CN105709845B - Carrier of hydrocracking catalyst and preparation method thereof - Google Patents
Carrier of hydrocracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of carrier of hydrocracking catalyst and preparation method thereof.The Modified Zeolite Y that the catalyst carrier is concentrated using a kind of big crystal grain, high silicon, effective pore sife distribution is as predominant cracking component, second Cracking Component is used as using amorphous silica-alumina, hydrocracking catalyst prepared therefrom, with higher activity and middle distillates oil selectivity, and the quality of produced intermediate oil is good.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, particularly hydrocracking process production are high
Carrier of hydrocracking catalyst of quality intermediate oil and preparation method thereof.
Background technology
The recovery and development of World Economics, make countries in the world refined products market to high-quality middle cut oil product（That is aviation
The power fuel of industry：Jet fuel, and the major impetus fuel of sea-lanes of communication industry：Diesel oil）Demand be continuously increased always.
At the same time, the reserves of World's Oil and Gas Resources are reduced year by year, and quality is deteriorated year by year, and the requirement to finished product oil quality is got over
Come higher.Therefore, hydrocracking technology turns into the optimal oil refining skill for producing high-quality intermediate oil with its exclusive technical advantage
Art.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, i.e., simultaneously
Contain acidic components and hydrogenation active component.It is wherein acid mainly by various molecular sieves and/or to form the heat resistant inorganic of carrier
Oxide provides, and the property of acidic components has very heavy to the activity of hydrocracking catalyst and the selectivity of intermediate oil
The influence wanted.Hydrogenation active component is selected generally from metal, metal oxide and/or the gold of VI B races and VIII race in the periodic table of elements
Belong to sulfide.The key component that cracking is played in hydrocracking catalyst is mostly molecular sieve, and the quality of molecular sieve performance will be straight
Connecing influences catalyst performance and oil quality.
US4401556 discloses a kind of hydrocracking catalyst for being used to produce intermediate oil.The catalyst is to pass through
The Y type molecular sieve for crossing dealuminzation is cracking active component, and its silica alumina ratio is 4.5~35,2.420~2.445nm of cell parameter,
Specific surface area is not less than 350m2/g.When the catalyst is using VGO as raw material, its activity is poor, and middle distillates oil selectivity is not also high.
US4894142 discloses a kind of hydrocracking catalyst, is mainly used in the technique of voluminous intermediate oil.This is urged
Agent contains amorphous silica-alumina and a kind of Y type molecular sieve of Low acid, is to handle raw material point at high temperature the characteristics of the molecular sieve
Son sieve, including 680~780 DEG C of hydro-thermal process or the dry type for the being passed through inert gas heat treatment higher than 700 DEG C.Due to the molecule
Acidity is sieved than relatively low, makes the activity of catalyst excessively relatively low, this requires to improve hydrocracking reaction temperature, the hot tearing of molecular sieve
Change trend strengthens, but inhibits hydrogenation reaction, the middle distillates oil selectivity of catalyst is improved unobvious, product quality is also by bad
Influence.
The Y type molecular sieve that the above method uses is essentially all in USP 3639099 and USP using GRACE companies of the U.S.
Common Y type molecular sieve prepared by the directing agent method proposed in 4166099, its crystal grain are generally 1 μm or so, big in each dimension
It there are about the structure cell of 400 or so.The Y type molecular sieve original powder bore dia for the typical die size the being conventionally synthesized hole less than 1nm point
Cloth ratio is 15% ~ 20%, and bore dia is 45% ~ 50% in 1nm ~ 10nm pore size distribution ratio, and bore dia is in the hole more than 10nm point
Cloth ratio is 30% ~ 40%.For macromolecular cracking reaction, be adapted to the preferable pore diameter range of raw material reaction and product diffusion be 1nm ~
10nm, although Y type molecular sieve can be also distributed by follow-up modification appropriateness modulation ideal pore diameter range, original molecular sieve
Pore-size distribution directly determine the pore diameter range distribution of successive modified molecular sieve, and reaming can influence the skeleton knot 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.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and its system
Preparation Method.The modification Y types point that the carrier of hydrocracking catalyst is more concentrated using a kind of big crystal grain, high silicon, effective pore sife distribution
Son sieve is used as predominant cracking component, is cooperateed with by the second Cracking Component, Modified Zeolite Y of amorphous silica-alumina with amorphous silica-alumina
Effect, the catalyst prepared by carrier of the present invention have intermediate oil high income and the excellent feature of product quality.
The carrier of hydrocracking catalyst of the present invention, comprising Modified Zeolite Y and amorphous silica-alumina, wherein modified Y types
The property of molecular sieve is as follows：Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm,
Relative crystallinity 110% ~ 150%, SiO2/Al2O3Mol ratio is 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, is preferably
2.427 ~ 2.434nm, bore dia are that the pore volume shared by 3nm ~ 7nm hole is the 70% ~ 95% of total pore volume, preferably 75% ~ 90%.
In Modified Zeolite Y of the present invention, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminium, preferably 0.1% ~ 0.5%.
In carrier of hydrocracking catalyst of the present invention, the pore volume of described Modified Zeolite Y is 0.35cm3/g~
0.50cm3/ g, specific surface area 800m2/g~980m2/g。
In carrier of hydrocracking catalyst of the present invention, infrared 0.1 ~ 0.5mmol/ of total acid of described Modified Zeolite Y
g。
In carrier of hydrocracking catalyst of the present invention, in described Modified Zeolite Y, Na2O weight content is
Below 0.15wt%.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of Modified Zeolite Y for 5% ~
25%, preferably 5% ~ 20%, the content of amorphous silica-alumina is 75% ~ 95%, preferably 80% ~ 95%.
The specific surface area of carrier of hydrocracking catalyst of the present invention is 300 ~ 500m2/ g, pore volume are 0.45 ~ 0.75mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention, including：Modified Zeolite Y, amorphous silica-alumina are mixed
Close, shaping, then dry and be calcined, the preparation method of catalyst carrier, wherein Modified Zeolite Y, including following step is made
Suddenly：
（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；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~
0.50MPa, temperature are 550 ~ 700 DEG C, and 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
Modified Zeolite Y.
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：It is 800m than surface2/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：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, temperature 550 ~
700 DEG C, preferably 600 ~ 700 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：Step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130
℃；Added into slurry（NH4）2SiF6The aqueous solution, 35 ~ 80 grams are added according to every 100 grams of Y molecular sieves（NH4）2SiF6Amount add
Enter（NH4）2SiF6The aqueous solution, 3 ~ 30 grams can be added per 100gY types molecular sieve per hour（NH4）2SiF6, add（NH4）2SiF6Water
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 carrier of the present invention is using the Y type molecular sieve that big crystal grain, high silicon, effective pore sife distribution are more concentrated as main
Cracking Component.Because the larger crystal molecular sieve not only has larger crystal grain so that structure cell quantity increases in each dimension
1000 ~ 2000, be advantageous to macromolecular and cracked, but also with more preferably pore size distribution range, can efficiently control
The cracking degree of reactant, and be advantageous to product and be diffused in duct, can relative increase activity so in cracking reaction
Center, and heavy oil macromolecular can be made to carry out the cracking reaction of suitable degree, the cracking capability of heavy oil was both improved, while reduce Jiao
Charcoal yield, catalyst can show good cracking activity and product selectivity.The carrier of hydrocracking catalyst is particularly suitable
As middle oily hydrocracking catalyst, hydrocracking catalyst prepared therefrom be used for produce high-quality intermediate oil, have compared with
High catalyst activity and selectivity.
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
Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst carrier of the present invention, by document
It is prepared by middle conventional method.SiO in obtained amorphous silica-alumina2Weight content be 30%~70%, preferably 35%~65%,
The pore volume of amorphous silica-alumina is 0.6~1.1ml/g, preferably 0.8~1.0ml/g, and specific surface area is 300~500m2/ g, preferably
For 350~500m2/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 process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation
In method, Na in high alkali deflection aluminium acid sodium solution2O content is 260 ~ 320g/L, Al2O3Content is 30 ~ 50g/L, can use routine side
Method is prepared.Na in low alkali aluminium acid sodium solution2O content is 100 ~ 130g/L, Al2O3Content is 60 ~ 90g/L, can use routine side
Method is prepared.Al in aluminum sulfate solution2O3Content be 80 ~ 100g/L.SiO in waterglass2Content be 200 ~ 300g/L, modulus
For 2.8 ~ 3.5.
In the preparation process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation
Method, specifically comprise 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 1.0 ~ 2.0 hours；
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.
In the preparation process of Modified Zeolite Y used in the present invention, step（2）Can using ammonium concentration as 0.1mol/L ~
1.0mol/L ammonium salt solution, one or more of the described ammonium salt in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate,
It is 50 ~ 100 DEG C in temperature, solvent and solute weight ratio 8：1~15：Under conditions of 1, constant temperature processing big crystal grain NaY, the time is 0.5 ~ 1.5
Hour, it is filtered, then repeat ammonium exchange under these conditions, obtained product is filtered, stand-by after drying.Wherein
The weight content for seeking sodium oxide molybdena in the larger crystal molecular sieve after controlling ammonium exchange is 2.5% ~ 5.0%.
In the preparation process of Modified Zeolite Y used in the present invention, step（3）It is by step（2）In obtained product water
It is heat-treated and obtains.With saturated steam processing step（2）In obtained molecular sieve, add step in pipe type water heat-treatment furnace
（2）In obtained molecular sieve, treatment conditions：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, 550 ~ 700 DEG C of temperature are excellent
Elect 600 ~ 700 DEG C as, 0.5 ~ 5 hour processing time, preferably 1 ~ 3 hour.
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：Step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130
℃；Added into slurry（NH4）2SiF6The aqueous solution, 35 ~ 80 grams are added according to every 100 grams of Y molecular sieves（NH4）2SiF6Amount add
Enter（NH4）2SiF6The aqueous solution, 3 ~ 30 grams can be added per 100gY types molecular sieve per hour（NH4）2SiF6, add（NH4）2SiF6Water
Solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.
Stirring described in the inventive method is using conventional stirring means, typically using mechanical agitation.
Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：Modified Zeolite Y, amorphous silica-alumina are mixed
Close, extruded moulding, then dry and be calcined, be prepared into carrier；It is small that drying can dry 3~6 at a temperature of 80 DEG C to 150 DEG C
When, roasting is calcined 2.5~6.0 hours at 500 DEG C~600 DEG C.
The following examples are used for the preparation method that carrier of the present invention is described in more detail, but the scope of the present invention not only limits
In the scope of these embodiments.
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, product 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, after being cooled to room temperature, add
Enter 22.5g sodium metaaluminates and high alkali deflection aluminium acid sodium solution is made.Then high alkali deflection aluminium acid sodium solution is added in 525g waterglass, is mixed
Aging 24 hours at room temperature after closing uniformly, it is 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 2.5~5.0wt%, 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 590 DEG C, in gauge pressure
Handle 2.0 hours under 0.30MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is
100 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 386mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry
The aqueous solution, 38.6 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member
LYNS-1, property are listed 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 650 DEG C, in gauge pressure 0.4MPa
Lower processing 1.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 120 DEG C, is stirred
Mix rotating speed is 300rpm.Within the time of 2 hours, 676mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether
67.6 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-2, property
It 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 600 DEG C, in gauge pressure
Handle 3.0 hours under 0.45MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is
110 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 435mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry
The aqueous solution, 43.5 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member
LYNS-3, property are listed 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 680 DEG C, in gauge pressure 0.3MPa
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 100 DEG C, is stirred
Mix rotating speed is 300rpm.Within the time of 2 hours, 723mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether
72.3 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-4, property
It is listed 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, DYNS-3, property are listed in table 2.
The property of the NaY type molecular sieves of table 1
Continued 1
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
Continued 2
| Production code member | DYNS-1 | DYNS-2 | DYNS-3 |
| Specific surface area, m2/g | 569 | 585 | 546 |
| Pore volume, cm3/g | 0.37 | 0.36 | 0.35 |
| Lattice constant, nm | 2.429 | 2.431 | 2.430 |
| Relative crystallinity, % | 79 | 81 | 59 |
| Average crystallite size, μm | 0.95 | 0.95 | 1.10 |
| SiO2/Al2O3Mol ratio | 23.5 | 16.9 | 22.4 |
| The pore volume that bore dia 3nm ~ 7nm is accounted for is total pore volume, % | 36 | 33 | 32 |
| Non-framework aluminum accounts for total aluminium content, % | 1.8 | 2.1 | 4.5 |
| Infrared total acid content, mmol/g | 0.29 | 0.38 | 0.77 |
| Na2O, wt% | 0.16 | 0.18 | 0.22 |
Embodiment 8
By 13.3 grams of LYNS-1 molecular sieves（Butt 90wt%）, 268.6 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 162.5 grams of peptizing agents（4g nitric acid/100g peptizing agents）It is put into and rolls
Mixed grind in machine, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier
ZYS-1。
Embodiment 9
By 33.3 grams of LYNS-2 molecular sieves（Butt 90wt%）, 242.9 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume
0.85ml/g, specific surface area 370m2/ g, butt 70wt%）, 168.2 grams of peptizing agents（4g nitric acid/100g peptizing agents）It is put into and rolls
Mixed grind in machine, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier
ZYS-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 HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Comparative example 8 ~ 10
As described in Example 9, change LYNS-2 into DYNS-1, DYNS-2, DYNS-3 respectively, be made carrier DZYS-1,
DZYS-2, DZYS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.
Embodiment 10
This embodiment describes the catalyst HC-2 Activity evaluations prepared by carrier of the present invention.In fixed bed hydrogenation
Evaluated on experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1. during liquid
0h-1, using VGO as feedstock oil, feedstock property is listed in table 4, and evaluation result is listed in table 5.
Comparative example 11 ~ 13
This comparative example describes catalyst DHC-1, DHC-2 and DHC-3 activity prepared by comparative example carrier of the present invention
Evaluation result.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio
1200, volume space velocity 1.0h during liquid-1, using VGO as feedstock oil, feedstock property is listed in table 4, and evaluation result is listed in table 5.
The composition of the catalyst carrier of table 3 and catalyst
| Carrier forms and property | |||||
| Numbering | ZYS-1 | ZYS-2 | DZYS-1 | DZYS-2 | DZYS-3 |
| Y type molecular sieve, wt% | 6 | 15 | 15 | 15 | 15 |
| Amorphous silica-alumina, wt% | 94 | 85 | 85 | 85 | 85 |
| Specific surface area, m2/g | 448 | 469 | 401 | 388 | 356 |
| Pore volume, mL/g | 0.65 | 0.60 | 0.51 | 0.50 | 0.49 |
| Catalyst forms and property | |||||
| Numbering | HC-1 | HC-2 | DHC-1 | DHC-2 | DHC-3 |
| WO3, wt% | 23.47 | 23.65 | 23.78 | 23.75 | 23.67 |
| NiO, wt% | 6.05 | 5.96 | 6.01 | 5.98 | 5.96 |
The feedstock oil main character of table 4
| Feedstock oil | Vacuum distillate |
| Density（20℃）, kg/m3 | 920.6 |
| Boiling range, DEG C | |
| IBP/10% | 328/413 |
| 30%/50% | 450/471 |
| 70%/90% | 493/522 |
| 95%/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
The catalyst performance comparative evaluation's result of table 5
| Catalyst | HC-2 | DHC-1 | DHC-2 | DHC-3 |
| Feedstock oil | VGO | VGO | VGO | VGO |
| Volume space velocity during liquid, h-1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 1200:1 | 1200:1 | 1200:1 | 1200:1 |
| React stagnation pressure, MPa | 14.7 | 14.7 | 14.7 | 14.7 |
| Reaction temperature, DEG C | 390 | 396 | 399 | 403 |
| Product yield and property | ||||
| Heavy naphtha | ||||
| Yield, wt% | 8.8 | 9.9 | 10.3 | 10.5 |
| Virtue is latent, wt% | 62.7 | 61.6 | 58.6 | 57.3 |
| Jet fuel | ||||
| Yield, wt% | 23.1 | 22.6 | 22.1 | 20.6 |
| Smoke point, mm | 23 | 22 | 21 | 21 |
| Aromatic hydrocarbons, v% | 10.0 | 12.5 | 13.6 | 14.2 |
| Diesel oil | ||||
| Yield, wt% | 35.5 | 33.2 | 32.1 | 31.6 |
| Cetane number | 62.0 | 60.1 | 59.6 | 60.3 |
| Tail oil | ||||
| Yield, wt% | 28.9 | 28.0 | 27.9 | 27.6 |
| BMCI values | 9.0 | 10.8 | 11.5 | 12.0 |
| Chemical hydrogen consumption, wt% | 2.18 | 2.24 | 2.32 | 2.36 |
| Liquid is received, wt% | 98.4 | 97.6 | 96.5 | 95.9 |
It can be seen from the evaluation result of table 5 under identical process conditions, using carrier prepared catalyst of the present invention
When, midbarrel oil yield and product quality are superior to reference catalyst.
Claims (27)
1. a kind of carrier of hydrocracking catalyst, carrier includes Modified Zeolite Y and amorphous silica-alumina, wherein described modification
Y type molecular sieve, its property are as follows：Average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity 110% ~ 150%, SiO2/Al2O3Rub
You are than being 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, and bore dia is that the pore volume shared by 3nm ~ 7nm hole is total pore volume
70%~95%。
2. according to the catalyst carrier described in claim 1, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight
Footpath is 2.0 ~ 4.5 μm.
3. according to the catalyst carrier described in claim 2, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight
Footpath is 3.0 ~ 4.5 μm.
4. according to the catalyst carrier described in claim 1, it is characterised in that：The bore dia of the Modified Zeolite Y is 3nm
Pore volume shared by ~ 7nm hole is the 75% ~ 90% of total pore volume.
5. according to the catalyst carrier described in claim 1, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always
The 0.1% ~ 1.0% of aluminium.
6. according to the catalyst carrier described in claim 5, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always
The 0.1% ~ 0.5% of aluminium.
7. according to the catalyst carrier 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 800m2/g~980m2/g。
8. according to the catalyst carrier described in claim 1, it is characterised in that：The infrared total acid 0.1 of the Modified Zeolite Y
~0.5mmol/g。
9. according to the catalyst carrier described in claim 1, it is characterised in that：In the Modified Zeolite Y, Na2O weight
Content is below 0.15wt%.
10. according to the catalyst carrier described in claim 1, it is characterised in that：Described carrier, in terms of the weight of carrier, bag
The content for including Modified Zeolite Y is 5%~25%, and the content of amorphous silica-alumina is 75%~95%.
11. according to the catalyst carrier described in claim 10, it is characterised in that：Described carrier, in terms of the weight of carrier, bag
The content for including Modified Zeolite Y is 5%~20%, and the content of amorphous silica-alumina is 80%~95%.
12. according to the catalyst carrier described in claim 1, it is characterised in that：SiO in amorphous silica-alumina used2Weight contain
Measure as 30%~70%, the pore volume of amorphous silica-alumina is 0.6~1.1mL/g, and specific surface area is 300~500m2/g。
13. the preparation method of any catalyst carrier of claim 1 ~ 12, including：By Modified Zeolite Y and amorphous
Sial mixes, and shaping, then dries and is calcined, and the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, including
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；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~
0.50MPa, temperature are 550 ~ 700 DEG C, and 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, and Y types are made
Molecular sieve.
14. in accordance with the method for claim 13, 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.
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 2.0 ~ 4.5 μm.
16. in accordance with the method for claim 15, 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.
17. in accordance with the method for claim 14, 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.
18. in accordance with the method for claim 13, 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.
19. in accordance with the method for claim 18, 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.
20. according to the method described in claim 13,14 or 18, it is characterised in that：Step（1）The property of the NaY types molecular sieve
Matter is as follows：It is 800m than surface2/g~1000m2/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m2/g~
100m2/g。
21. in accordance with the method for claim 13, 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%.
22. in accordance with the method for claim 13, it is characterised in that：Step（3）Hydrothermal conditions it is as follows：Gauge pressure is
0.30 ~ 0.50MPa, temperature are 600 ~ 700 DEG C, and processing time is 1.0 ~ 3.0 hours.
23. in accordance with the method for claim 13, 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 8：1~15：1, temperature is 95 ~ 130 DEG C, is added by every 100 grams of Y molecular sieves
Enter 35 ~ 80 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.
24. in accordance with the method for claim 13, 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.
25. in accordance with the method for claim 24, 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）.
26. in accordance with the method for claim 24, 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.
27. in accordance with the method for claim 24, 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.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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