter cake are stopped in baking oven close to after 7 with the pH value of cleaning solution
In 120 DEG C of dryings 5 hours, obtain CY-4.CY-4 physico-chemical property is shown in Table 1.
2nd, by 40 grams of CY-4 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, specific surface area
350m2/ g, butt 70wt%), (0.25) mol ratio of butt 20wt%, nitric acid and small porous aluminum oxide is puts for 120 grams of adhesives
Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, obtain carrier TCCAT-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst CCAT-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
The property of the Y type molecular sieve of table 1
| Production code member | NY-1 | NY-2 | Y-1 | Y-2 | Y-3 | CY-1 | CY-2 | CY-3 | CY-4 |
| Feed intake SiO2/Al2O3Mol ratio | 9.1 | 10.1 | |||||||
| SiO2/Al2O3Mol ratio | 7.5 | 8.4 | 66 | 84 | 105 | 54 | 25 | 28 | 63 |
| Specific surface area, m2/g | 916 | 898 | 970 | 990 | 1020 | 926 | 788 | 865 | 921 |
| Pore volume, mL/g | 0.39 | 0.38 | 219 | 0.58 | 0.62 | 0.49 | 0.32 | 0.34 | 0.48 |
| Secondary pore（1.7-10nm）, % | 0.56 | 66.4 | 71.1 | 45.1 | 27.5 | 35.2 | 42.1 | ||
| External surface area, m2/g | 191 | 182 | 60.1 | 249 | 240 | 196 | 164 | 195 | 189 |
| Lattice constant, nm | 2.461 | 2.462 | 2.436 | 2.432 | 2.430 | 2.437 | 2.450 | 2.443 | 2.436 |
| Relative crystallinity, % | 101 | 110 | 115 | 118 | 116 | 114 | 80 | 85 | 116 |
| Average crystallite size, nm | 380 | 430 | 380 | 380 | 430 | 400 | 450 | 400 | 400 |
The carrier of table 2 and the physico-chemical property of catalyst agent
| Bearer number | TCAT-1 | TCAT-2 | TCAT-3 | TCCAT-1 | TCCAT-2 | TCCAT-3 | TCCAT-4 |
| Small-grain Y molecular sieve, wt% | 18 | 22 | 29 | 29 | 29 | 22 | 22 |
| Amorphous silica-alumina, wt% | 62 | 58 | 51 | 51 | 51 | 58 | 58 |
| Aluminum oxide, wt% | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Specific surface area, m2/g | 514 | 524 | 549 | 455 | 438 | 430 | 490 |
| Pore volume, ml/g | 0.60 | 0.61 | 0.65 | 0.51 | 0.47 | 0.46 | 0.55 |
| Pore size distribution（4-10nm）, % | 64 | 65 | 74 | 47 | 45 | 42 | 53 |
| Catalyst is numbered | CAT-3 | CCAT-1 | CCAT-4 | ||||
| Specific surface area, m2/g | 427 | 321 | 360 | ||||
| Pore volume, ml/g | 0.57 | 0.46 | 0.49 | ||||
| Pore size distribution（4-10nm）, % | 70 | 43 | 50 |
The invention described above catalyst CAT-3 and comparative example catalyst CCAT-1, CCAT-4 are subjected to active evaluation test.Examination
Test and carried out on 200ml small hydrogenation devices, using one-stage serial technological process, raw materials used oil nature is shown in Table 3.Operation
Condition is as follows：Hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500：1, air speed 1.5h- 1, the μ g/g of control cracking zone nitrogen content 5~10.
Catalyst Activating Test the results are shown in Table 4.
The raw material oil nature of table 3
| Feedstock oil | Iranian VGO |
| Density (20 DEG C), g/cm3 | 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 values | 41.5 |
| Refractive power/nD 70 | 1.48570 |
The catalyst activity evaluation result of table 4
| Catalyst is numbered | CAT-3 | CCAT-1 | CCAT-4 |
| Reaction temperature, DEG C | 377 | 380 | 382 |
| <370 DEG C of conversion ratios, wt% | 65.0 | 64.8 | 64.5 |
| Middle distillates oil selectivity, %（132~370 DEG C） | 87.3 | 81.8 | 84.1 |
| Major product property | |||
| Jet fuel（132~282℃） | |||
| Freezing point, DEG C | <- 60 | <- 60 | <- 60 |
| Aromatic hydrocarbons, wt% | 3.1 | 4.0 | 4.0 |
| Smoke point, mm | 27 | 26 | 26 |
| Diesel oil（282~370℃） | |||
| Cetane number | 63 | 59 | 60 |
| Condensation point, DEG C | -6 | -2 | -3 |
It can be seen that by the evaluation result of the catalyst of table 4, the catalyst prepared by the present invention is on the basis of greater activity, tool
There is good selectivity, product property is good.
Claims (23)
1. a kind of preparation method of carrier of hydrocracking catalyst, including：By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and use
, then through drying and being calcined, carrier is made in the adhesive mixing that aluminum oxide is made, extruded moulding；The small crystal grain Y-shaped molecular sieve
Preparation method, including：
（1）The preparation of fine grain NaY type molecular sieve；
（2）Fine grain NaY is used and contains alkaline solution treatment；
（3）By step（2）Obtained fine grain NaY type molecular sieve is prepared into Na2O content≤2.5wt% little crystal grain NH4NaY；
（4）Step（3）The molecular sieve of gained carries out dealumination complement silicon with hexafluorosilicic acid aqueous ammonium, obtained molecular sieve and accessory substance
Separation；
（5）To step（4）Obtain little crystal grain NH4NaY molecular sieve carries out hydro-thermal process；
（6）By step（5）Obtained molecular sieve, which is used, contains NH4 +And H+Mixed solution processing, it is scrubbed and dry, obtain little crystal grain
Y type molecular sieve；
Wherein step（1）Fine grain NaY type molecular sieve used, its property is as follows： SiO2/Al2O3Mol ratio is more than 6.0 and not
Higher than 9.0, average grain diameter is 200~700nm, than the m of surface 800~10002/ g, 0.30~0.45mL/g of pore volume, relatively
Crystallinity is 90%~130%, and cell parameter is 2.460~2.470nm, the relative crystallization after being calcined 3 hours in 650 DEG C of air
Spend for more than 90%, be more than 90% through relative crystallinity after 700 DEG C of water vapour hydro-thermal process 2 hours.
2. in accordance with the method for claim 1, it is characterised in that：The SiO of fine grain NaY type molecular sieve used2/Al2O3Rub
You are than being 6.5~9.0.
3. in accordance with the method for claim 1, it is characterised in that：The SiO of fine grain NaY type molecular sieve used2/Al2O3Rub
You are than being 7.0~8.0.
4. in accordance with the method for claim 1, it is characterised in that：The crystal grain of fine grain NaY type molecular sieve used is averagely straight
Footpath is 300~500nm.
5. in accordance with the method for claim 1, it is characterised in that：Fine grain NaY type molecular sieve used is through in 650 DEG C of air
Relative crystallinity is 90%~110% after roasting 3 hours, is through relative crystallinity after 700 DEG C of water vapour hydro-thermal process 2 hours
90%~110%.
6. in accordance with the method for claim 1, it is characterised in that：The preparation method of fine grain NaY type molecular sieve used, bag
Include：
I, preparation directed agents：Silicon source, silicon source, alkali source and water are fed intake according to following proportioning：(6~30) Na2O：Al2O3：(6~
30)SiO2：(100~460) H2O, after stirring, mixture is stirred to be aged to be made for 0.5~24 hour at 0~20 DEG C and led
To agent；
II, using preparing amorphous silicon alumnium using carbonization predecessor, on the basis of the weight of the butt of amorphous silica-alumina predecessor,
The content that silicon is counted using silica is 40wt%~75wt%；Its preparation process includes：
A, respectively preparation sodium aluminate solution and sodium silicate solution；
The part sodium silicate solution that step a is prepared is added in b, the sodium aluminate solution prepared to step a, CO is then passed to2Gas,
Controlling reaction temperature is 10 ~ 40 DEG C, and the pH value for controlling cemented into bundles is 8 ~ 11；Wherein as the CO being passed through2Gas flow, which is accounted for, to be always passed through
Amount 60% ~ 100% when, add remainder sodium silicate solution, remainder sodium silicate solution is with silica in wherein step b
Meter accounts for step b and adds 5wt% ~ 85wt% of the sodium silicate solution total amount in terms of silica；
C, at step b control temperature and pH value, said mixture ventilation stablizes 10 ~ 30 minutes；
III, prepare silica-alumina gel：By (0.5~6) Na2O：Al2O3：(8~15) SiO2：(100~460) H2O's always feeds intake mole
Than adding water, silicon source, guiding into the amorphous silica-alumina predecessor obtained by step II under conditions of 0~40 DEG C of quick stirring
Agent and alkali source, and control ph is 9.5 ~ 12.0, uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for sial and coagulated
The 1%~20% of glue weight,
Reactant mixture obtained by IV, step III is washed through two step dynamic crystallizations, then through filtering, is dried, is obtained little crystal grain
NaY type molecular sieves.
7. in accordance with the method for claim 6, it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous silicon
On the basis of the weight of the butt of aluminium predecessor, the content that silicon is counted using silica is 55 wt%~70wt%.
8. in accordance with the method for claim 6, it is characterised in that：Step b controlling reaction temperatures are 15~35 DEG C.
9. in accordance with the method for claim 6, it is characterised in that：In step b, as the CO being passed through2Gas flow accounts for total intake
When 80% ~ 100%, remainder sodium silicate solution is added.
10. in accordance with the method for claim 6, it is characterised in that：Remainder sodium silicate solution is with silica in step b
Meter accounts for step b and adds 30wt% ~ 70wt% of the sodium silicate solution total amount in terms of silica.
11. in accordance with the method for claim 6, it is characterised in that in step I and III, silicon source, alkali source are respectively selected from sodium metasilicate
And sodium hydroxide, in step I, silicon source is selected from sodium metaaluminate.
12. in accordance with the method for claim 6, it is characterised in that in step III, 10 ~ 30 DEG C of controlling reaction temperature, pH value 10
~11.
13. in accordance with the method for claim 6, it is characterised in that step IV uses two step dynamic crystallizations, wherein the first stepping
The condition of Mobile state crystallization is as follows：Temperature control is at 50~90 DEG C, and crystallization time is 0.5~18 hour；Second step enters Mobile state
The condition of crystallization is as follows：Temperature control is at 80~140 DEG C, and crystallization time is 3~10 hours.
14. in accordance with the method for claim 6, it is characterised in that step IV uses two step dynamic crystallizations, wherein the first stepping
The condition of Mobile state crystallization is as follows：Temperature control is at 60~80 DEG C, and crystallization time is 1~10 hour；It is brilliant that second step enters Mobile state
The condition of change is as follows：Temperature control is at 80~120 DEG C, and crystallization time is 5~10 hours.
15. in accordance with the method for claim 1, it is characterised in that step（2）In, by fine grain NaY type molecular sieve and alkali
Aqueous solution mashing is well mixed, and maintains 1~4h of stir process under 60~120 DEG C of temperature conditionss；Alkali wherein used is
NaOH, KOH or NaOH and KOH mixture；The concentration of the aqueous solution of alkali is the concentration of molecular sieve in 0.1~3 mol/L, slurries
For 0.05~1.0g/mL.
16. in accordance with the method for claim 1, it is characterised in that step（4）In, compare 1 by solid-liquid weight in aqueous medium：4
~1：8 add little crystal grain NH4NaY molecular sieve, stirs and is warming up to 90~120 DEG C, be then added dropwise to hexafluorosilicic acid aqueous ammonium,
Constant temperature is stirred 1~2 hour after completion of dropping, separation molecular sieve and accessory substance, and is filtered, dried；Hexafluorosilicic acid aqueous ammonium
Concentration 10wt% ~ 40wt%, ammonium hexafluorosilicate addition be little crystal grain NH410wt% ~ 50wt% of NaY molecular sieve.
17. in accordance with the method for claim 1, it is characterised in that step（5）In, the condition of described hydro-thermal process is as follows：
Treatment temperature control is at 500~750 DEG C, and pressure is 0.01~0.50MPa, and processing time is 1.0~4.0 hours.
18. in accordance with the method for claim 1, it is characterised in that step（5）In, the condition of described hydro-thermal process is as follows：
Treatment temperature control is at 600~700 DEG C, and pressure is 0.05~0.30MPa, and processing time is 1.0~4.0 hours.
19. in accordance with the method for claim 1, it is characterised in that step（6）In, by the molecular sieve after hydro-thermal process with acid and
Containing NH4 +Salt composition mixed solution contact, acid therein is the one or more in hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, containing NH4 +Salt be containing more than acid acid group ammonium salt in one or more；H in mixed solution+Concentration be 0.05~0.6mol/L,
NH4 +Concentration be 0.5~3.0mol/L, exchange temperature is 70~120 DEG C, exchange the concentration of molecular sieve in slurries for 0.1~
0.5g/mL, swap time is 0.5~3.0 hour, and exchange step repeats 1~4 time.
20. in accordance with the method for claim 1, it is characterised in that：Step（3）The method exchanged using ammonium salt, process is as follows：
Using fine grain NaY type molecular sieve as raw material, exchanged 0.5~3.0 hour at 70~120 DEG C with the aqueous solution of soluble ammonium salt,
Concentration of the molecular sieve in slurries are exchanged is 0.05~0.50g/mL, and repeated exchanged l~5 time filter off mother liquor, washed, dry；Ammonium
Salt is the one or more in ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, ammonium salt solution
Concentration be 0.5~5.0mol/L.
21. in accordance with the method for claim 1, it is characterised in that：Used in being mixed with small crystal grain Y-shaped molecular sieve and adhesive
SiO in amorphous silica-alumina2Weight content be 20%~60%, the pore volume of amorphous silica-alumina is 0.6~1.1 mL/g, compares surface
Product is 300~500m2/g。
22. in accordance with the method for claim 1, it is characterised in that：Carrier drying and the condition of roasting are as follows：80 DEG C~
Dry 3~10 hours and be calcined 3~6 hours at 500 DEG C~600 DEG C at a temperature of 150 DEG C.
23. in accordance with the method for claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, with the weight of carrier
On the basis of amount, its composition includes：The content of small crystal grain Y-shaped molecular sieve is 5wt%~40wt%, and the content of amorphous silica-alumina is
20wt%~65wt%, the content of aluminum oxide is 10wt%~40wt%.
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| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve 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 |
| CN102049282A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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