CN105709844A - Hydrocracking catalyst carrier and preparation method thereof - Google Patents
Hydrocracking catalyst carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst carrier and a preparation method thereof. The catalyst carrier adopts a modified Y type molecular sieve and a beta molecular sieve to serve as a cracking center together, wherein the Y type molecular sieve is a large-grained and high-silicon Y type molecular sieve with centralized effective aperture distribution. The hydrocracking catalyst prepared from the carrier can be used for a hydrocracking process with high yield of high-quality middle distillate oil products, has the characteristics of high activity and good selectivity, and also can produce high-quality hydrogenation tail oil.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, be particularly suitable for carrier of hydrocracking catalyst of high-output qulified low solidifying intermediate oil and preparation method thereof.
Background technology
In recent years, the demand of high-quality middle cut oil product is constantly increased by countries in the world refined products market always, and along with economic develops rapidly, this imbalance between supply and demand seems more prominent.Hydrocracking technology has become heavy oil deep processing with its exclusive advantage and has produced the best means of high-quality cleaning intermediate oil.At present, in countries in the world, the activity of oil type hydrocracking catalyst is not as high, and the condensation point of gained diesel oil is also higher, is difficult to meet refinery and existing apparatus is transformed or increases treating capacity to reach to increase production further the purpose of intermediate oil.
Hydrogenation cracking raise productivity and improve the quality low solidifying intermediate oil it is critical only that exploitation and use suitable catalyst.Although the hydrocracking catalyst containing single molecular sieve component has significantly high activity, but its middle distillates oil selectivity is poor, and the catalyst containing composite molecular screen shows and can improve activity and can improve again selective synergism.
Can having Y type, β type and ZSM type molecular sieve etc. as the molecular sieve of cracking active component in residual oil cracking field at present, wherein Y type molecular sieve application is the most general.The method of current commercial production Y type molecular sieve is essentially all the directing agent method adopting GRACE company of the U.S. to propose in USP3639099 and USP4166099, the crystal grain of the common Y type molecular sieve prepared is generally about 1 μm, the structure cell of nearly about 400 in each dimension.The former powder bore dia of Y type molecular sieve of the typical die size the being conventionally synthesized pore size distribution ratio less than 1nm is 15% ~ 20%, and bore dia is 45% ~ 50% in the pore size distribution ratio of 1nm ~ 10nm, bore dia in the pore size distribution ratio more than 10nm 30% ~ 40%.For macromole cracking reaction, the desirable pore diameter range being suitable for raw material reaction and product diffusion is 1nm ~ 10nm, although Y type molecular sieve is also by follow-up modification appropriateness modulation ideal pore diameter range distribution, but the pore-size distribution of original molecular sieve directly determines the pore diameter range distribution of successive modified molecular sieve, and reaming can affect the framing structure of molecular sieve, and then affect activity and the stability of molecular sieve.
US4,820,402 hydrocracking catalysts disclosing a kind of high selectivity to middle distillates, are characterized in using molecular sieve such as ZSM-20, Y and the β of a kind of high silica alumina ratio, and molecular sieve silica alumina ratio is at least 50:1, it is preferred to more than 200:1.When difference high silica alumina ratio molecular sieve is used for hydrocracking catalyst by the method, middle distillates oil selectivity is ZSM-20 most preferably, next to that β.The activity of this catalyst and middle distillates oil selectivity await further raising.
CN97122139.1 describes a kind of amorphous silicon Al catalysts.This catalyst is with amorphous silica-alumina and aluminium oxide for carrier, and with tungsten, nickel for hydrogenation active metals component, prepared by the method carrying out hydrothermal treatment consists after adopting carrier molding again.Although the activity of this catalyst and the middle distillates oil selectivity amorphous silicon Al catalysts more conventional than it are all significantly improved, but desired reaction temperature is higher, and catalyst activity is poor.
US4,419,271 discloses a kind of hydrocarbon conversion catalyst.Cracking Component is modified HY molecular sieve (LZ-10) and decentralized sial, and active metal component is tungsten, nickel.Wherein the content of LZ-10 molecular sieve is 10wt%～70wt%, and the content of decentralized sial is 30wt%～90wt%, WO3The content that content is 10wt%～30wt%, NiO be 3wt%～10wt%.This catalyst can be used for heavy gas oil hydrogenation cracking and produces intermediate oil (such as turbine fuel and diesel oil).This catalyst middle distillates oil selectivity is low.
CN101578353A describes a kind of method utilizing beta-molecular sieve to be optionally hydrogenated with cracking.Beta-molecular sieve does not carry out the mol ratio of hydrothermal treatment consists or hydrothermal treatment consists, silicon dioxide and aluminium oxide at relatively low temperatures less than the SF of 30:1 and at least 28wt%6Adsorbance, by the catalyst that the modified this beta-molecular sieve obtained is prepared as cracking component, the selectivity of intermediate oil is not high.
US5,350,501, US5,447,623, US5,279,726, US5,536,687 describe a kind of catalyst containing beta-molecular sieve and Y type molecular sieve.During for producing intermediate oil, it consists of: Y type molecular sieve (1 ~ 15w%), beta-molecular sieve (1 ~ 15w%), decentralized sial, aluminium oxide, metal W and Ni.The wherein used NaY that Y type molecular sieve is typical die degree exchanges through ammonium exchange, hydrothermal treatment consists, ammonium, prepared by the method for hydrothermal treatment consists, and the degree of crystallinity of modified molecular screen is not high, and product selectivity is poor.This catalyst reaction activity and middle distillates oil selectivity are not high, it is difficult to meet manufacturer's aggrandizement apparatus disposal ability, increase production the needs of intermediate oil further.
From the molecular sieve with cracking function Industrial Catalysis process should be for, its performance depends primarily on following two aspect: selective absorption and reaction.When reactant molecule is smaller in size than molecular sieve aperture and overcomes molecular sieve crystal surface energy barrier, just diffusing in molecular sieve pore passage, specific catalytic reaction occurs, at this moment adsorbed molecule plays conclusive effect through the hole of molecular sieve crystal and the diffusion of cage.And compare with conventional die molecular sieve, larger crystal molecular sieve has more internal surface area, it is more suitable for the pore passage structure of macromolecular reaction, the second pyrolysis transforming machine meeting in molecular sieve of the more macromole can be provided, therefore larger crystal molecular sieve can process the raw material that the bigger oil product of molecule is heavier, improves the aspects such as macromole conversion probability and shows more superior performance.But for larger crystal molecular sieve, particle diameter is more big, and duct is more long, not only affects the diffusion of reactant, and reactant is susceptible to repeatedly cracking reaction in molecular sieve pore passage, reduce selectivity of catalyst.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and preparation method thereof.This catalyst carrier adopts Modified Zeolite Y and beta-molecular sieve collectively as cracking center, Y type molecular sieve wherein used is the Y type molecular sieve of a kind of big crystal grain, high silicon, effective pore sife distribution concentration, hydrocracking catalyst prepared therefrom is in the hydrocracking process of high-output qulified midbarrel oil product, active height and the good feature of selectivity, can hold concurrently simultaneously and produce the hydrogenation tail oil of high-quality.
Carrier of hydrocracking catalyst of the present invention, comprises Modified Zeolite Y, beta-molecular sieve and aluminium oxide, and wherein the character of Modified Zeolite Y is as follows:
Average grain diameter is 2.0 ~ 5.0 μm, it is preferable that 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, relative crystallinity 110% ~ 150%, SiO2/Al2O3Mol ratio is 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, it is preferred to 2.427 ~ 2.434nm, and bore dia is the pore volume shared by the hole of 3nm ~ 7nm is the 70% ~ 95% of total pore volume, it is preferred to 75% ~ 90%.
In Modified Zeolite Y of the present invention, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminum, it is preferable that 0.1% ~ 0.5%.
In carrier of hydrocracking catalyst of the present invention, the pore volume of described Modified Zeolite Y is 0.35cm3/g~0.50cm3/ g, specific surface area is 800m2/g~980m2/g。
In carrier of hydrocracking catalyst of the present invention, the infrared total acid 0.1 ~ 0.5mmol/g of described Modified Zeolite Y.
In carrier of hydrocracking catalyst of the present invention, in described Modified Zeolite Y, Na2The weight content of O is below 0.15wt%.
In carrier of hydrocracking catalyst of the present invention, the character of described beta-molecular sieve is as follows: average grain diameter is 200 ~ 400nm, and specific surface area is 600m2/g~800m2/ g, pore volume is 0.35cm3/g~0.50cm3/ g, relative crystallinity 100% ~ 140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/Al2O3Mol ratio is 40 ~ 80.This beta-molecular sieve can adopt hydrothermal crystallization method to synthesize, and generally with organic amine for template, the method then passing through the ammonium exchange of routine, acid treatment and hydrothermal treatment consists modifiies and obtains.
Described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminium oxide is 40% ~ 85%.
Carrier of hydrocracking catalyst character of the present invention is as follows: specific surface area is 300 ~ 500m2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention, including: by Modified Zeolite Y, beta-molecular sieve, aluminium oxide mixing, molding, then dry and roasting, making catalyst carrier, wherein the preparation method of Modified Zeolite Y, comprises the steps:
(1) preparation of big crystal NaY type molecular sieve；
(2) the big crystal NaY type molecular sieve of step (1) gained is become big crystal grain NH4NaY；
(3) step (2) gained Y type molecular sieve is carried out hydrothermal treatment consists；Wherein hydrothermal conditions: gauge pressure is 0.28 ~ 0.50MPa, temperature is 550 ~ 700 DEG C, and the process time is 0.5 ~ 5.0 hour；
(4) with (NH4)2SiF6Aqueous solution contacts with the material of step (3) gained, is then passed through filter and dry, prepares Modified Zeolite Y.
In the preparation process of Modified Zeolite Y used by the present invention, the character of the big crystal NaY type molecular sieve described in step (1) is as follows:
Average grain diameter is 2.0 ~ 5.0 μm, it is preferable that 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, and bore dia is that the pore volume shared by the hole of 1nm ~ 10nm accounts for the 70% ~ 90% of total pore volume, it is preferred to 70% ~ 85%, and specific surface is 800m2/g~1000m2/ g, total pore volume is 0.30mL/g ~ 0.40mL/g, and external surface area is 60m2/g~100m2/ g, relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.
The NaY type molecular sieve of the present invention, it is preferred that character is as follows: specific surface is 800m2/g~1000m2/ g, total pore volume is 0.30mL/g ~ 0.40mL/g, and external surface area is 60m2/g~100m2/g。
The NaY type molecular sieve of the present invention, it is preferred that character is as follows: SiO2/Al2O3Mol ratio 3.5 ~ 6.5, it is preferred to 4.0 ~ 6.0.
In the preparation process of Modified Zeolite Y used by the present invention, big crystal grain NH prepared by step (2)4In NaY, the weight content of sodium oxide is 2.5% ~ 5.0%.
In the preparation process of Modified Zeolite Y used by the present invention, the hydrothermal treatment consists of step (3) is to process, with saturated steam, the molecular sieve obtained in step (2), treatment conditions: gauge pressure 0.28 ~ 0.50MPa, it is preferably 0.3 ~ 0.5MPa, temperature 550 ~ 700 DEG C, it is preferably 600 ~ 700 DEG C, processes 0.5 ~ 5.0 hour time, it is preferable that 1.0 ~ 3.0 hours.
In the inventive method, step (4) is by the material obtained in step (3) and (NH4)2SiF6Aqueous solution contact, process is as follows: the molecular sieve obtained in step (3) is pulled an oar in aqueous, and solvent and solute weight ratio is 8:1 ~ 15:1, and temperature is 95 ~ 130 DEG C；(NH is added in slurry4)2SiF6Aqueous solution, adds 35 ~ 80 grams of (NH according to every 100 grams of Y molecular sieves4)2SiF6Amount add (NH4)2SiF6Aqueous solution, every 100gY type molecular sieve can add 3 ~ 30 grams of (NH per hour4)2SiF6, add (NH4)2SiF6Aqueous solution with disposed slurry, stirs 0.5 ~ 5.0 hour, then filtration drying, obtains product at temperature is for 80 ~ 120 DEG C.
In the preparation process of Modified Zeolite Y used by the present invention, in step (1), the preparation method of NaY type molecular sieve, comprises the steps:
I, directly prepare gel: at 20 DEG C ~ 40 DEG C temperature, it is desirable to be at 25 DEG C ~ 35 DEG C temperature, according to Na2O:Al2O3: SiO2: H2The molar ratio of O=10 ~ 15:1:10 ~ 20:500 ~ 600, when stirring, waterglass is slowly added into mix homogeneously in high alkali deflection aluminium acid sodium solution, afterwards, it is sequentially added into aluminum sulfate solution and low alkali aluminium acid sodium solution, stirs at the temperature disclosed above；Then constant temperature is aging in confined conditions, obtains gel；
II, crystallization: the gel that step (2) is obtained at the Water Under thermal crystallisation 12 ~ 24 hours of 80 DEG C ~ 120 DEG C and stirring, after crystallization through filtering, washing, dry, obtain big crystal NaY type molecular sieve.
In the preparation process of NaY type molecular sieve used by the present invention, step I feeds intake according to following mol ratio, Na2O:Al2O3: SiO2: H2O=10 ~ 15:1:10 ~ 20:500 ~ 600, wherein water can be individually added into, it is also possible to together adds with solution.
In the preparation process of NaY type molecular sieve used by the present invention, in step I, the ratio of the addition of aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali sodium metaaluminate, it is calculated as 1:(0.5 ~ 0.7 with aluminium oxide): (0.6 ~ 0.8).
In the preparation process of NaY type molecular sieve used by the present invention, step I is added without the additives such as directed agents, template, surfactant in reaction system, by selecting the raw material and the optimized fabrication process that are suitable for, a hydrothermal crystallizing is adopted to synthesize big crystal NaY type molecular sieve, the utilization ratio in silicon source and aluminum source is high, technological process is simple, and cost is low.The granularity of NaY type molecular sieve prepared by the method reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, heat stability and hydrothermal stability good.
The big grain Y-molecular sieve that catalyst carrier of the present invention adopts, owing to this larger crystal molecular sieve not only has bigger crystal grain, structure cell quantity in each dimension is made to increase to 1000 ~ 2000, macromole is conducive to crack, but also there is pore size distribution range more preferably, the cracking degree of reactant can be efficiently controlled, and be conducive to product to be diffused in duct, so in cracking reaction, can relatively increase active center, and macromole can be made to carry out the cracking reaction of suitable degree, catalyst can show good cracking activity and product selectivity.
Catalyst carrier of the present invention adopts Modified Zeolite Y and beta-molecular sieve collectively as cracking center, both its respective performance characteristics had been given full play to, the concerted catalysis effect that two kinds of molecular sieves produce can be made again, namely the long side chain on alkane or aromatic hydrocarbons is had good isomerization by beta molecular sieve, can effectively reduce the condensation point of product, aromatic hydrocarbons is had significantly high selectivity of ring-opening by Y type molecular sieve simultaneously, improves the product property of purpose product.The active height of hydrocracking catalyst prepared by carrier of the present invention, can high-output qulified midbarrel oil product (boat coal+diesel oil), can hold concurrently simultaneously and produce the hydrogenation tail oil of high-quality.
When the hydrocracking catalyst prepared by carrier of the present invention is for heavy oil hydrocracking, under condition of high voltage (12 ~ 20MPa), particularly process wax slop (VGO, CGO and DAO), poor ignition quality fuel (coker gas oil and catalytic diesel oil etc.) can also be added, there is significantly high catalysis activity and intermediate oil selectivity, and the condensation point of diesel oil distillate reduction amplitude is big, the product property of intermediate oil improves, and can meet refinery and increase operating flexibility, increases device disposal ability, increases production the needs of intermediate oil further.
Accompanying drawing explanation
Fig. 1 is the SEM electromicroscopic photograph of embodiment 1 gained LY-1；
Fig. 2 is the SEM electromicroscopic photograph of comparative example 1 gained DLY-1；
Fig. 3 is the XRD diffraction pattern of embodiment 1 gained LY-1.
Detailed description of the invention
In carrier of hydrocracking catalyst of the present invention, aluminium oxide can adopt aluminium oxide used in conventional hydrocracking catalyst, such as macroporous aluminium oxide and or little porous aluminum oxide.Pore volume 0.7 ~ the 1.0mL/g, specific surface area 200 ~ 500m of macroporous aluminium oxide used2/ g.The pore volume of little porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Catalyst support preparation process of the present invention can also add the shaping assistant such as peptization acid of routine, extrusion aid etc..
In the preparation process of Modified Zeolite Y used by the present invention, in the preparation method of the big crystal NaY type molecular sieve of step (1), Na in high alkali deflection aluminium acid sodium solution2O content is 260 ~ 320g/L, Al2O3Content is 30 ~ 50g/L, and conventional method can be adopted to prepare.Na in low alkali aluminium acid sodium solution2O content is 100 ~ 130g/L, Al2O3Content is 60 ~ 90g/L, and conventional method can be adopted to prepare.Al in aluminum sulfate solution2O3Content be 80 ~ 100g/L.SiO in waterglass2Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.
In the preparation process of Modified Zeolite Y used by the present invention, the preparation method of the big crystal NaY type molecular sieve of step (1), specifically include following steps:
I, according to Na2O:Al2O3: SiO2: H2The molar ratio of O=10 ~ 15:1:10 ~ 20:500 ~ 600, at 20 DEG C ~ 40 DEG C temperature, it is preferably at 25 ~ 35 DEG C of temperature, when stirring, waterglass is slowly added into mix homogeneously in high alkali deflection aluminium acid sodium solution, afterwards, add aluminum sulfate solution and low alkali aluminium acid sodium solution, stir at the temperature disclosed above, be generally 0.5 ~ 1.0 hour；Then being enclosed in synthesis reactor by mixed liquor, static constant temperature is aging, it is preferable that ageing time is 1.0 ~ 2.0 hours；
II, by synthesis mother liquid in confined conditions, the method adopting a thermostatic crystallization.A described thermostatic crystallization refers to crystallization under agitation.Under agitation, first speed (being typically in 2 ~ 4 DEG C/minute) slower for gel is warmed up under 90 DEG C ~ 110 DEG C conditions, and thermostatic crystallization 12 ~ 24 hours at this temperature.After crystallization terminates, quickly synthesis reactor is cooled, through filtering, wash and being dry, obtain big crystal NaY type molecular sieve.
In the preparation process of Modified Zeolite Y used by the present invention, step (2) can ammonium concentration be the ammonium salt solution of 0.1mol/L ~ 1.0mol/L, described ammonium salt is selected from one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate, being 50 ~ 100 DEG C in temperature, when solvent and solute weight ratio is 8:1 ~ 15:1, constant temperature processes big crystal NaY, time is 0.5 ~ 1.5 hour, through filter, then repeat under these conditions ammonium exchange, the product obtained through filter, stand-by after drying.Wherein require that in the larger crystal molecular sieve after controlling ammonium exchange, the weight content of sodium oxide is 2.5% ~ 5.0%.
In the preparation process of Modified Zeolite Y used by the present invention, step (3) is to be obtained by the product water heat treatment obtained in step (2).The molecular sieve obtained in step (2) is processed with saturated steam, pipe type water heat-treatment furnace adds the molecular sieve obtained in step (2), treatment conditions: gauge pressure 0.28 ~ 0.50MPa, it is preferably 0.3 ~ 0.5MPa, temperature 550 ~ 700 DEG C, it is preferably 600 ~ 700 DEG C, processes 0.5 ~ 5 hour time, it is preferable that 1 ~ 3 hour.
In the inventive method, step (4) is by the material obtained in step (3) and (NH4)2SiF6Aqueous solution contact, process is as follows: the molecular sieve obtained in step (3) is pulled an oar in aqueous, and solvent and solute weight ratio is 8:1 ~ 15:1, and temperature is 95 ~ 130 DEG C；(NH is added in slurry4)2SiF6Aqueous solution, adds 35 ~ 80 grams of (NH according to every 100 grams of Y molecular sieves4)2SiF6Amount add (NH4)2SiF6Aqueous solution, every 100gY type molecular sieve can add 3 ~ 30 grams of (NH per hour4)2SiF6, add (NH4)2SiF6Aqueous solution with disposed slurry, stirs 0.5 ~ 5.0 hour, then filtration drying, obtains product at temperature is for 80 ~ 120 DEG C.
Stirring described in the inventive method is to adopt conventional stirring means, is generally adopted mechanical agitation.
Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows: by Modified Zeolite Y, beta-molecular sieve, aluminium oxide mixing, extruded moulding, then dry and roasting, prepare into carrier；Drying and can dry 3～6 hours at the temperature of 80 DEG C to 150 DEG C, roasting is 500 DEG C～600 DEG C roastings 2.5～6.0 hours.
The following examples preparation method for illustrating in greater detail carrier of the present invention, but the scope of the present invention is not limited solely to the scope of these embodiments.
The present invention analyzes method: specific surface area, pore volume and external surface area, pore size distribution adopt low temperature liquid nitrogen physisorphtion to record, relative crystallinity and cell parameter adopt X-ray diffraction method to record, silica alumina ratio adopts chemical analysis to record, and the grain size of molecular sieve adopts SEM(scanning electron microscope) mode measure.
The feedstock property that the embodiment of the present invention 1 prepares big crystal NaY molecular sieve and comparative example 1 is prepared used by DLY-3 molecular sieve is as follows:
High alkali deflection aluminium acid sodium solution: Na2O content 291g/L, Al2O3Content 42g/L；
Low alkali aluminium acid sodium solution: Na2O content 117g/L, Al2O3Content 77g/L；
Aluminum sulfate solution: Al2O3Content 90g/L；
Waterglass: SiO2Content 250g/L, modulus 3.2.
Embodiment 1
The present embodiment is to adopt the inventive method to prepare big crystal NaY molecular sieve.
The preparation of LY-1
(1) preparation of gel: temperature is 25 DEG C, under stirring condition, it is slowly added to 165mL waterglass in the high alkali deflection aluminium acid sodium solution of 63mL, after mix homogeneously, it is sequentially added into aluminum sulfate solution and the 35.6mL low alkali aluminium acid sodium solution of 42.5mL, constant temperature stirs 0.5 hour, then by the synthesis liquid that obtains static aging 1 hour at the temperature disclosed above, gel is obtained；
(2) crystallization: under agitation, with the heating rates of 2.5 DEG C/minute, the gel in synthesis reactor is raised to 100 DEG C, constant temperature stirring crystallization 16 hours, after crystallization terminates, quickly lower the temperature with cold water, and open the molecular sieve that synthesis reactor taking-up is synthetic, through filtering, wash and being dry, obtaining product LY-1, product property is in Table 1.
The preparation of LY-2:
(1) preparation of gel: temperature is 35 DEG C, under stirring condition, it is slowly added to 156mL waterglass in the high alkali deflection aluminium acid sodium solution of 48mL, after mix homogeneously, it is sequentially added into aluminum sulfate solution and the 28.5mL low alkali aluminium acid sodium solution of 39.6mL, constant temperature constant speed stirs 1 hour, then by the synthesis liquid that obtains static aging 2 hours at the temperature disclosed above, gel is obtained；
(2) crystallization: under agitation, with the heating rates of 3 DEG C/minute, the gel in synthesis reactor is raised to 110 DEG C, constant temperature stirring crystallization 24 hours, after crystallization terminates, quickly lower the temperature with cold water, and open the molecular sieve that synthesis reactor taking-up is synthetic, through filtering, wash and being dry, obtaining product LY-2, product property is in Table 1.
Comparative example 1
This comparative example is to adopt art methods to prepare big crystal NaY molecular sieve raw material.
DLY-1:
Adopt USP3639099, adopt directing agent method to prepare molecular sieve.Concrete preparation process is: the preparation of directed agents, is dissolved in by 26g aluminium hydroxide in 153g sodium hydroxide and 279mL water, forms A raw material；Then in A raw material, add 525g waterglass (modulus 3.3), after above-mentioned gel is quickly stirred, at room temperature aging 24 hours, stand-by；
At 37.8 DEG C, in 2223g waterglass (modulus 3.3), containing 601g aluminum sulfate solution, (aluminum sulfate content is with Al in addition2O3Meter=16.9wt%), then 392g directed agents is joined in above-mentioned solution, stir, then 191g sodium aluminate solution (containing 126g aluminium hydroxide and 96.5g sodium hydroxide) is added, above-mentioned solution is quickly stirred and then within 10 hours, obtains NaY molecular sieve at 98.8 DEG C of hydrothermal crystallizings, sample number into spectrum is DLY-1, and product property is in Table 1.
DLY-2:
The method adopting CN101481120A prepares molecular sieve.0.699g Ludox (40wt%), 0.156g sodium hydroxide, 0.212g sodium aluminate and 2.94mL water purification are at room temperature stirred, obtain white gels, then 2.4gOP10,1.6g n-butyl alcohol, 1.8mL hexamethylene, stir, 100 DEG C of hydrothermal crystallizings 24 hours, obtaining product DLY-2, product property is in Table 1.
DLY-3:
The preparation of directed agents, takes 153g sodium hydrate solid and is dissolved in 279mL deionized water, after being cooled to room temperature, adds 22.5g sodium metaaluminate and makes high alkali deflection aluminium acid sodium solution.Then in 525g waterglass, add high alkali deflection aluminium acid sodium solution, after mix homogeneously at room temperature aging 24 hours, stand-by.
1547g waterglass is sequentially added into 720g deionized water, 222.5g low alkali aluminium acid sodium solution and 242g directed agents under stirring, after mix homogeneously, load in stainless steel cauldron, 100 DEG C of static crystallization 24 hours, it is then passed through filter, washing and dries, obtaining product DLY-3, product property is in Table 1.
Embodiment 2
First the big crystal NaY molecular sieve LY-1 of raw material is carried out ammonium exchange.Compound concentration is 0.5mol/L aqueous ammonium nitrate solution 10 liters.Weighing small crystal grain NaY molecular sieve 2000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, and at 90 DEG C, constant temperature stirs 1 hour, then filtering molecular sieve, and stays sample, analyzes Na2O content；Repeat aforesaid operations, until Na in molecular sieve2O content reach 2.5～5.0wt%, obtaining dried sample number into spectrum is LYN-1.
Embodiment 3
Big crystal NaY molecular sieve LY-1 in embodiment 2 is changed into LY-2, repeats the process of embodiment 2, prepared sample, be numbered LYN-2.
Embodiment 4
Weigh 200gLYN-1 molecular sieve and put in pipe type water heat-treatment furnace, temperature programming to 590 DEG C, process 2.0 hours under gauge pressure 0.30MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 100 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 386mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 38.6 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, dry, obtains production code member LYNS-1, and character is listed in table 2
Embodiment 5
Weigh 200gLYN-1 molecular sieve and put in pipe type water heat-treatment furnace, temperature programming to 650 DEG C, process 1.0 hours under gauge pressure 0.4MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 120 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 676mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 67.6 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, dry, obtains production code member LYNS-2, and character is listed in table 2.
Embodiment 6
Weigh 200gLYN-2 molecular sieve and put in pipe type water heat-treatment furnace, temperature programming to 600 DEG C, process 3.0 hours under gauge pressure 0.45MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 110 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 435mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 43.5 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, dry, obtains production code member LYNS-3, and character is listed in table 2.
Embodiment 7
Weigh 200gLYN-2 molecular sieve and put in pipe type water heat-treatment furnace, temperature programming to 680 DEG C, process 1.5 hours under gauge pressure 0.3MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 100 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 723mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 72.3 grams of ammonium hexafluorosilicate altogether, then constant temperature constant speed stirs 2 hours, filters, dry, obtains production code member LYNS-4, and character is listed in table 2.
Comparative example 2 ~ 4
Big crystal NaY molecular sieve LY-1 in embodiment 2 is changed into respectively DLY-1, DLY-2 and DLY-3, repeats the process of embodiment 2, prepared sample, be numbered DLYN-1, DLYN-2 and DLYN-3.
Comparative example 5 ~ 7
LYN-1 in embodiment 5 changing into DLYN-1, DLYN-2 and DLYN-3 respectively, repeats the process of embodiment 5, prepared sample, be numbered DYNS-1, DYNS-2, DYNS-3, character is listed in table 2.
The character of table 1NaY type molecular sieve
Continued 1
Note: in table 1, * roasting condition is as follows: roasting 3 hours in 600 DEG C of air；
* the condition of hydrothermal treatment consists is as follows: 650 DEG C of steam treatment 1 hour.
The character of table 2Y type molecular sieve
Continued 2
Embodiment 8
By 44.44 grams of LYNS-1 molecular sieves (butt 90wt%), 22.22 grams of beta-molecular sieve (crystal grain=250nm, SiO2/Al2O3=50, pore volume 0.45ml/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g butt 90wt%), 142.7 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of binding agents (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar dries 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtains carrier ZS-1.
Embodiment 9
By 44.44 grams of LYNS-2 molecular sieves (butt 90wt%), 33.3 grams of beta-molecular sieve (crystal grain=250nm, SiO2/Al2O3=50, pore volume 0.45ml/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g butt 90wt%), 128.6 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of binding agents (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar dries 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtains carrier ZS-2.
The impregnation liquid room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C dry 4 hours, and 500 DEG C of roastings of temperature programming 4 hours obtain catalyst Z C-2, carrier and corresponding catalyst character in Table 3.
Embodiment 10
By 66.66 grams of LYNS-3 molecular sieves (butt 90wt%), 11.11 grams of beta-molecular sieve (crystal grain=250nm, SiO2/Al2O3=50, pore volume 0.45ml/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g butt 90wt%), 142.7 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of binding agents (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar dries 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtains carrier ZS-3.
Embodiment 11
By 55.55 grams of LYNS-4 molecular sieves (butt 90wt%), 44.44 grams of beta-molecular sieve (crystal grain=250nm, SiO2/Al2O3=50, pore volume 0.45ml/g, specific surface area 750m2/ g, infrared total acid 0.29mmoL/g butt 90wt%), 142.7 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific surface area 400m2/ g, butt 70wt%), 133.3 grams of binding agents (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar dries 4 hours at 110 DEG C, then 550 DEG C of roastings 4 hours, obtains carrier ZS-4.
Comparative example 8 ~ 10
By the method for embodiment 9 into, LYNS-2 is changed respectively DYNS-1, DYNS-2, DYNS-3, make carrier DZS-1, DZS-2, DZS-3 and catalyst DZC-1, DZC-2 and DZC-3, carrier and catalyst and form in Table 3.
Embodiment 12
This embodiment describes and prepared catalyst Z C-2 Activity evaluation by carrier of the present invention.Being evaluated on fixed bed hydrogenation assay device, appreciation condition is: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250:1, volume space velocity 1.5h during liquid-1, adopting one-stage serial once by technological process, use vacuum distillate (VGO) as raw oil, raw oil character is listed in table 4, and evaluation result is listed in table 5.
Comparative example 11 ~ 13
This comparative example describes catalyst DZC-1, DZC-2 and the DZC-3 Activity evaluation prepared by comparative example carrier of the present invention.Being evaluated on fixed bed hydrogenation assay device, appreciation condition is: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250:1, volume space velocity 1.5h during liquid-1, adopting one-stage serial once by technological process, use vacuum distillate (VGO) as raw oil, raw oil character is listed in table 4, and evaluation result is listed in table 5.
The physico-chemical property of table 3 catalyst carrier and catalyst
Table 4 raw oil character
Table 5 catalyst performance comparative evaluation's result
By the evaluation result of table 5 it can be seen that under identical process conditions, adopt carrier prepared catalyst of the present invention, intermediate oil selectivity, yield and product quality are superior to reference catalyst.
Claims (18)
1. a carrier of hydrocracking catalyst, comprises Modified Zeolite Y, beta-molecular sieve and aluminium oxide, and wherein the character of Modified Zeolite Y is as follows: average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, relative crystallinity 110% ~ 150%, SiO2/Al2O3Mol ratio is 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, and bore dia is the pore volume shared by the hole of 3nm ~ 7nm is the 70% ~ 95% of total pore volume, it is preferred to 75% ~ 90%.
2. the catalyst carrier described in claim 1, it is characterised in that: described Modified Zeolite Y, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminum, it is preferable that 0.1% ~ 0.5%.
3. the catalyst carrier described in claim 1, it is characterised in that: the pore volume of described Modified Zeolite Y is 0.35cm3/g~0.50cm3/ g, specific surface area is 800m2/g~980m2/g。
4. the catalyst carrier described in claim 1, it is characterised in that: the infrared total acid 0.1 ~ 0.5mmol/g of described Modified Zeolite Y.
5. the catalyst carrier described in claim 1, it is characterised in that: in described Modified Zeolite Y, Na2The weight content of O is below 0.15wt%.
6. the catalyst carrier described in claim 1, it is characterised in that: the character of described beta-molecular sieve is as follows: average grain diameter is 200 ~ 400nm, and specific surface area is 600m2/g~800m2/ g, pore volume is 0.35cm3/g~0.50cm3/ g, relative crystallinity 100% ~ 140%, infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO2/Al2O3Mol ratio is 40 ~ 80.
7. the catalyst carrier described in claim 1, it is characterised in that: described carrier, with the weight of carrier for benchmark, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminium oxide is 40% ~ 85%.
8. the preparation method of the arbitrary described catalyst carrier of claim 1 ~ 7, including: by Modified Zeolite Y, beta-molecular sieve, aluminium oxide mixing, molding, then dry and roasting, making catalyst carrier, wherein the preparation method of Modified Zeolite Y, comprises the steps:
(1) preparation of big crystal NaY type molecular sieve；
(2) the big crystal NaY type molecular sieve of step (1) gained is become big crystal grain NH4NaY；
(3) step (2) gained Y type molecular sieve is carried out hydrothermal treatment consists；Wherein hydrothermal conditions: gauge pressure is 0.28 ~ 0.50MPa, temperature is 550 ~ 700 DEG C, and the process time is 0.5 ~ 5.0 hour；
(4) with (NH4)2SiF6Aqueous solution contacts with the material of step (3) gained, is then passed through filter and dry, prepares Y type molecular sieve.
9. in accordance with the method for claim 8, it is characterised in that: the character of the big crystal NaY type molecular sieve described in step (1) is as follows:
Average grain diameter is 2.0 ~ 5.0 μm, it is preferable that 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, bore dia is that the pore volume shared by the hole of 1nm ~ 10nm accounts for the 70% ~ 90% of total pore volume, being preferably 70% ~ 85%, relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.
10. in accordance with the method for claim 8, it is characterised in that: the character of step (1) described NaY type molecular sieve is as follows: SiO2/Al2O3Mol ratio 3.5 ~ 6.5, it is preferred to 4.0 ~ 6.0.
11. according to the method described in claim 8,9 or 10, it is characterised in that: the character of step (1) described NaY type molecular sieve is as follows: specific surface area is 800m2/g~1000m2/ g, total pore volume is 0.30mL/g ~ 0.40mL/g, and external surface area is 60m2/g~100m2/g。
12. in accordance with the method for claim 7, it is characterised in that: big crystal grain NH prepared by step (2)4In NaY, the weight content of sodium oxide is 2.5% ~ 5.0%.
13. in accordance with the method for claim 8, it is characterised in that: the hydrothermal conditions of step (3) is as follows: gauge pressure is 0.30 ~ 0.50MPa, and temperature is 600 ~ 700 DEG C, and the process time is 1.0 ~ 3.0 hours.
14. in accordance with the method for claim 7, it is characterised in that: step (4) is by the material obtained in step (3) and (NH4)2SiF6Aqueous solution contact, solvent and solute weight ratio is 8:1 ~ 15:1, and temperature is 95 ~ 130 DEG C, adds 35 ~ 80 grams of (NH by every 100 grams of Y molecular sieves4)2SiF6Amount add (NH4)2SiF6Aqueous solution, every 100gY type molecular sieve adds 3 ~ 30 grams of (NH per hour4)2SiF6, add (NH4)2SiF6Aqueous solution, stirs 0.5 ~ 5.0 hour with disposed slurry at temperature is for 80 ~ 120 DEG C.
15. in accordance with the method for claim 8, it is characterised in that: the preparation method of big crystal NaY type molecular sieve in step (1), comprise the steps:
I, at 20 DEG C ~ 40 DEG C temperature under, according to Na2O:Al2O3: SiO2: H2The molar ratio of O=10 ~ 15:1:10 ~ 20:500 ~ 600, when stirring, waterglass is slowly added into mix homogeneously in high alkali deflection aluminium acid sodium solution, afterwards, it is sequentially added into aluminum sulfate solution and low alkali aluminium acid sodium solution, stirs at the temperature disclosed above；Then constant temperature is aging in confined conditions, obtains gel；
II, the gel that step I is obtained at the Water Under thermal crystallisation 12 ~ 24 hours of 80 DEG C ~ 120 DEG C and stirring, after crystallization through filtering, washing, dry, obtain big crystal NaY type molecular sieve.
16. in accordance with the method for claim 15, it is characterised in that: in step I, the ratio of the addition of aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali sodium metaaluminate, it is calculated as 1:(0.5 ~ 0.7 with aluminium oxide): (0.6 ~ 0.8).
17. in accordance with the method for claim 15, it is characterised in that: in step I, Na in described high alkali deflection aluminium acid sodium solution2O content is 260 ~ 320g/L, Al2O3Content is 30 ~ 50g/L；Na in described low alkali aluminium acid sodium solution2O content is 100 ~ 130g/L, Al2O3Content is 60 ~ 90g/L, Al in described aluminum sulfate solution2O3Content be 80 ~ 100g/L；SiO in described waterglass2Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.
18. in accordance with the method for claim 15, it is characterised in that: in step II, under agitation, temperature is warmed up to crystallization temperature that is 80 DEG C ~ 120 DEG C with 2 ~ 4 DEG C/minute.
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| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| 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 |
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