CN105709799B - A kind of catalyst for hydro-upgrading and preparation method thereof - Google Patents
A kind of catalyst for hydro-upgrading and preparation method thereof Download PDFInfo
- Publication number
- CN105709799B CN105709799B CN201410711587.7A CN201410711587A CN105709799B CN 105709799 B CN105709799 B CN 105709799B CN 201410711587 A CN201410711587 A CN 201410711587A CN 105709799 B CN105709799 B CN 105709799B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- content
- modified zeolite
- molecular sieve
- accordance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst for hydro-upgrading and preparation method thereof.Catalyst for hydro-upgrading of the present invention is using the Y type molecular sieve that a kind of big crystal grain, effective pore sife distribution are concentrated as modification component, suitably it is used as catalyst for hydro-upgrading of inferior diesel, with very high catalytic activity and diesel yield, the Cetane number of modification diesel oil can be increased substantially, the density of diesel product is effectively reduced.
Description
Technical field
Can be using poor ignition quality fuel as original the present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, particularly one kind
Material, the diesel oil of production have the diesel oil hydrogenation modification catalysis that diesel product yield is high, Cetane number is high and density reduction amplitude is big
Agent and preparation method thereof.
Background technology
From oil Refining Technologies angle, diesel oil is from normal pressure straight-run diesel oil and the diesel oil distillate of secondary operation production.It is and secondary
The main path of processing technology has catalytic cracking, is hydrocracked and delayed coking.Due to the raising of clean fuel standards, cause bad
Matter catalytic diesel oil（Especially heavy MIP diesel oil, its density are up to 0.95g/cm3More than）It can not meet index with coker gas oil
It is required that.How alap investment and operating cost, production environment friendly fuel oil for vehicles, it has also become oil refining enterprise urgently are used
Problem to be solved.
For cleaning diesel production, prior art mainly includes the technologies such as hydrofinishing and MHUG.Hydrogenation essence
System can effectively reduce the sulfur content of modification diesel oil, but to improving Cetane number and reducing T95Temperature capability is limited.Medium pressure hydrogenation changes
Matter is to utilize suitably to crack diesel oil under conditions of middle pressure, generating portion naphtha and wide cut diesel fuel, and middle pressure bavin at present
Cracking Component employed in oily modifying catalyst is mainly modified Y type molecular sieve, and prepares the NaY of Modified Zeolite Y
The crystal grain of former powder is at 1 μm or so, and it is advantageous to solid tumor and effective pore size distribution of reaction is not concentrated so that existing diesel oil
Dry large-minded, diesel product the yield of modifying catalyst is low, Cetane number improves amplitude is small, T95The point big grade of low and density lacks
Point.
The method of industrial production Y type molecular sieve is essentially all in the Hes of USP 3639099 using GRACE companies of the U.S. at present
The directing agent method proposed in USP 4166099, the crystal grain of obtained common Y type molecular sieve is generally 1 μm or so, in each dimension
On the structure cell of about 400 or so.The Y type molecular sieve original powder bore dia for the typical die size being conventionally synthesized is less than 1nm's
Pore size distribution ratio is 15% ~ 20%, and pore size distribution ratio of the bore dia in 1nm ~ 10nm is 45% ~ 50%, and aperture is in the hole more than 10nm
Distribution proportion is 30% ~ 40%.For macromolecular cracking reaction, it is adapted to the preferable pore diameter range of raw material reaction and product diffusion to be
1nm ~ 10nm, although Y type molecular sieve can be also distributed by follow-up modification appropriateness modulation ideal pore diameter range, original point
The pore-size distribution of son sieve directly determines the pore diameter range distribution of successive modified molecular sieve, and reaming can influence the skeleton of molecular sieve
Structure, and then influence the activity and stability of molecular sieve.
From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following
Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface
It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal
Hole and cage diffusion serve it is conclusive.And compared with conventional die molecular sieve, larger crystal molecular sieve has more
Internal surface area, be more suitable for the pore passage structure of macromolecular reaction, using the teaching of the invention it is possible to provide more two secondary fissures of the macromolecular in molecular sieve
Transforming machine meeting is solved, therefore larger crystal molecular sieve can handle the heavier raw material of the bigger oil product of molecule, improve macromolecular conversion probability
Etc. show more superior performance.But for larger crystal molecular sieve, particle diameter is bigger, and duct is longer, not only influences
The diffusion of reactant, and multiple cracking reaction easily occurs in molecular sieve pore passage for reactant, reduces the selectivity of catalyst.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, the composition of the catalyst for aluminum oxide 40wt% ~
80wt%, 0 ~ 20wt% of amorphous silica-alumina, molecular sieve 5wt% ~ 30wt%, described molecular sieve are 0.40 ~ 0.52mL/g of pore volume, compare table
750 ~ 900m of area2/ g, 2.420 ~ 2.500nm of lattice constant, silica alumina ratio are 7 ~ 15 Y type molecular sieve, and the crystal grain of molecular sieve is big
Small is 1 μm or so.CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopts
Mixed, be molded and be calcined with the predecessor of silica-alumina, aluminum oxide and/or aluminum oxide and Y type molecular sieve, be molded afterwards
Species introduce the hydrogenation metal of effective dose.Above-mentioned catalyst uses the Y type molecular sieve of typical die size, its desulfurization and denitrogenation
Activity is higher, but the amplitude that the yield of gained diesel product is low, the Cetane number of diesel oil improves is small, condensation point is high and density is big.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of catalyst for hydro-upgrading and its preparation side
Method.The Modified Zeolite Y that the catalyst for hydro-upgrading is more concentrated using a kind of big crystal grain, effective pore sife distribution, which is used as, mainly to be changed
Matter Cracking Component, it is used for using catalyst of the present invention in poor ignition quality fuel hydrogenation process, has diesel yield high and quality waits well spy
Point.
Catalyst for hydro-upgrading provided by the invention, comprising hydrogenation active metal component and carrier, carrier includes modified Y types
The property of molecular sieve and aluminum oxide, wherein Modified Zeolite Y is as follows：Average grain diameter be 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, is preferably
12 ~ 45, cell parameter is 2.436 ~ 2.450nm, and bore dia is that the pore volume shared by 2nm ~ 6nm hole is the 60% ~ 90% of total pore volume,
Preferably 70% ~ 85%.
In described Modified Zeolite Y, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminium, preferably 0.1% ~ 0.5%.
The pore volume of described Modified Zeolite Y is 0.35cm3/g~0.50cm3/ g, specific surface area 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, Na2O weight content is below 0.15wt%.
The specific surface area of catalyst for hydro-upgrading of the present invention is 330 ~ 500m2/ g, pore volume are 0.35 ~ 0.55mL/g.
Hydrogenation active metals of the present invention are the metal of vib and group VIII, and vib metals are preferably molybdenum
He ∕ or tungsten, the metal of group VIII is preferably Gu He ∕ or nickel.In terms of the weight of catalyst, vib metals（With oxide
Meter）Content be 15.0%~30.0%, group VIII metal（In terms of oxide）Content be 4.0%~8.0%.
Described catalyst for hydro-upgrading carrier, on the basis of the weight of carrier, the content of Modified Zeolite Y for 5% ~
40%, preferably 10% ~ 35%, the content of aluminum oxide is 60% ~ 95%, preferably 65% ~ 90%.
The preparation method of catalyst for hydro-upgrading of the present invention, include preparation and the load hydrogenation active metal component of carrier,
The preparation process of wherein carrier is as follows：Modified Zeolite Y, aluminum oxide are mixed, shaping, then dries and is calcined, be made and urge
The preparation method of agent carrier, wherein Modified Zeolite Y, comprises the following steps：
（1）The preparation of big crystal grain NaY type molecular sieves；
（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH4NaY；
（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：0.05 ~ 0.25MPa of gauge pressure,
400 ~ 550 DEG C of temperature, 0.5 ~ 5.0 hour processing time；
（4）With（NH4）2SiF6The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, is made
The Modified Zeolite Y of the present invention.
In the preparation process of Modified Zeolite Y used in the present invention, step（1）Described big crystal grain NaY type molecular sieves
Property 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, and bore dia is
Pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, and relative crystallinity is 110% ~ 150%,
Cell parameter 2.460nm ~ 2.465nm.
The NaY type molecular sieves of the present invention, preferable property are as follows：Specific surface area is 800m2/g~1000m2/ g, total pore volume are
0.30mL/g ~ 0.40mL/g, external surface area 60m2/g~100m2/g。
The NaY type molecular sieves of the present invention, preferable property are as follows：SiO2/Al2O3Mol ratio 3.5 ~ 6.5, preferably 4.0 ~
6.0。
In the preparation process of Modified Zeolite Y used in the present invention, step（2）The big crystal grain NH of preparation4Sodium oxide molybdena in NaY
Weight content be 2.5% ~ 5.0%.
In the preparation process of Modified Zeolite Y used in the present invention, step（3）Hydro-thermal process be with saturated steam
Manage step（2）In obtained molecular sieve, treatment conditions：0.05 ~ 0.25MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, temperature 400 ~
550 DEG C, preferably 450 ~ 550 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.
In the inventive method, step（4）It is by step（3）In obtained material with（NH4）2SiF6The aqueous solution contact, mistake
Journey is as follows：First by step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 3：1~8：1, temperature 70
~90℃；Then, added into slurry（NH4）2SiF6The aqueous solution, 10 ~ 35 grams are added according to every 100 grams of Y molecular sieves（NH4）2SiF6
Amount add（NH4）2SiF6The aqueous solution, add 3 ~ 30 grams per 100gY types molecular sieve per hour（NH4）2SiF6, add（NH4）2SiF6The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.
In the preparation process of Modified Zeolite Y used in the present invention, step（1）The preparation method of middle NaY types molecular sieve, bag
Include following steps：
I, gel is directly prepared：At a temperature of 20 DEG C ~ 40 DEG C, at a temperature of preferably 25 DEG C ~ 35 DEG C, according to Na2O：Al2O3：
SiO2：H2O=10~15：1：10~20：500 ~ 600 molar ratio, height is slowly added under conditions of stirring by waterglass
It is well mixed in alkali sodium aluminate solution, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution is sequentially added, in said temperature
Under stir；Then constant temperature aging in confined conditions, obtains gel；
II, crystallization：By step（2）Hydrothermal crystallizing 12 ~ 24 is small at 80 DEG C ~ 120 DEG C and under conditions of stirring for obtained gel
When, through filtering, washing, drying after crystallization, obtain big crystal grain NaY type molecular sieves.
In the preparation process of NaY types molecular sieve used in the present invention, step I feeds intake according to following mol ratio, Na2O：
Al2O3：SiO2：H2O=10~15：1：10~20：500 ~ 600, its reclaimed water can be individually added into, and can also together be added with solution.
In the preparation process of NaY types molecular sieve used in the present invention, in step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali are inclined
The ratio of the addition of sodium aluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.
In the preparation process of NaY types molecular sieve used in the present invention, step I is added without directed agents, template in reaction system
The additives such as agent, surfactant are big using a hydrothermal crystallizing synthesis by selecting suitable raw material and optimization preparation process
The utilization ratio of crystal NaY type molecular sieve, silicon source and silicon source is high, and technological process is simple, and cost is low.NaY types prepared by this method
The granularity of molecular sieve reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, heat endurance and hydrothermally stable
Property is good.
Catalyst of the present invention is using the Y type molecular sieve that big crystal grain, effective pore sife distribution are more concentrated as modification component.Due to
The larger crystal molecular sieve not only has larger crystal grain so that structure cell quantity increases to 1000 ~ 2000 in each dimension, favorably
Cracked in macromolecular, but also there is more preferably pore size distribution range, the cracking degree of reactant can be efficiently controlled,
And be advantageous to product and be diffused in duct, so in cracking reaction, can relative increase activated centre, and macromolecular can be made
The cracking reaction of suitable degree is carried out, had both improved the cracking capability of macromolecular, while reduces coke yield, catalyst can show
Go out good activity and product selectivity.
When being used for poor ignition quality fuel modification by catalyst for hydro-upgrading of the present invention, particularly in middle press strip part（4~12MPa）Under
Handle poor ignition quality fuel（Heavy MIP diesel oil and coker gas oil）With very high catalytic activity and diesel yield, can significantly carry
The Cetane number of height modification diesel oil, the density of diesel product are effectively reduced, and can meet refinery's increase operating flexibility, increase
The needs of device disposal ability, the diesel oil that further raises productivity and improves the quality.
The operating condition that catalyst for hydro-upgrading of the present invention is used for when poor ignition quality fuel modifies is as follows：Reaction stagnation pressure 4.0 ~
12.0MPa, 1.0 ~ 3.0h of volume space velocity during liquid-1, hydrogen to oil volume ratio 400：1~1000：1,345 ~ 435 DEG C of reaction temperature.
Brief description of the drawings
Fig. 1 is the gained LY-1 of embodiment 1 SEM electromicroscopic photographs；
Fig. 2 is the gained DLY-1 of comparative example 1 SEM electromicroscopic photographs；
Fig. 3 is the gained LY-1 of embodiment 1 XRD diffraction patterns.
Embodiment
Aluminum oxide can use aluminum oxide used in conventional hydro modifying catalyst in catalyst for hydro-upgrading of the present invention,
Such as macroporous aluminium oxide.0.7 ~ 1.0mL/g of pore volume of macroporous aluminium oxide used, 200 ~ 500m of specific surface area2/g。
Conventional shaping assistant such as peptization acid, extrusion aid can also be added in catalyst carrier preparation process of the present invention
Deng.
In the preparation method of big crystal grain NaY type molecular sieves of the present invention, Na in high alkali deflection aluminium acid sodium solution2O content be 260 ~
320g/L, Al2O3Content is 30 ~ 50g/L, conventional method can be used to prepare.Na in low alkali aluminium acid sodium solution2O content be 100 ~
130g/L, Al2O3Content is 60 ~ 90g/L, conventional method can be used to prepare.Al in aluminum sulfate solution2O3Content for 80 ~
100g/L.SiO in waterglass2Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.
The preparation method of big crystal grain NaY type molecular sieves of the present invention, specifically comprises the following steps：
I, according to Na2O：Al2O3：SiO2：H2O=10~15：1：10~20：500 ~ 600 molar ratio, at 20 DEG C ~ 40 DEG C
At a temperature of, at a temperature of preferably 25 ~ 35 DEG C, waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring
It is well mixed, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution are added, is stirred at the temperature disclosed above, generally 0.5
~ 1.0 hours；Then mixed liquor is enclosed in synthesis reactor, static constant temperature aging, preferably ageing time are 1 ~ 2 hour；
II, by synthesis mother liquid in confined conditions, using the method for a thermostatic crystallization.A described thermostatic crystallization is
Refer to crystallization under agitation.Under agitation, first by the slower speed of gel（Typically at 2 ~ 4 DEG C/minute）It is warming up to
Under the conditions of 90 DEG C ~ 110 DEG C, and thermostatic crystallization 12 ~ 24 hours at this temperature.After crystallization terminates, quickly synthesis reactor is cooled down
Cooling, filtered, washing and drying, obtain big crystal grain NaY type molecular sieves.
Stirring described in the inventive method is using conventional stirring means, typically using mechanical agitation.
Step in the inventive method（2）Ammonium salt solution that can be using ammonium concentration as 0.1mol/L ~ 1.0mol/L, it is described
One or more of the ammonium salt in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate, it is 50 ~ 100 DEG C in temperature, the solid weight of liquid
Than for 8：1~15：Under conditions of 1, constant temperature processing big crystal grain NaY, the time is 0.5 ~ 1.5 hour, filtered, then in above-mentioned bar
Repeat ammonium exchange under part, obtained product is filtered, stand-by after drying.Wherein require the big crystal grain point after control ammonium exchange
The weight content of sodium oxide molybdena is 2.5% ~ 5.0% in son sieve.
Step of the present invention（3）It is by step（2）In obtained product hydro-thermal process and obtain.Handled and walked with saturated steam
Suddenly（2）In obtained molecular sieve, add step in pipe type water heat-treatment furnace（2）In obtained molecular sieve, treatment conditions：Gauge pressure
0.05 ~ 0.25MPa, preferably 0.10 ~ 0.20MPa, preferably 400 ~ 550 DEG C of temperature, 450 ~ 550 DEG C, processing time 0.5 ~ 5.0
Hour, preferably 1.0 ~ 3.0 hours.
In the inventive method, step（4）It is by step（3）In obtained material with（NH4）2SiF6The aqueous solution contact, mistake
Journey is as follows：First by step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 3：1~8：1, temperature 70
~90℃；Then, added into slurry（NH4）2SiF6The aqueous solution, 10 ~ 35 grams are added according to every 100 grams of Y molecular sieves（NH4）2SiF6
Amount add（NH4）2SiF6The aqueous solution, add 3 ~ 30 grams per 100gY types molecular sieve per hour（NH4）2SiF6, add（NH4）2SiF6The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.
Detailed process prepared by catalyst for hydro-upgrading carrier of the present invention is：
Modified Zeolite Y, aluminum oxide are mixed, extruded moulding, is then dried and is calcined, be prepared into carrier, institute
The drying stated can be dried 3 ~ 6 hours at a temperature of 80 DEG C ~ 150 DEG C, and roasting is small in 500 DEG C ~ 600 DEG C roastings 2.5 ~ 6.0
When.
In catalyst for hydro-upgrading of the present invention, the load of active metal, tungsten（In terms of oxide）Weight content be
15.0%~30.0%, metallic nickel（In terms of oxide）Weight content be 4.0%~8.0%；Can be using routine in the prior art
Carrying method, preferably infusion process, it can be saturation leaching, excessive leaching or complexing leaching, i.e., be soaked with the solution containing required active component
Stain catalyst carrier, carrier after dipping was in 100 DEG C~150 DEG C dryings 1~12 hour, then in 450 DEG C~550 DEG C roastings
2.5~6.0 hours, final catalyst is made.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this
The scope of a little embodiments.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area, pore volume and external surface area, pore size distribution use low temperature liquid nitrogen physisorphtion
Measuring, relative crystallinity and cell parameter are measured using X-ray diffraction method, and silica alumina ratio is measured using chemical analysis, point
The grain size of son sieve uses SEM（SEM）Mode determine.
The preparation big crystal grain NaY molecular sieve of the embodiment of the present invention 1 and comparative example 1 prepare feed stock used in DLY-3 molecular sieves
Matter 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 prepare big crystal grain NaY molecular sieve using the inventive method.
LY-1 preparation
（1）The preparation of gel：Temperature is 25 DEG C, under stirring condition, is slowly added into 63mL high alkali deflection aluminium acid sodium solution
Enter 165mL waterglass, after being well mixed, sequentially add 42.5mL aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solutions,
Constant temperature stirs 0.5 hour, then by obtained Synthesis liquid static aging 1 hour at the temperature disclosed above, obtains gel；
（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 100 DEG C with 2.5 DEG C/minute of heating rate, perseverance
Temperature stirring crystallization 16 hours, after crystallization terminates, is quickly cooled with cold water, and is opened synthesis reactor and taken out synthetic molecular sieve, warp
It is filtered, washed and dried, obtains product LY-1, product property is shown in Table 1.
LY-2 preparation：
（1）The preparation of gel：Temperature is 35 DEG C, under stirring condition, is slowly added into 48mL high alkali deflection aluminium acid sodium solution
Enter 156mL waterglass, after being well mixed, sequentially add 39.6mL aluminum sulfate solution and 28.5mL low alkali aluminium acid sodium solutions,
Constant temperature constant speed stirs 1 hour, then by obtained Synthesis liquid static aging 2 hours at the temperature disclosed above, obtains gel；
（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 110 DEG C with 3 DEG C/minute of heating rate, constant temperature
Stir crystallization 24 hours, after crystallization terminates, quickly cooled with cold water, and open synthesis reactor and take out synthetic molecular sieve, pass through
Filter, wash and dry, obtain product LY-2, product property is shown in Table 1.
Comparative example 1
This comparative example is to prepare big crystal grain NaY molecular sieve raw material using art methods.
DLY-1：
Using USP 3639099, molecular sieve is prepared using directing agent method.Specifically preparation process is：The preparation of directed agents, will
26g aluminium hydroxides are dissolved in 153g sodium hydroxides and 279mL water, form A raw materials；Then 525g water glass is added into A raw materials
Glass（Modulus 3.3）, after above-mentioned gel quickly stirring, aging 24 hours, stand-by at room temperature；
At 37.8 DEG C, to 2223g waterglass（Modulus 3.3）Middle addition aluminum sulfate solution containing 601g（Sulfuric acid aluminium content with
Al2O3Count=16.9 wt%）, then 392g directed agents are added in above-mentioned solution, stirred, then add 191g aluminic acids
Sodium solution（Contain 126g aluminium hydroxides and 96.5g sodium hydroxides）, above-mentioned solution is quickly stirred and then in 98.8 DEG C of hydro-thermal crystalline substances
Change 10 hours and obtain NaY molecular sieve, sample number into spectrum DLY-1, physico-chemical property is shown in Table 1.
DLY-2：
Molecular sieve is prepared using CN101481120A method.By 0.699g Ludox（40wt%）, 0.156g hydroxides
Sodium, 0.212g sodium aluminates and 2.94mL water purification are stirred at room temperature uniformly, obtain white gels, and then 2.4g OP10,1.6g be just
Butanol, 1.8mL hexamethylenes, stir, and 100 DEG C of hydrothermal crystallizings 24 hours, obtain product DLY-2, product property is shown in Table 1.
DLY-3：The preparation of directed agents, take 153g sodium hydrate solids to be dissolved in 279mL deionized waters, be cooled to room temperature
Afterwards, 22.5g sodium metaaluminates are added and high alkali deflection aluminium acid sodium solution is made.Then it is molten that high alkali deflection aluminium acid sodium is added in 525g waterglass
Liquid, aging 24 hours at room temperature after being well mixed are stand-by.
In 1547g waterglass stir under sequentially add 720g deionized waters, 222.5g low alkali aluminium acid sodium solutions and
242g directed agents, after being well mixed, it is fitted into stainless steel cauldron, it is then filtered, wash in 100 DEG C of static crystallization 24 hours
Wash and dry, obtain product DLY-3, product property is shown in Table 1.
Embodiment 2
Ammonium exchange is carried out to raw material big crystal grain NaY molecular sieve LY-1 first.Compound concentration is that 0.5mol/L ammonium nitrate is water-soluble
10 liters of liquid.2000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is
300rpm, constant temperature stirs 1 hour at 90 DEG C, and then filtering molecular sieves, and stays sample, analyzes Na2O content；Repeat above-mentioned behaviour
Make, until Na in molecular sieve2O content reaches 2.5~5wt%, and it is LYN-1 to obtain dried sample number into spectrum.
Embodiment 3
Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into LY-2, repeat the process of embodiment 2, obtained sample
Product, numbering LYN-2.
Embodiment 4
Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 430 DEG C, in gauge pressure 0.1MPa
Lower processing 2.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 90 DEG C, stirring
Rotating speed is 300rpm.Within the time of 2 hours, 195mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, are added altogether
Enter 19.5 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, and dries, and obtains production code member LYNS-1, property row
In table 2.
Embodiment 5
Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 530 DEG C, in gauge pressure
Handle 1 hour, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, temperature 80 under 0.15MPa
DEG C, speed of agitator 300rpm.Within the time of 2 hours, it is water-soluble that 286mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry
Liquid, 28.6 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-2,
Property is listed in table 2.
Embodiment 6
Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 500 DEG C, in gauge pressure 0.2MPa
Lower processing 3.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 75 DEG C, stirring
Rotating speed is 300rpm.Within the time of 2 hours, 246mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, are added altogether
Enter 24.6 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, and dries, and obtains production code member LYNS-3, property row
In table 2.
Embodiment 7
Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 540 DEG C, in gauge pressure 0.1MPa
Lower processing 1.5 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 85 DEG C, stirring
Rotating speed is 300rpm.Within the time of 2 hours, 301mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, are added altogether
Enter 30.1 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, and dries, and obtains production code member LYNS-4, property row
In table 2.
Comparative example 2 ~ 4
Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into DLY-1, DLY-2 and DLY-3 respectively, repeat embodiment
2 process, obtained sample, numbering DLYN-1, DLYN-2 and DLYN-3.
Comparative example 5 ~ 7
Change the LYN-1 in embodiment 5 into DLYN-1, DLYN-2 and DLYN-3 respectively, repeat the process of embodiment 5, system
The sample obtained, numbering DYNS-1, DYNS-2 and DYNS-3, property are listed in table 2.
The property of the NaY type molecular sieves of table 1
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 is accounted for accounts for total pore volume, % | 51 | 56 | 43 |
| Relative crystallinity * after roasting, % | 69 | 81 | 44 |
| Relative crystallinity * after hydro-thermal process, % | 70 | 70 | 76 |
Note：In table 1, * roasting conditions are as follows：It is calcined 3 hours in 600 DEG C of air；
* the condition of hydro-thermal process is as follows：650 DEG C of steam treatments 1 hour.
The property of the Y type molecular sieve of table 2
| 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 is accounted for is total pore volume, % | 72 | 78 | 75 | 80 |
| Non-framework aluminum accounts for total aluminium 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 is accounted for is total pore volume, % | 29 | 32 | 35 |
| Non-framework aluminum accounts for the total aluminium 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, compare surface
Product 400m2/ g, butt 70wt%）, 171.4 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into
Paste, extrusion, extrusion bar are dried 4 hours at 110 DEG C, are then calcined 4 hours at 550 DEG C, obtain carrier GDS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FC-1 is obtained, carrier and corresponding catalyst property are shown 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, compare surface
Product 400m2/ g, butt 70wt%）, 184.1 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into
Paste, extrusion, extrusion bar are dried 4 hours at 110 DEG C, are then calcined 4 hours at 550 DEG C, obtain carrier GDS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FC-2 is obtained, carrier and corresponding catalyst property are shown 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, compare surface
Product 400m2/ g, butt 70wt%）, 168.8 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into
Paste, extrusion, extrusion bar are dried 4 hours at 110 DEG C, are then calcined 4 hours at 550 DEG C, obtain carrier GDS-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FC-3 is obtained, carrier and corresponding catalyst property are shown 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, compare surface
Product 400m2/ g, butt 70wt%）, 190.4 grams of peptizing agents（4g nitric acid/100g peptizing agents）Mixed grind in roller is put into, is rolled into
Paste, extrusion, extrusion bar are dried 4 hours at 110 DEG C, are then calcined 4 hours at 550 DEG C, obtain carrier GDS-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FC-4 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 8 ~ 10
According to the method for embodiment 9, LYNS-2 is changed into DYNS-1, DYNS-2, DYNS-3 respectively, carrier DGDS- is made
1st, DGDS-2, DGDS-3 and catalyst DFC-1, DFC-2, DFC-3, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 12 ~ 15
This embodiment describes the Activity evaluation by catalyst FC-1, FC-2, FC-3 and FC-4 of the present invention.In fixation
Evaluated on bed hydroprocessing experimental rig, appreciation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700：1, volume during liquid
Air speed 2.0h-1, using catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 4, and evaluation result is listed in table 5.
Comparative example 9 ~ 11
This comparative example is described by comparative example catalyst DFC-1, DFC-2, DFC-3 of the present invention Activity evaluation.
Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700：1, during liquid
Volume space velocity 2.0h-1, using catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 4, and evaluation result is listed in table 5.
The physico-chemical property of the catalyst carrier of table 3 and catalyst
| Carrier forms and property | ||||
| Numbering | GDS-1 | GDS-2 | GDS-3 | GDS-4 |
| Y type molecular sieve, wt% | 20 | 40 | 15 | 50 |
| Aluminum 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 forms and property | ||||
| 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 forms and property | |||
| Numbering | DGDS-1 | DGDS-2 | DGDS-3 |
| Y type molecular sieve, wt% | 40 | 40 | 40 |
| Aluminum oxide, wt% | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 398 | 364 | 378 |
| Pore volume, mL/g | 0.56 | 0.61 | 0.59 |
| Catalyst forms and property | |||
| 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 |
The raw material oil nature of table 4
| Feedstock oil | MIP catalytic diesel oils |
| 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 |
| Sulphur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | <20.0 |
| C, wt% | 88.49 |
| H, wt% | 11.04 |
The catalyst performance comparative evaluation's result of table 5
| Catalyst | FC-1 | FC-2 | FC-3 | FC-4 |
| Feedstock oil | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils |
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 | 2.0 |
| React 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 property | ||||
| Naphtha | ||||
| Yield, wt% | 2.2 | 2.1 | 2.1 | 1.8 |
| Virtue is latent, 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 |
| Sulphur, 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 |
| Feedstock oil | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils |
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 |
| React 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 property | |||
| Naphtha | |||
| Yield, wt% | 3.8 | 3.9 | 4.6 |
| Virtue is latent, 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 |
| Sulphur, μ g/g | 15 | 17 | 19 |
| Liquid is received, wt% | 96.8 | 95.6 | 93.2 |
It can be seen from the evaluation result of table 5 under identical process conditions, during using catalyst of the present invention, diesel oil is received
Rate and product quality are superior to reference catalyst.
Claims (26)
1. a kind of catalyst for hydro-upgrading, comprising hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y and oxygen
Change aluminium, the property of wherein Modified Zeolite Y is as follows：Average grain diameter is 2.0 ~ 5.0 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 2nm ~ 6nm hole
For the 60% ~ 90% of total pore volume；Described carrier, on the basis of the weight of carrier, including Modified Zeolite Y content for 5% ~
40%, the content of aluminum oxide is 60% ~ 95%.
2. according to the catalyst described in claim 1, it is characterised in that：The average grain diameter of the Modified Zeolite Y is
2.0~4.5μm。
3. according to the catalyst described in claim 2, it is characterised in that：The average grain diameter of the Modified Zeolite Y is
3.0~4.5μm。
4. according to the catalyst described in claim 1, it is characterised in that：The bore dia of the Modified Zeolite Y is 2nm ~ 6nm
Hole shared by pore volume be total pore volume 70% ~ 85%.
5. according to the catalyst described in claim 1, it is characterised in that：In the Modified Zeolite Y, non-framework aluminum accounts for total aluminium
0.1% ~ 1.0%.
6. according to the catalyst described in claim 5, it is characterised in that：In the Modified Zeolite Y, non-framework aluminum accounts for total aluminium
0.1% ~ 0.5%.
7. according to the catalyst described in claim 1, it is characterised in that：The pore volume of the Modified Zeolite Y is 0.35cm3/g~
0.50cm3/ g, specific surface area 750m2/g~950m2/g。
8. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid 0.5 of the Modified Zeolite Y ~
1.0mmol/g。
9. according to the catalyst described in claim 1, it is characterised in that：In the Modified Zeolite Y, Na2O weight content
For below 0.15wt%.
10. according to the catalyst described in claim 1, it is characterised in that：Described carrier, on the basis of the weight of carrier, bag
The content for including Modified Zeolite Y is 10% ~ 35%, and the content of aluminum oxide is 65% ~ 90%.
11. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are using vib and the
The metal of VIII, vib metals be Mu He ∕ or tungsten, group VIII metal is Gu He ∕ or nickel, using the weight of catalyst as
Benchmark, using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide is vib metals
4.0%~8.0%。
12. the preparation method of any catalyst of claim 1 ~ 11, include preparation and the load hydrogenation active metals of carrier
The preparation process of component, wherein carrier is as follows：Modified Zeolite Y, aluminum oxide are mixed, shaping, then dries and is calcined, system
Into the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprise the following steps：
（1）The preparation of big crystal grain NaY type molecular sieves；
（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH4NaY；
（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Hydrothermal conditions：Gauge pressure is 0.05 ~ 0.25MPa, temperature
Spend for 400 ~ 550 DEG C, processing time is 0.5 ~ 5.0 hour；
（4）With（NH4）2SiF6The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, is made and is modified
Y type molecular sieve.
13. in accordance with the method for claim 12, it is characterised in that：Step（1）The property of described big crystal grain NaY type molecular sieves
Matter is as follows：
Average grain diameter is 2.0 ~ 5.0 μm, and bore dia is that the pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume,
Relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.
14. in accordance with the method for claim 13, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves
Grain average diameter is 2.0 ~ 4.5 μm.
15. in accordance with the method for claim 14, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves
Grain average diameter is 3.0 ~ 4.5 μm.
16. in accordance with the method for claim 13, it is characterised in that：Step（1）The hole of described big crystal grain NaY type molecular sieves
Pore volume shared by a diameter of 1nm ~ 10nm hole accounts for the 70% ~ 85% of total pore volume.
17. in accordance with the method for claim 12, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows：
SiO2/Al2O3Mol ratio 3.5 ~ 6.5.
18. in accordance with the method for claim 17, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows：
SiO2/Al2O3Mol ratio is 4.0 ~ 6.0.
19. according to the method described in claim 12,13 or 17, it is characterised in that：Step（1）The property of the NaY types molecular sieve
Matter is as follows：Specific surface area is 800m2/g~1000m2/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m2/g
~100m2/g。
20. in accordance with the method for claim 12, it is characterised in that：Step（2）The big crystal grain NH of preparation4Sodium oxide molybdena in NaY
Weight content is 2.5% ~ 5.0%.
21. in accordance with the method for claim 12, it is characterised in that：Step（3）Hydrothermal conditions be gauge pressure be 0.1 ~
0.2MPa, temperature are 450 ~ 550 DEG C, and processing time is 1.0 ~ 3.0 hours.
22. in accordance with the method for claim 12, it is characterised in that：Step（4）It is by step（3）In obtained material with
（NH4）2SiF6The aqueous solution contact, solvent and solute weight ratio 3：1~8：1, temperature is 70 ~ 90 DEG C, is added by every 100 grams of Y molecular sieves
10 ~ 35 grams（NH4）2SiF6Amount add（NH4）2SiF6The aqueous solution, add 3 ~ 30 grams per 100gY types molecular sieve per hour
（NH4）2SiF6, add（NH4）2SiF6The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour.
23. in accordance with the method for claim 12, it is characterised in that：Step（1）The preparation side of middle big crystal grain NaY type molecular sieves
Method, comprise the following steps：
I, at a temperature of 20 DEG C ~ 40 DEG C, according to Na2O：Al2O3：SiO2：H2O=10~15：1：10~20：500 ~ 600 feed intake mole
Than waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring and is well mixed, afterwards, sequentially adds sulphur
Sour aluminum solutions and low alkali aluminium acid sodium solution, stir at the temperature disclosed above；Then constant temperature aging in confined conditions, is obtained
Gel；
II, hydrothermal crystallizing 12 ~ 24 hours by the gel that step I is obtained at 80 DEG C ~ 120 DEG C and under conditions of stirring, are passed through after crystallization
Filtering, washing, dry, obtain big crystal grain NaY type molecular sieves.
24. in accordance with the method for claim 23, it is characterised in that：In step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali
The ratio of the addition of sodium metaaluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.
25. in accordance with the method for claim 23, it is characterised in that：In step I, in described high alkali deflection aluminium acid sodium solution
Na2O 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；Described water
SiO in glass2Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.
26. in accordance with the method for claim 23, it is characterised in that：In step II, under agitation, by temperature with 2 ~ 4
DEG C/minute it is warming up to crystallization temperature i.e. 80 DEG C ~ 120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410711587.7A CN105709799B (en) | 2014-12-01 | 2014-12-01 | A kind of catalyst for hydro-upgrading and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410711587.7A CN105709799B (en) | 2014-12-01 | 2014-12-01 | A kind of catalyst for hydro-upgrading and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105709799A CN105709799A (en) | 2016-06-29 |
| CN105709799B true CN105709799B (en) | 2018-04-10 |
Family
ID=56145657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410711587.7A Active CN105709799B (en) | 2014-12-01 | 2014-12-01 | A kind of catalyst for hydro-upgrading and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105709799B (en) |
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 |
-
2014
- 2014-12-01 CN CN201410711587.7A patent/CN105709799B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105709799A (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102049283A (en) | Hydro-cracking catalyst and preparation method thereof | |
| CN105621449B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| CN107344721B (en) | A kind of Modified Zeolite Y and its preparation method and application | |
| CN104588076B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN104588078B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN105713657B (en) | Hydrocracking method | |
| CN107286987B (en) | A kind of group technology handling poor ignition quality fuel | |
| CN104826652B (en) | The method for preparing hydrocracking catalyst | |
| CN104826667B (en) | The method for preparing carrier of hydrocracking catalyst | |
| CN104588122B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN105709845B (en) | Carrier of hydrocracking catalyst and preparation method thereof | |
| CN106140281B (en) | A kind of preparation method of middle oil type hydrocracking catalyst | |
| CN106140319B (en) | A kind of preparation method of middle oil type hydrocracking catalyst carrier | |
| CN105709799B (en) | A kind of catalyst for hydro-upgrading and preparation method thereof | |
| CN105709848B (en) | A kind of carrier of hydrocracking catalyst and preparation method thereof | |
| CN105709797B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN105709846B (en) | A kind of catalyst for hydro-upgrading carrier and preparation method thereof | |
| CN107344116B (en) | Hydrocracking catalyst and its preparation method and application | |
| CN106947521B (en) | A kind of processing method of poor ignition quality fuel | |
| CN105709798B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN107286988B (en) | A kind of process handling poor ignition quality fuel | |
| CN107345153B (en) | A kind of method for hydrogen cracking producing low-coagulation diesel oil | |
| CN105709819B (en) | Hydrocracking catalyst and its preparation method | |
| CN105618125B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN105709847B (en) | A kind of carrier of hydrocracking catalyst and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |