CN105709847B - A kind of carrier of hydrocracking catalyst and its preparation method - Google Patents
A kind of carrier of hydrocracking catalyst and its preparation method Download PDFInfo
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Abstract
The invention discloses a kind of carrier of hydrocracking catalyst and its preparation method.The Y type molecular sieve that carrier of hydrocracking catalyst of the present invention is concentrated using a kind of big crystal grain, effective pore sife distribution, suitable for the hydrocracking catalyst for the heavy naphtha that raises productivity and improves the quality, has higher catalytic activity and selectivity as acidic components.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, particularly a kind of voluminous catalytic reforming is former
Material（Heavy naphtha）Carrier of hydrocracking catalyst and preparation method thereof.
Background technology
With developing rapidly for World Economics, in the present and the future's longer one period market to all kinds of industrial chemicals especially
Be aromatic hydrocarbons raw material demand by sustainable growth, the catalytic reforming technology as production aromatic hydrocarbons raw material is quickly grown, and this makes
Obtaining can also dramatically increase as the demand of the heavy naphtha of catalytic reforming raw material.As heavy oil lighting Main Means it
One, hydrocracking technology is rationally to utilize limited petroleum resources, the optimum oil Refining Technologies of the heavy naphtha that raises productivity and improves the quality.Hydrogenation splits
Change the core that catalyst is hydrocracking technology, this requires to develop the stronger hydrocracking catalyst of specific aim to adapt to city
The demand of field.
Carrier is the important component of catalyst, not only provides scattered place, while carrier sheet for metal active constituent
Body also assists in reaction, is cooperateed with together with other active components and completes whole catalytic reaction.Existing catalyst carrier for hydrgenating typically contains
Molecular sieve, aluminum oxide, and other refractory oxides, it is generally used for heavy oil hydrocracking, distillate hydrogenation removing impurities matter, poor quality
The processes such as diesel oil hydrogenation modification.
US5670590 discloses a kind of hydrocracking catalyst, it is therefore intended that voluminous naphtha cut, is characterized in using
A kind of USY molecular sieve.The USY molecular sieve is the crystalline substance as obtained from NaY originals powder by the exchange of ammonium nitrate twice and double roasting
Born of the same parents 2.438~2.442nm of parameter, sodium content is higher, typically in 1wt% or so.The catalyst activity is low, the selection of heavy naphtha
Property be not it is very high, hydrogen consumption it is also larger.
US4672048 discloses a kind of light oil type hydrogen cracking catalyst, using Y type molecular sieve, is characterized in that sial rubs
You are than being 11~15.Y type molecular sieve preparation method is that ammonium type Y molecular sieve is handled in acidic buffer solution with ammonium hexafluorosilicate,
Gained molecular sieve sodium content is typically low in 0.5wt% or so, catalyst activity.
Above-mentioned hydrocracking catalyst uses the modified Y molecular sieve of different performance, belongs to the Y molecules of conventional die size
Sieve, this is due to the influence of method of modifying and zeolite crystal size, causes the property of Y type molecular sieve different, so that catalysis
Very big difference be present in agent performance.
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 directing agent method proposed in USP 3639099 and USP 4166099, the crystal grain one of obtained common Y type molecular sieve
As be 1 μm or so, the structure cell of about 400 or so in each dimension.The Y type molecules for the typical die size being conventionally synthesized
It is 15% ~ 20% to sieve pore size distribution ratio of the former powder bore dia less than 1nm, bore dia 1nm ~ 10nm pore size distribution ratio for 45% ~
50%, bore dia is in the pore size distribution ratio more than 10nm 30% ~ 40%.For macromolecular cracking reaction, it is adapted to raw material reaction and production
The preferable pore diameter range of thing diffusion is 1nm ~ 10nm, although Y type molecular sieve can also be managed by follow-up modification appropriateness modulation
Think that pore diameter range is distributed, but the pore-size distribution of original molecular sieve directly determines the pore diameter range distribution of successive modified molecular sieve, and
And reaming can influence the skeleton structure of molecular sieve, and then influence the activity and stability of molecular sieve.
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 Y type molecular sieve conduct that carrier of hydrocracking catalyst of the present invention is concentrated using a kind of big crystal grain, effective pore sife distribution
Acidic components, suitable for the hydrocracking catalyst for the heavy naphtha that raises productivity and improves the quality, there is higher catalytic activity and selectivity.
The carrier of hydrocracking catalyst of the present invention, including Modified Zeolite Y and aluminum oxide, wherein modified Y type molecules
The property of 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, relatively
Crystallinity 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, preferably 12 ~ 45, and cell parameter is 2.436 ~ 2.450nm, hole
Pore volume shared by a diameter of 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 carrier of hydrocracking catalyst of the present invention is 500 ~ 650m2/ g, pore volume are 0.4 ~ 0.8mL/g.
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of Modified Zeolite Y for 45% ~
70%, preferably 50% ~ 70%, the content of aluminum oxide is 30% ~ 55%, preferably 30% ~ 50%.
The preparation method of carrier of hydrocracking catalyst of the present invention, including：Modified Zeolite Y, aluminum oxide are mixed, into
Type, then dry and be calcined, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, 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.
The Y type molecular sieve that catalyst carrier of the present invention is more concentrated using big crystal grain, effective pore sife distribution is as Cracking Component.
Because the larger crystal molecular sieve not only has larger crystal grain so that structure cell quantity increases to 1000 ~ 2000 in each dimension,
Be advantageous to macromolecular to be cracked, but also with more preferably pore size distribution range, the cracking of reactant can be efficiently controlled
Degree, and be advantageous to product and be diffused in duct, so in cracking reaction, can relative increase activated centre, and can make
Heavy oil macromolecular carries out the cracking reaction of suitable degree, has both improved the cracking capability of heavy oil, while reduces coke yield, is catalyzed
Agent can show good cracking activity and product selectivity.The hydrocracking catalyst is especially suitable for voluminous reformer feed
Hydrocracking process, there is higher 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
Aluminum oxide can include macroporous aluminium oxide and small porous aluminum oxide in carrier of hydrocracking catalyst of the present invention, and its is medium and small
Porous aluminum oxide is partly or entirely used as adhesive.On the basis of the percentage by weight of carrier：Macroporous aluminium oxide content be 20%~
50%, preferably 20%~40%, aperture alumina content are 5%~25%, preferably 10%~25%.
Macroporous aluminium oxide used in the present invention, its pore volume are 0.6~1.3mL/g, preferably 0.7~1.1mL/g, compare surface
Product is 300~450m2/g。
Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used
Aluminium pore volume is 0.3~0.5ml/g, and specific surface area is 200~400m2/g。
In 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.
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, 400 ~ 550 DEG C of temperature, preferably 450 ~ 550 DEG C, processing time 0.5 ~ 5 is small
When, preferably 1 ~ 3 hour.
Step in the inventive method（4）It is by step（3）In obtained product use（NH4）2SiF6The aqueous solution processing, 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.
Stirring described in the inventive method is using conventional stirring means, typically using mechanical agitation.
Detailed process prepared by carrier of hydrocracking catalyst 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 carried out 3.0 ~ 6.0 hours at a temperature of 80 DEG C ~ 150 DEG C, roasting be 500 DEG C ~ 600 DEG C be calcined 2.5 ~
6.0 hour.
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, 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, 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 2.5~5wt%, 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
| Production code member | LY-1 | LY-2 |
| Specific surface area, m2/g | 897 | 956 |
| Pore volume, cm3/g | 0.35 | 0.37 |
| External surface area, m2/g | 80 | 82 |
| Lattice constant, nm | 2.465 | 2.463 |
| Relative crystallinity, % | 118 | 128 |
| Average crystallite size, μm | 3.0 | 2.5 |
| SiO2/Al2O3Mol ratio | 5.68 | 5.32 |
| The pore volume that bore dia 1nm ~ 10nm is accounted for accounts for total pore volume, % | 78 | 87 |
| Relative crystallinity * after roasting, % | 95 | 92 |
| Relative crystallinity * after hydro-thermal process, % | 108 | 115 |
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 | 72 |
| Average crystallite size, μm | 0.95 | 0.95 | 1.10 |
| 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 | 4.3 |
| Infrared total acid content, mmol/g | 1.02 | 0.87 | 0.76 |
| Na2O, wt% | 0.16 | 0.18 | 0.20 |
Embodiment 8
By 111.0 grams of LYNS-1 molecular sieves（Butt 90wt%）, 100.0 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, compare surface
Product 400m2/ g, butt 70wt%）, 100.0 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）Put
Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, obtain carrier FHS-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, obtain catalyst FHC-1, carrier composition and property and corresponding catalyst composition is shown in Table 3.
Embodiment 9
By 144.4 grams of LYNS-2 molecular sieves（Butt 90wt%）, 57.1 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, compare surface
Product 400m2/ g, butt 70wt%）, 100.0 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）Put
Enter mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier FHS-2 is obtained, composition and property are listed in table 3.
Comparative example 8 ~ 10
According to the method for embodiment 8, change LYNS-1 into DYNS-1, DYNS-2, DYNS-3 respectively, be made carrier DHS-1,
DHS-2, DHS-3 and catalyst DHC-1, DHC-2, DHC-3, carrier composition and property and corresponding catalyst composition are shown in Table 3.
Embodiment 10
This embodiment describes the catalyst FHC-1 Activity evaluations prepared by carrier of the present invention.In fixed bed plus
Evaluated on hydrogen experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200:1, volume space velocity during liquid
1.60h-1；Feedstock oil is vacuum distillate（VGO）, property is listed in table 4, and evaluation result is listed in table 5.
Comparative example 9 ~ 11
This comparative example describes catalyst DHC-1, DHC-2, DHC-3 for being prepared by comparative example carrier of the present invention activity
Evaluation result.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio
1200:1, volume space velocity 1.60h during liquid-1；Feedstock oil is vacuum distillate（VGO）, raw material oil nature is listed in table 4, evaluation result
It is listed in table 5.
The composition of the catalyst carrier of table 3 and catalyst
| Carrier forms and property | |||||
| Numbering | FHS-1 | FHS-2 | DHS-1 | DHS-2 | DHS-3 |
| Modified Zeolite Y, wt% | 50.0 | 65.0 | 50.0 | 50.0 | 50.0 |
| Macroporous aluminium oxide, wt% | 35.0 | 20.0 | 35.0 | 35.0 | 35.0 |
| Adhesive, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.66 | 0.61 | 0.48 | 0.46 | 0.44 |
| Specific surface area, m2/g | 589 | 649 | 539 | 499 | 456 |
| Catalyst forms | |||||
| Numbering | FHC-1 | FHC-2 | DHC-1 | DHC-2 | DHC-3 |
| WO3, wt% | 22.46 | 22.51 | 22.42 | 22.50 | 22.48 |
| NiO, wt% | 5.96 | 6.00 | 6.02 | 6.01 | 5.98 |
The feedstock oil main character of table 4
| Feedstock oil | Vacuum distillate |
| Density（20℃）, kg/m3 | 910.6 |
| 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 COMPARATIVE CATALYST's evaluation result of table 5
| Catalyst | FHC-1 | DHC-1 | DHC-2 | DHC-3 |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Volume space velocity during liquid, h-1 | 1.60 | 1.60 | 1.60 | 1.60 |
| React stagnation pressure, MPa | 14.7 | 14.7 | 14.7 | 14.7 |
| Hydrogen to oil volume ratio | 1200:1 | 1200:1 | 1200:1 | 1200:1 |
| Reaction temperature, DEG C | 356 | 365 | 367 | 370 |
| Product yield and property | ||||
| Heavy naphtha | ||||
| Yield, wt% | 42.0 | 40.1 | 41.2 | 38.6 |
| Virtue is latent, wt% | 58.1 | 56.2 | 55.4 | 54.6 |
| Jet fuel | ||||
| Yield, wt% | 20.1 | 19.4 | 20.0 | 19.7 |
| Smoke point, mm | 28 | 27 | 25 | 24 |
| Aromatic hydrocarbons, v% | 5.1 | 6.2 | 6.6 | 8.0 |
| Diesel oil | ||||
| Yield, wt% | 10.3 | 9.3 | 8.6 | 12.6 |
| Cetane number | 64.6 | 62.8 | 60.3 | 60.5 |
| Tail oil | ||||
| Yield, wt% | 18.2 | 18.9 | 18.6 | 18.9 |
| BMCI values | 9.1 | 11.20 | 12.3 | 11.9 |
| Chemical hydrogen consumption, wt% | 2.68 | 2.88 | 2.90 | 2.89 |
| Liquid is received, wt% | 95.2 | 94.1 | 93.6 | 94.2 |
It can be seen from the evaluation result of table 5 under identical process conditions, prepared by catalyst carrier of the present invention
Hydrocracking catalyst, the yield of heavy naphtha, quality etc. is superior to reference catalyst.
Claims (26)
- A kind of 1. property of carrier of hydrocracking catalyst, including Modified Zeolite Y and aluminum oxide, wherein Modified Zeolite Y Matter is as follows：Average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity 110% ~ 150%, SiO2/Al2O3Mol ratio is 10 ~ 50, brilliant Born of the same parents' 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；Described urges Agent carrier, in terms of the weight of carrier, including the content of Modified Zeolite Y is 45% ~ 70%, the content of aluminum oxide for 30% ~ 55%。
- 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 2nm Pore volume shared by ~ 6nm hole is the 70% ~ 85% of total pore volume.
- 5. according to the catalyst carrier described in claim 1, it is characterised in that：In the Modified Zeolite Y, non-framework aluminum accounts for The 0.1% ~ 1.0% of total aluminium.
- 6. according to the catalyst carrier described in claim 5, it is characterised in that：In the Modified Zeolite Y, non-framework aluminum accounts for The 0.1% ~ 0.5% of total 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 750m2/g~950m2/g。
- 8. according to the catalyst carrier 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 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 50% ~ 70%, and the content of aluminum oxide is 30% ~ 50%.
- 11. the preparation method of any catalyst carrier of claim 1 ~ 10, including：Modified Zeolite Y, aluminum oxide 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；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.
- 12. in accordance with the method for claim 11, 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.
- 13. in accordance with the method for claim 12, 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.
- 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 3.0 ~ 4.5 μm.
- 15. in accordance with the method for claim 12, 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.
- 16. in accordance with the method for claim 11, 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.
- 17. in accordance with the method for claim 16, 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.
- 18. according to the method described in claim 11,12 or 16, 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。
- 19. in accordance with the method for claim 11, 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%.
- 20. in accordance with the method for claim 11, 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.
- 21. in accordance with the method for claim 11, 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.
- 22. in accordance with the method for claim 11, 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.
- 23. in accordance with the method for claim 22, 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）.
- 24. in accordance with the method for claim 22, 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.
- 25. in accordance with the method for claim 22, 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.
- 26. in accordance with the method for claim 11, it is characterised in that：The drying of the catalyst carrier is at 80 DEG C ~ 150 DEG C At a temperature of dry 3 ~ 6 hours, roasting be 500 DEG C ~ 600 DEG C be calcined 2.5 ~ 6.0 hours.
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| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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