CN105709799A - Hydro-upgrading catalyst and preparation method thereof - Google Patents
Hydro-upgrading catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydro-upgrading catalyst and a preparation method thereof. The hydro-upgrading catalyst provided by the invention adopts a large-grained Y type molecular sieve with concentrated effective pore size distribution as the modification component, is suitable to serve as an inferior diesel hydro-upgrading catalyst, has very high catalytic activity and diesel yield, can greatly improve the cetane value of upgraded diesel, and effectively reduces the density of the diesel product.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly one can with poor ignition quality fuel for raw material, the diesel oil hydrogenation modification Catalysts and its preparation method that the diesel oil of production has diesel product yield height, Cetane number is high and decrease in density amplitude is big.
Background technology
From oil Refining Technologies angle, diesel oil derives from normal pressure straight-run diesel oil and the diesel oil distillate of secondary operations production.And the main path of secondary operations technique has catalytic cracking, hydrogenation cracking and delayed coking.Due to the raising of clean fuel standards, (especially heavy MIP diesel oil, its density is up to 0.95g/cm to cause catalytic diesel oil inferior3Above) and coker gas oil can not meet index request.How to use alap investment and operating cost, the fuel oil for vehicles that production environment is friendly, it has also become the problem that oil refining enterprise is urgently to be resolved hurrily.
For cleaning diesel production, prior art mainly includes the technology such as hydrofinishing and MHUG.Hydrofinishing can effectively reduce the sulfur content of upgrading diesel oil, but to improving Cetane number and reducing T95Temperature capability is limited.MHUG is to utilize suitably to be cracked by diesel oil when middle pressure, generating portion Petroleum and wide cut diesel fuel, and the Y type molecular sieve that the Cracking Component adopted in pressure diesel modifying catalyst at present mainly modifiies, and the crystal grain of the former powder of NaY preparing Modified Zeolite Y is at about 1 μm, and it is conducive to effective pore size distribution of solid tumor and reaction not concentrate so that the amplitude that the yield dry large-minded, diesel product of existing diesel modifying catalyst is low, Cetane number improves is little, T95The shortcomings such as the low and density of point is big.
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, aperture 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.
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.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40wt% ~ 80wt%, amorphous silica-alumina 0 ~ 20wt%, molecular sieve 5wt% ~ 30wt%, described molecular sieve is pore volume 0.40 ~ 0.52mL/g, specific surface area 750 ~ 900m2/ g, lattice constant 2.420 ~ 2.500nm, silica alumina ratio is the Y type molecular sieve of 7 ~ 15, and the grain size of molecular sieve is about 1 μm.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopt predecessor and Y type molecular sieve mixing, molding and the roasting of silica-alumina, aluminium oxide and/or aluminium oxide, introduce the hydrogenation metal of effective dose afterwards at molding species.Above-mentioned catalyst all adopts the Y type molecular sieve of typical die size, and its desulfurization and denitrification activity are higher, but the amplitude that the yield of gained diesel product is low, diesel-fuel cetane number improves is little, condensation point is high and density is big.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of catalyst for hydro-upgrading and preparation method thereof.The Modified Zeolite Y that this catalyst for hydro-upgrading a kind of big crystal grain of employing, effective pore sife distribution are more concentrated, as main upgrading Cracking Component, adopts catalyst of the present invention for, in poor ignition quality fuel hydrogenation process, having the features such as diesel yield height is good with quality.
Catalyst for hydro-upgrading provided by the invention, comprise hydrogenation active metals component and carrier, carrier includes Modified Zeolite Y and aluminium oxide, 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 10 ~ 50, it is preferred to 12 ~ 45, and cell parameter is 2.436 ~ 2.450nm, and bore dia is the pore volume shared by the hole of 2nm ~ 6nm is the 60% ~ 90% of total pore volume, it is preferred to 70% ~ 85%.
In 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%.
The pore volume of described Modified Zeolite Y is 0.35cm3/g~0.50cm3/ g, specific surface area is 750m2/g~950m2/g。
The infrared total acid content of described Modified Zeolite Y is 0.5 ~ 1.0mmol/g.
In described Modified Zeolite Y, Na2The weight content of O is below 0.15wt%.
The specific surface area of catalyst for hydro-upgrading of the present invention is 330 ~ 500m2/ g, pore volume is 0.35 ~ 0.55mL/g.
Hydrogenation active metals of the present invention is the metal of vib and group VIII, vib metals be preferably molybdenum and or tungsten, the metal of group VIII be preferably cobalt and or nickel.With the weighing scale of catalyst, the content that vib metals (is counted with oxide) is 15.0%～30.0%, and the content that group VIII metal (is counted with oxide) is 4.0%～8.0%.
Described catalyst for hydro-upgrading carrier, with the weight of carrier for benchmark, the content of Modified Zeolite Y is 5% ~ 40%, it is preferred to 10% ~ 35%, and the content of aluminium oxide is 60% ~ 95%, it is preferred to 65% ~ 90%.
The preparation method of catalyst for hydro-upgrading of the present invention, preparation and load hydrogenation active metals component including carrier, wherein the preparation process of carrier is as follows: by Modified Zeolite Y, 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；Hydrothermal conditions: gauge pressure 0.05 ~ 0.25MPa, temperature 400 ~ 550 DEG C, process 0.5 ~ 5.0 hour time；
(4) with (NH4)2SiF6Aqueous solution contacts with the material of step (3) gained, is then passed through filter and dry, prepares the Modified Zeolite Y of the present invention.
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, 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.
The NaY type molecular sieve of the present invention, it is preferred that character 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。
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 0.05 ~ 0.25MPa, it is preferably 0.10 ~ 0.20MPa, temperature 400 ~ 550 DEG C, it is preferably 450 ~ 550 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: first pulled an oar in aqueous by the molecular sieve obtained in step (3), and solvent and solute weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C；Then, in slurry, (NH is added4)2SiF6Aqueous solution, adds 10 ~ 35 grams of (NH according to 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 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 Y type molecular sieve that the catalyst of the present invention big crystal grain of employing, effective pore sife distribution are more concentrated is as upgrading component.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, both having improve the cracking capability of macromole, and reduced coke yield simultaneously, catalyst can show good activity and product selectivity.
During by catalyst for hydro-upgrading of the present invention for poor ignition quality fuel upgrading, under middle press strip part (4 ~ 12MPa), particularly process poor ignition quality fuel (heavy MIP diesel oil and coker gas oil) there is significantly high catalysis activity and diesel yield, upgrading diesel-fuel cetane number can be increased substantially, the density of diesel product is effectively reduced, and can meet that refinery increases operating flexibility, increases device disposal ability, raise productivity and improve the quality the needs of diesel oil further.
Operating condition when catalyst for hydro-upgrading of the present invention is for poor ignition quality fuel upgrading is as follows: reaction stagnation pressure 4.0 ~ 12.0MPa, volume space velocity 1.0 ~ 3.0h during liquid-1, hydrogen to oil volume ratio is 400:1 ~ 1000:1, reaction temperature 345 ~ 435 DEG C.
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 catalyst for hydro-upgrading of the present invention, aluminium oxide can adopt aluminium oxide used in conventional hydro modifying catalyst, such as macroporous aluminium oxide.Pore volume 0.7 ~ the 1.0mL/g, specific surface area 200 ~ 500m of macroporous aluminium oxide used2/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 method of the big crystal NaY type molecular sieve of the present invention, 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.
The preparation method of the big crystal NaY type molecular sieve of the present invention, specifically includes 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 ~ 2 hour；
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.
Stirring described in the inventive method is to adopt conventional stirring means, is generally adopted mechanical agitation.
In the inventive method, 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, it it is 50 ~ 100 DEG C in temperature, when solvent and solute weight ratio is 8:1 ~ 15:1, constant temperature processes big crystal NaY, and the time is 0.5 ~ 1.5 hour, through filtering, 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%.
Step of the present invention (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 0.05 ~ 0.25MPa, it is preferably 0.10 ~ 0.20MPa, temperature 400 ~ 550 DEG C, it is preferably 450 ~ 550 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: first pulled an oar in aqueous by the molecular sieve obtained in step (3), and solvent and solute weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C；Then, in slurry, (NH is added4)2SiF6Aqueous solution, adds 10 ~ 35 grams of (NH according to 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 with disposed slurry, stirs 0.5 ~ 5.0 hour, then filtration drying, obtains product at temperature is for 80 ~ 120 DEG C.
Detailed process prepared by catalyst for hydro-upgrading carrier of the present invention is:
By Modified Zeolite Y, aluminium oxide mixing, extruded moulding, being then dried and roasting, prepare into carrier, described drying can dry 3 ~ 6 hours at the temperature of 80 DEG C ~ 150 DEG C, and roasting is 500 DEG C ~ 600 DEG C roastings 2.5 ~ 6.0 hours.
In catalyst for hydro-upgrading of the present invention, the load of active metal, the weight content that tungsten (is counted with oxide) is 15.0%～30.0%, and the weight content that metallic nickel (is counted with oxide) is 4.0%～8.0%；Carrying method conventional in prior art can be adopted, preferred infusion process, can be saturated leaching, excessive leaching or complexation leaching, namely with the solution impregnated catalyst carrier containing required active component, carrier after dipping dries 1～12 hour at 100 DEG C～150 DEG C, then 450 DEG C～550 DEG C roastings 2.5～6.0 hours, final catalyst is prepared.
The following examples are used for illustrating in greater detail technical scheme, but the scope of the present invention is not limited solely to the scope of these embodiments.In the present invention, wt% is mass fraction.
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 physico-chemical 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 2.5～5wt%, 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 430 DEG C, process 2.0 hours under gauge pressure 0.1MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 195mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 19.5 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 530 DEG C, process 1 hour under gauge pressure 0.15MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 80 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 286mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 28.6 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 500 DEG C, process 3.0 hours under gauge pressure 0.2MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 75 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 246mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 24.6 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 540 DEG C, process 1.5 hours under gauge pressure 0.1MPa, after hydrothermal treatment consists, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 85 DEG C, and speed of agitator is 300rpm.Within the time of 2 hours, at the uniform velocity adding 301mL hexafluorosilicic acid aqueous ammonium in molecular sieve slurry, add 30.1 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 and DYNS-3, character is listed in table 2.
The character of table 1NaY type molecular sieve
Continued 1
| Production code member | DLY-1 | DLY-2 | DLY-3 |
| Specific surface area, m2/g | 840 | 820 | 738 |
| Pore volume, cm3/g | 0.32 | 0.32 | 0.30 |
| External surface area, m2/g | 150 | 132 | 121 |
| Lattice constant, nm | 2.468 | 2.468 | 2.472 |
| Relative crystallinity, % | 96 | 146.7 | 92 |
| Average crystallite size, μm | 0.95 | 1.80 | 1.10 |
| SiO2/Al2O3Mol ratio | 4.21 | 4.35 | 5.10 |
| The pore volume that bore dia 1nm ~ 10nm accounts for accounts for total pore volume, % | 51 | 56 | 43 |
| Relative crystallinity *, % after roasting | 69 | 81 | 44 |
| Relative crystallinity *, % after hydrothermal treatment consists | 70 | 70 | 76 |
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
| Production code member | LYNS-1 | LYNS-2 | LYNS-3 | LYNS-4 |
| Specific surface area, m2/g | 933 | 920 | 899 | 887 |
| Pore volume, cm3/g | 0.43 | 0.44 | 0.45 | 0.47 |
| Lattice constant, nm | 2.446 | 2.440 | 2.442 | 2.438 |
| Relative crystallinity, % | 128 | 133 | 130 | 136 |
| Average crystallite size, μm | 3.0 | 3.0 | 3.0 | 3.0 |
| SiO2/Al2O3Mol ratio | 13.6 | 33.5 | 28.4 | 39.5 |
| The pore volume that bore dia 2nm ~ 6nm accounts for is total pore volume, % | 72 | 78 | 75 | 80 |
| Non-framework aluminum accounts for total aluminum content, % | 0.4 | 0.3 | 0.2 | 0.2 |
| Infrared total acid content, mmol/g | 0.88 | 0.67 | 0.75 | 0.61 |
| Na2O, wt% | 0.13 | 0.12 | 0.10 | 0.10 |
Continued 2
| Production code member | DYNS-1 | DYNS-2 | DYNS-3 |
| Specific surface area, m2/g | 611 | 650 | 630 |
| Pore volume, cm3/g | 0.36 | 0.35 | 0.36 |
| Lattice constant, nm | 2.443 | 2.439 | 2.441 |
| Relative crystallinity, % | 91 | 81 | 80 |
| Average crystallite size, μm | 0.95 | 0.95 | 0.95 |
| SiO2/Al2O3Mol ratio | 9.8 | 15.3 | 20.8 |
| The pore volume that bore dia 2nm ~ 6nm accounts for is total pore volume, % | 29 | 32 | 35 |
| Non-framework aluminum accounts for the total aluminum content of molecular sieve, % | 1.8 | 1.5 | 43 |
| Infrared total acid content, mmol/g | 1.02 | 0.87 | 0.76 |
| Na2O, wt% | 0.16 | 0.18 | 0.20 |
Embodiment 8
By 44.4 grams of LYNS-1 molecular sieves (butt 90wt%), 228.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 171.4 grams of peptizers (4g nitric acid/100g peptizer) put into mixed grind in chaser, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GDS-1.
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 FC-1, carrier and corresponding catalyst character in Table 3.
Embodiment 9
By 88.9 grams of LYNS-2 molecular sieves (butt 90wt%), 171.4 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 184.1 grams of peptizers (4g nitric acid/100g peptizer) put into mixed grind in chaser, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GDS-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 FC-2, carrier and corresponding catalyst character in Table 3.
Embodiment 10
By 33.3 grams of LYNS-3 molecular sieves (butt 90wt%), 242.9 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 168.8 grams of peptizers (4g nitric acid/100g peptizer) put into mixed grind in chaser, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GDS-3.
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 FC-3, carrier and corresponding catalyst character in Table 3.
Embodiment 11
By 111.1 grams of LYNS-4 molecular sieves (butt 90wt%), 142.9 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 190.4 grams of peptizers (4g nitric acid/100g peptizer) put into mixed grind in chaser, be rolled into paste, extrusion, extrusion bar 110 DEG C dry 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GDS-4.
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 FC-4, carrier and corresponding catalyst character in Table 3.
Comparative example 8 ~ 10
According to the method for embodiment 9 into, LYNS-2 is changed respectively DYNS-1, DYNS-2, DYNS-3, make carrier DGDS-1, DGDS-2, DGDS-3 and catalyst DFC-1, DFC-2, DFC-3, carrier and corresponding catalyst character in Table 3.
Embodiment 12 ~ 15
This embodiment describes by catalyst FC-1 of the present invention, FC-2, FC-3 and FC-4 Activity evaluation.Being evaluated on fixed bed hydrogenation assay device, appreciation condition is: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700:1, volume space velocity 2.0h during liquid-1, use catalytic diesel oil as raw oil, raw oil character is listed in table 4, and evaluation result is listed in table 5.
Comparative example 9 ~ 11
This comparative example describes by the Activity evaluation of comparative example catalyst DFC-1, DFC-2, DFC-3 of the present invention.Being evaluated on fixed bed hydrogenation assay device, appreciation condition is: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700:1, volume space velocity 2.0h during liquid-1, use catalytic diesel oil 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
| Carrier composition and character | ||||
| Numbering | GDS-1 | GDS-2 | GDS-3 | GDS-4 |
| Y type molecular sieve, wt% | 20 | 40 | 15 | 50 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 513 | 564 | 488 | 586 |
| Pore volume, mL/g | 0.78 | 0.69 | 0.79 | 0.65 |
| Catalyst composition and character | ||||
| Numbering | FC-1 | FC-2 | FC-3 | FC-4 |
| WO3, wt% | 23.5 | 24.3 | 19.6 | 21.6 |
| NiO, wt% | 5.6 | 5.8 | 4.9 | 5.3 |
| Specific surface area, m2/g | 0.53 | 0.48 | 0.55 | 0.45 |
| Pore volume, mL/g | 359 | 395 | 341 | 386 |
Continued 3
| Carrier composition and character | |||
| Numbering | DGDS-1 | DGDS-2 | DGDS-3 |
| Y type molecular sieve, wt% | 40 | 40 | 40 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 398 | 364 | 378 |
| Pore volume, mL/g | 0.56 | 0.61 | 0.59 |
| Catalyst composition and character | |||
| Numbering | DFC-1 | DFC-2 | DFC-3 |
| WO3, wt% | 24.4 | 24.5 | 24.4 |
| NiO, wt% | 6.1 | 6.0 | 5.9 |
| Specific surface area, m2/g | 0.38 | 0.41 | 0.39 |
| Pore volume, mL/g | 276 | 255 | 261 |
Table 4 raw oil character
| Raw oil | MIP catalytic diesel oil |
| Density (20 DEG C), g/cm3 | 0.9537 |
| Boiling range, DEG C | |
| IBP/10% | 200/234 |
| 30%/50% | 256/277 |
| 70%/90% | 305/348 |
| 95%/EBP | 363/367 |
| Condensation point, DEG C | 5 |
| Sulfur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | <20.0 |
| C, wt% | 88.49 |
| H, wt% | 11.04 |
Table 5 catalyst performance comparative evaluation's result
| Catalyst | FC-1 | FC-2 | FC-3 | FC-4 |
| Raw oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil |
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 | 2.0 |
| Reaction stagnation pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 700:1 | 700:1 | 700:1 | 700:1 |
| Reaction temperature, DEG C | 370 | 365 | 372 | 360 |
| Product yield and character | ||||
| Petroleum | ||||
| Yield, wt% | 2.2 | 2.1 | 2.1 | 1.8 |
| Virtue is dived, wt% | 57.2 | 58.6 | 58.9 | 60.2 |
| Diesel oil | ||||
| Yield, wt% | 96.1 | 96.7 | 96.4 | 97.3 |
| Density (20 DEG C)/g.cm-3 | 0.8342 | 0.8353 | 0.8350 | 0.8366 |
| T95, DEG C | 343 | 345 | 345 | 347 |
| Cetane number | 3835 | 39.6 | 40.3 | 40.6 |
| Sulfur, μ g/g | 7 | 6 | 5 | 5 |
| Liquid is received, wt% | 98.3 | 98.8 | 98.5 | 99.1 |
Continued 5
| Catalyst | DFC-1 | DFC-2 | DFC-3 |
| Raw oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil |
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 |
| Reaction stagnation pressure, MPa | 10.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 700:1 | 700:1 | 700:1 |
| Reaction temperature, DEG C | 373 | 386 | 389 |
| Product yield and character | |||
| Petroleum | |||
| Yield, wt% | 3.8 | 3.9 | 4.6 |
| Virtue is dived, wt% | 51.3 | 50.4 | 47.9 |
| Diesel oil | |||
| Yield, wt% | 93.0 | 91.7 | 88.6 |
| Density (20 DEG C)/g.cm-3 | 0.8595 | 0.8509 | 0.8501 |
| T95, DEG C | 353 | 354 | 352 |
| Cetane number | 31.0 | 31.1 | 31.0 |
| Sulfur, μ g/g | 15 | 17 | 19 |
| Liquid is received, wt% | 96.8 | 95.6 | 93.2 |
By the evaluation result of table 5 it can be seen that under identical process conditions, when adopting catalyst of the present invention, diesel yield and product quality are superior to reference catalyst.
Claims (18)
1. a catalyst for hydro-upgrading, comprise hydrogenation active metals component and carrier, carrier includes Modified Zeolite Y and aluminium oxide, 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 10 ~ 50, and cell parameter is 2.436 ~ 2.450nm, and bore dia is the pore volume shared by the hole of 2nm ~ 6nm is the 60% ~ 90% of total pore volume, it is preferred to 70% ~ 85%.
2. the catalyst described in claim 1, it is characterised in that: in 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 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 750m2/g~950m2/g。
4. the catalyst described in claim 1, it is characterised in that: the infrared total acid 0.5 ~ 1.0mmol/g of described Modified Zeolite Y.
5. the catalyst 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 described in claim 1, it is characterised in that: described carrier, with the weight of carrier for benchmark, the content including Modified Zeolite Y is 5% ~ 40%, it is preferred to 10% ~ 35%, and the content of aluminium oxide is 60% ~ 95%, it is preferred to 65% ~ 90%.
7. the catalyst described in claim 1, it is characterized in that: described hydrogenation active metals adopts the metal of vib and group VIII, vib metals be molybdenum and or tungsten, group VIII metal be cobalt and or nickel, with the weight of catalyst for benchmark, the content that vib metals is counted with oxide is for 10.0% ~ 30.0%, and the content that group VIII metal is counted with oxide is for 4.0% ~ 8.0%.
8. the preparation method of the arbitrary described catalyst of claim 1 ~ 7, preparation and load hydrogenation active metals component including carrier, wherein the preparation process of carrier is as follows: by Modified Zeolite Y, 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；Hydrothermal conditions: gauge pressure is 0.05 ~ 0.25MPa, temperature is 400 ~ 550 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.
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 8, 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 gauge pressure is 0.1 ~ 0.2MPa, and temperature is 450 ~ 550 DEG C, and the process time is 1.0 ~ 3.0 hours.
14. in accordance with the method for claim 8, 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 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, adds 10 ~ 35 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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| 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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