CN107344109B - Produce the hydrocracking catalyst and preparation method thereof of high-quality hydrocracking tail oil - Google Patents
Produce the hydrocracking catalyst and preparation method thereof of high-quality hydrocracking tail oil Download PDFInfo
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- CN107344109B CN107344109B CN201610288609.2A CN201610288609A CN107344109B CN 107344109 B CN107344109 B CN 107344109B CN 201610288609 A CN201610288609 A CN 201610288609A CN 107344109 B CN107344109 B CN 107344109B
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7861—MRE-type, e.g. ZSM-48
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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Abstract
The present invention discloses a kind of catalyst and preparation method thereof for producing high-quality hydrocracking tail oil.Alumina powder and modified Y/ZSM-48 composite molecular screen powder: (1) being uniformly mixed, acid solution be then added, forms after sufficiently rolling by the method for preparing catalyst, including following content, and then dry, roasting obtains catalyst carrier；(2) catalyst carrier obtained with the dipping solution impregnation steps (1) containing active metal component, then dry, roasting, obtains hydrocracking catalyst.The catalyst of this method preparation makes catalyst have the characteristics that hydrogenation cracking activity is high, isomery performance is good using novel remodeling molecular sieve, obtained hydrocracking tail oil has the characteristics that linear paraffin content is few, naphthene content is low, can be used as good lube base oil.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof for producing high-quality hydrocracking tail oil, this method preparation is urged
Agent has the characteristics that plus hydrogen open loop activity height, isomery performance are good, and the hydrocracking tail oil that can be used for producing high viscosity index (HVI) is made
For lube base oil.
Background technique
In the production process of lube base oil, the composition and structure of lubricating oil viscosity index and its hydrocarbon-containifirst have close
The relationship cut.The viscosity index (VI) of different hydrocarbons is quite different.Even if being made of identical hydrocarbon system, viscosity index (VI) also has difference, this
Kind difference is that there is caused by difference in structure as hydro carbons of the same clan.With the viscous warm nature of alkane in hydro carbons contained by lubricating oil
Can be best, if the viscosity index (VI) of n-alkane is up to 180 or more.The viscosity index (VI) of isoparaffin is lower than n-alkane, and point
Zhi Chengdu more high viscosity refers to lower, and the chain index with side chain is lower, the viscosity index (VI) of cycloalkane and aromatic hydrocarbon with side chain then with
Its structural group composition is related, and in molecule when moieties dominance, viscosity temperature characteristic is good, there is higher viscosity index (VI).Monocyclic hydrocarbon
Class is with the increase of carbon atom number in molecule, and viscosity index (VI) increase, bicyclic and polycyclic hydro carbons, viscosity index (VI) is also with the number of side chain
Increase with length and increase, the viscosity temperature characteristic of polycyclic short-side chain cyclic hydrocarbon is worst.M.ushi. equal to be handled with linear regression analysis
The viscosity index (VI) and composition data of hydrotreating base oil obtain the viscosity index (VI) of different the hydrocarbon components in lubricating base oil, each group
The viscosity index (VI) divided is reduced according to alkane-cycloalkane-aromatic hydrocarbons sequence.Isoparaffin, the monocyclic hydrocarbon of belt length side chain are lubricating oil
Highly desirable existing component in composition., ought when there are a lot although having very high viscosity index (VI) for linear paraffin, meeting
Therefore the low temperature flow for influencing lubricating oil should be removed.The cyclic hydrocarbon of polycyclic short-side chain is that lubricating oil is made to lose excellent glue
The main component of warm nature energy, therefore should also be removed.
The bifunctional catalyst that hydrocracking catalyst is made of hydrogenating function and cracking function, wherein hydrogenating function be
It is provided by hydrogenation active metals, improves the Hydrogenation of hydrocracking catalyst, be conducive to the saturation of aromatic hydrocarbons；Cracking function be by
What amorphous silicon aluminium or molecular sieve provided, it can crack the macromolecular of long-chain and make the further open loop of polycyclic aromatic hydrocarbon after saturation
Conversion.
Molecular sieve is split as the component of lytic activity and heterogeneous activity, performance is provided in hydrocracking catalyst to adding hydrogen
The performance for changing catalyst is most important, is conducive to further increase hydrocracking catalyst using the modified molecular screen haveing excellent performance
Catalytic performance.The study on the modification of molecular sieve is mainly modified de- to carry out desiliconization by conventional acid, alkali and hydro-thermal process
Aluminium, while generating a large amount of secondary mesopore structure.The a large amount of secondary pores generated are conducive to the reaction and diffusion of macromolecular.Current
Modified method is mainly the sour processing of progress after the hydro-thermal process for first passing through certain temperature, has not only carried out dealuminzation to molecular sieve, has mentioned
High hydrothermal stability, while can produce a large amount of secondary pore structure.But the molecular sieve secondary pore of this method preparation is main
It concentrates on surface and amount is limited, just need advanced treating molecular sieve to improve the amount of secondary pore, this will lead to molecule and is sieved through
Dealuminzation is spent, the acid amount of molecular sieve, which reduces, is unable to satisfy requirement.In recent years, by the research of aqueous slkali desiliconization achieve it is huge into
Step, can greatly increase the amount of secondary pore by further progress alkali process after pickling, while can also improve the acid of molecular sieve
Amount, just right solves the problems, such as that original advanced treating bring acid amount is insufficient.Although but by first hydro-thermal process, then
Pickling dealuminzation, further alkali cleaning desiliconization can bring up a large amount of secondary pore structure, while acid amount can also be met the requirements.But it makes
The aperture of standby secondary pore structure is concentrated mainly on 3 ~ 5nm, for some two rings and its more than aromatic hydrocarbons macromolecular conversion also
It is helpless, therefore preparing the molecular sieve with more macroporous structure is a critically important direction of scientific rersearch.
Ke Ming etc. (the molecular sieve modified progress of MCM-22 [J], contemporary chemical industry, 2015,44(11): 2629 ~ 2634) lead to
It crosses discovery molecular sieve after alkali process after MCM-22 molecular sieve is carried out alkali process and hydro-thermal process and is maintaining original micropore
While structure, there is more meso-hole structures and macroporous structure.(Y molecular sieve is modified to its structure and acidity by Cheng Shiwen etc.
Influence [J], petrochemical technology and application, 2011,29(5): result of study 401 ~ 405) shows by hydro-thermal process, hydro-thermal-
Oxalic acid treatment etc. is modified, and Y molecular sieve can form a large amount of secondary pores, this illustrates that steam treatment can play the role of reaming,
Can be further increased after oxalic acid removing non-framework aluminum mesoporous hole hold and can adjust in a big way Y molecular sieve acids type and
Acid amount, modified total acid content decline, and strong L acid amount increases after hydro-thermal process, and strong B acid can be improved in hydro-thermal-oxalic acid combination dealuminzation
Amount.Qin Zhen etc. (it the physicochemical property of the small-grain Y molecular sieve of different silica alumina ratios and its is hydrocracked performance [J], petrochemical industry chemical industry,
2013,42(10): result of study 1080 ~ 1085) show the skeleton stability of small-grain Y molecular sieve with the increase of silica alumina ratio and
Increase；Acid amount is reduced with the increase of silica alumina ratio, and there is the small-grain Y molecular sieve of different silica alumina ratios different acid sites to be distributed；
The pore structure of small-grain Y molecular sieve is not the small-grain Y molecule it is obvious that compared with industrial Y molecular sieve with the variation of silica alumina ratio
Sifter device has biggish specific surface area, this is advantageous to heavy oil conversion.The small-grain Y acidic zeolite that silica alumina ratio is 5.2 is moderate, duct
Prosperity, skeleton stability is preferable, and high as the activity of the hydrocracking catalyst of carrier using it, light oil selectivity and industrial chemicals are received
Rate is high, is the active component of preferred light oil type hydrogen cracking catalyst.Wang Yingjun etc. (super steady Y molecular sieve modified research into
Open up [J], silicate notification, 2015,34(11): 3243 ~ 3250) describe the Dealumination of super steady Y molecular sieve, load acid changes
Property, loading cation or the methods of oxide modifying and molecular sieve are composite modified, show super steady Y molecular sieve by modified tool
There are good crystallinity, higher silica alumina ratio, biggish pore size and pore volume, high specific surface area and hydrothermal stability, fit
Suitable acid amount and acid strength, so that preparing catalyst as carrier or acidic components shows preferable catalytic performance.Simultaneously
Think that the study on the modification of ultra-steady Y molecular sieve is still to continue, on the one hand the research in terms of acid centre, USY molecular sieve has
How B acid and the acid site L, prepare the catalyst in specific acid site, is the project for needing to capture to reach best catalytic activity；
On the other hand it to improve secondary with recycling for the catalyst of super steady Y molecular sieve (or modified super steady Y molecular sieve) preparation
Number reduces increased production cost production efficiency.(the modified Y molecular sieve centering fraction selective hydrogenation Cracking catalyst such as Peng Chenghua
Influence [J], petroleum journal (PETROLEUM PROCESSING), 2006(supplementary issue): result of study 171 ~ 173) shows Y modified point
The middle fraction selectivity that sub- sifter device has lower total acid content and higher L acid ratio to be conducive to improve catalyst, and keep preferable living
Property；When product (< 370 DEG C of distillates) conversion ratio is 60%, (150-370 DEG C evaporates the middle fraction of pilot scale sizing catalyst HC-670
Divide oil) selectivity is 68.3%, and the middle fraction of similar industrial catalyst selectively only 61.8%.(the hydro-thermal process such as Li Mingxiao
Influence [J] with nitric acid treatment to modified Y molecular sieve performance, petrochemical industry, 2012,43(4): result of study table 412 ~ 419)
Bright, with the raising of hydro-thermal process temperature, the dealuminzation amount of Y molecular sieve increases, and specific surface area reduces, and total acid content reduces；It is dense with nitric acid
The increase of degree, the non-framework aluminum removing in Y molecular sieve, relative crystallinity, specific surface area and silica alumina ratio increase.With modified Y
The activity and selectivity of the standby hydrocracking catalyst of system with molecular sieve for preparing is improved, wherein Y molecular sieve through 680 DEG C of hydro-thermal process and
The hydrocracking catalyst prepared after 0.6mol/L nitric acid treatment has under the premise of keeping higher n-dodecane conversion ratio
Good middle oil (C4~8Hydrocarbon) selectivity, middle oil yield is 51.07%.Wang Wenlan (the being hydrocracked property of combination Modified Zeolite Y
Energy [J], chemistry of fuel journal, 2009,37(4): result of study 454 ~ 458) shows the mistake in Y type molecular sieve oxalic acid dealuminzation
Cheng Zhong, CTAB, which is added, can make Y type molecular sieve keep very high relative crystallinity, while improve SiO2/Al2O3Than reducing structure cell
Constant.The acid amount that CTAB participates in modified Y type molecular sieve significantly reduces, raising and partially acidic position of the reason by silica alumina ratio
Amine poisoning determines.The hydrocracking catalyst that CTAB participates in Modified Zeolite Y preparation has higher activity and midbarrel
Oil yield, VGO high conversion rate 2.42%, midbarrel than the middle fraction oil type hydrocracking catalyst of current industrial application
The high income 4.20% of oil.The reason is that CTAB, which participates in modified Y type molecular sieve, to be had richer mesoporous, make big point in VGO
Son can be more close to the acidic site of catalyst, while crackate can quickly leave the active sites of catalyst and avoid two
Secondary cracking, thus make catalyst that there is higher activity and midbarrel oil yield.Patent 200610001864.0 describes one
The method of modifying of kind Y type molecular sieve, this method have obtained high silicon using the method that surfactant is added in sour dealumination process
The Y type molecular sieve (mole silica alumina ratio 9 ~ 15 of silica and aluminium oxide) of aluminium ratio simultaneously maintains higher crystallinity, modified Y type point
The secondary pore of son sieve, which has, to be greatly improved, and sour structure has also obtained further improvement.Patent 200810104303.2 describes
A kind of method of modifying of HY type molecular sieve, this method are used by the silica solution of HY type molecular sieve dipping a certain amount of 5% ~ 10%, so
Afterwards by 120 DEG C of dry and 450 DEG C of roastings, dealumination treatment is finally carried out using certain density ammonium fluoride aqueous solution, is obtained
Micro--mesoporous remodeling molecular sieve.
Patent 200810105644.1 describes a kind of method of modifying of NaY type molecular sieve, and this method will be from using sieve
Sub-exchange resin is kept apart with molecular sieve pulp, in the discontiguous situation of the two, using concentration difference realize hydrogen ion with
The exchange of sodium ion, the problem of alleviating subsequent wastewater treatment.The sodium oxide content of obtained remodeling molecular sieve can be reduced to
1wt% is hereinafter, crystallinity is maintained at 80% or more.Patent 201110331019.0 describes a kind of modification side of NaY type molecular sieve
Method, this method are added in the mixed liquor of NaY molecular sieve, buffer and water using mixed acid and are beaten uniformly, then and adjust pH
Value is 4.0 ~ 6.5, and exchange reaction under the conditions of 70 ~ 95 DEG C, finally washs, and dries.The method achieve no ammoniums to discharge, and alleviates
The problem of subsequent wastewater treatment.The sodium oxide content of obtained remodeling molecular sieve can be reduced to 0.5wt% hereinafter, crystallinity
It is maintained at 85% or more.Patent 201310114414.2 describes a kind of method of modifying of USY molecular sieve, and this method uses
0.10mol/L ~ 0.35mol/L citric acid is modified at 50 DEG C ~ 120 DEG C, and rising to set temperature in temperature is 60 DEG C ~ 90 DEG C
Afterwards, ammonium fluosilicate solution is added with the speed of 0.1ml/min ~ 3.5ml/min, after reacting 1h ~ 6h after charging, washs, does
It is dry to obtain modified USY molecular sieve.The specific surface of molecular sieve, secondary pore hole hold and middle strong acid ratio significantly improves.Patent
201310240740.8 and 201410131823.8 describe the combination method of modifying rich in mesoporous ultra-steady Y molecular sieve, this method
Using organic acid and inorganic salt solution mixed solution, under stirring conditions, temperature reaction is carried out in closed container, reaction reaches
It is washed after to setting time, filters to neutrality, be dried to obtain modified molecular screen.Modified molecular sieve secondary pore content is significant
It improves, silica alumina ratio increases, and lattice constant reduces.Patent 201410131458.0 describes a kind of method of modifying of USY molecular sieve,
This method with ammonium fluosilicate and citric acid mixed solution 50 DEG C ~ 120 DEG C at a temperature of be modified processing, finally obtain and be rich in
The high and middle strong acid modified USY molecular sieve abundant of secondary pore structure, crystallinity.Patent 201510131458.0 describes one kind and changes
Property Y molecular sieve and its method of modifying, this method use alkaline solution to handle Y type molecular sieve first, then take dealuminzation
The method for mending silicon obtains the Y type molecular sieve of high silica alumina ratio.The modified molecular screen has strong acid ratio big, especially strong B acid ratio
Big feature.
Different types of modified molecular screen can provide different reactivity worth for hydrocracking catalyst, using some new
The strong modified molecular screen of the isomerism ability of type can strengthen in hydrocracking process plus hydrogen ring-opening reaction and hydroisomerizing is anti-
It answers, the raising of this reactivity worth can effectively improve the property of hydrocracked product, can produce good lubrication oil base
Plinth oil product.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of catalyst for producing high-quality hydrocracking tail oil and its preparation
Method.Catalyst prepared by the present invention makes catalyst have hydrogenation cracking activity height, isomery using novel remodeling molecular sieve
The good feature of performance, obtained hydrocracking tail oil have the characteristics that linear paraffin content is few, naphthene content is low, can be used as
Good lube base oil.
Method for preparing catalyst of the present invention, including following content:
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, then dry, roasting obtains catalyst carrier；
(2) catalyst carrier obtained with the dipping solution impregnation steps (1) containing active metal component, then dry,
Roasting, obtains hydrocracking catalyst.
In the method for the present invention, modification Y/ZSM-48 composite molecular screen, is had the property that with Y/ described in step (1)
On the basis of ZSM-48 composite molecular screen weight, Y type molecular sieve content is 40% ~ 90%, preferably 50% ~ 85%；Compound point of Y/ZSM-48
The silica alumina ratio (molar ratio that silica alumina ratio described herein is silica and aluminium oxide) of son sieve is 8 ~ 35, preferably 15 ~ 25；Compare table
Area is 450 ~ 880m2/ g, preferably 550 ~ 750m2/g；Pore volume is 0.24 ~ 0.35ml/g, preferably 0.28 ~ 0.34ml/g.
In the method for the present invention, the preparation step of modification Y/ZSM-48 composite molecular screen described in step (1) is as follows:
Y type molecular sieve is roasted 1 ~ 12 hour under the conditions of 350 ~ 650 DEG C, then by the Y after unsaturated olefin and roasting
The contact of type molecular sieve, in the inert gas atmospheres such as nitrogen, helium and argon gas, roasts 1 ~ 8 hour under the conditions of 450 ~ 650 DEG C
Roasting carbon deposit reaction is carried out, Y type molecular sieve surface desiliconization processing is then carried out, obtains Modified Zeolite Y；It will modified Y type point
Son sieve powder is added in the solution containing sodium hydroxide and template, and ageing 0.5 ~ 12 is small at 50 ~ 180 DEG C in confined conditions
When, it is aged 1.0 ~ 6 hours preferably at 80 ~ 160 DEG C, white carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel body
System, reaction mixture in confined conditions wash by crystallization 2 ~ 5 days at 150 ~ 180 DEG C, finally cooling, in 50 ~ 120 DEG C of conditions
Then lower drying 8 ~ 24 hours roasts 1 ~ 6 hour under the conditions of 450 ~ 650 DEG C, and molten using the ammonium nitrate of 0.5 ~ 3.0mol/L
Liquid exchanges 1 ~ 2 time under the conditions of 80 ~ 120 DEG C, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 15, and each swap time is 1.0 ~
3.0 hours, finally obtain modified Y/ZSM-48 composite molecular screen.The Y type molecular sieve has the property that silica/oxygen
Changing al mole ratio is between 4.8 ~ 20, and specific surface area is 650 ~ 860m20.33 ~ 55ml/g of/g, Kong Rongwei；The ethylenic unsaturation
Hydrocarbon is the positive structure that carbon atom number is 2 ~ 10 or isomeric olefine, diene hydrocarbon mixture；Wherein the alkene sufficiently connects with molecular sieve
Touching refers to that unsaturated olefin diffuses into inside molecular sieve；When using gaseous state unsaturated olefin, gaseous state unsaturated olefin with point
Son sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid insatiable hunger
With alkene and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 hour, molecular sieve answer thorough impregnation in
In liquefied olefines.The alkene comes into full contact with molecular sieve and generally carries out at normal temperature, the unsaturated hydrocarbons state phase
It is phase under room temperature；The desiliconization treatment process be the Y type molecular sieve after carbon distribution reacts is added to 0.35 ~
In the sodium hydroxide solution of 1.20mol/L, then handles 0.5 ~ 3 hour, be washed out to pH value less than 10 at 50 ~ 90 DEG C；Y
The mass ratio of water is 1:3 ~ 20 in the additional amount and solution of type molecular sieve；The molar ratio of the reaction mixture gel system with
Following substance meter (not including Modified Zeolite Y) are as follows: 1.1 ~ 1.4Na2O:21~25SiO2: 0.4 ~ 0.6 template: 350 ~
450H2O；Wherein the template is hexamethylene bromide and/or Chloor-hexaviet；It is with reaction mixture gel weight
Benchmark, the additional amount of Modified Zeolite Y account for 5wt% ~ 20wt% of reaction mixture gel system, preferably 8wt% ~ 15wt%.
In the method for the present invention, the specific surface area of alumina powder described in step (1) is 400 ~ 820m2/ g, preferably 450 ~ 750
m20.55 ~ 1.55 ml/g of/g, Kong Rongwei, preferably 0.75 ~ 1.05 ml/g.
In the method for the present invention, acid solution described in step (1) can be the inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, can also be with
It is the organic acids such as acetic acid and citric acid, preferably nitric acid solution；Acid solutions are 2wt% ~ 10wt%, preferably 3wt% ~ 6wt%.
In the method for the present invention, drying temperature described in step (1) is 50 ~ 150 DEG C, and preferably 100 ~ 120 DEG C, drying time is
6 ~ 12 hours；Maturing temperature is 450 ~ 650 DEG C, and calcining time is 2 ~ 12 hours.
Containing active metal component in the method for the present invention, described in step (2) is group vib metal and group VIII metal；VIB
The preferred tungsten of race's metal (W) and molybdenum (Mo), the preferred cobalt of group VIII metal (Co) and nickel (Ni), dipping solution are formulated as this field skill
Art personnel are known；Dipping method is using supersaturation dipping.
In the method for the present invention, drying temperature described in step (2) is 50 ~ 150 DEG C, and preferably 100 ~ 120 DEG C, drying time is
6 ~ 12 hours；Maturing temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
The hydrocracking catalyst of the method for the present invention preparation, based on catalyst weight percent, each component in catalyst
Content are as follows: modified Y/ZSM-48 composite molecular screen component is generally 6 ~ 35%, preferably 10 ~ 30%；Aluminium oxide is generally 40% ~ 75%,
It is preferred that 50 ~ 70%；Group vib metal (in terms of oxide) is generally 10% ~ 30%, preferably 14 ~ 24%；Group VIII metal is (with oxide
Meter) it is generally 3% ~ 10%, preferably 3 ~ 8%.
Catalyst of the present invention when handling VGO, reaction condition in the presence of hydrogen, 10 ~ 20MPa of reaction pressure,
350 ~ 430 DEG C of reaction temperature, hydrogen to oil volume ratio 500 ~ 1800,0.5 ~ 5.0h of volume space velocity when liquid-1。
The method of the present invention compared with the prior art, has the advantages that catalyst due to using while having in preparation process
Have and well hydrogen open-loop performance and isomerization performance is added preferably to be modified Y/ZSM-48 composite molecular screen, enhances during the reaction
The isomerization reaction for adding hydrogen ring-opening reaction and linear paraffin of polycyclic aromatic hydrocarbon in VGO feedstock, makes the cycloalkane in reaction product
It declines to a great extent with linear paraffin content, the viscosity index (VI) of hydrocracking tail oil product is greatly improved.Therefore, the present invention urges
Agent has good plus hydrogen open loop ability and isomerization performance, can greatly improve the viscosity index (VI) of hydrocracking tail oil.
Specific embodiment
Preparation process of the invention is further illustrated below with reference to embodiment, but following embodiment is not constituted to present invention side
The limitation of method.
Embodiment 1
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 8 hours dry under the conditions of 120 DEG C, it is then roasted under the conditions of 550 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of W and Ni, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 8 hours at 120 DEG C.Then it is roasted 6 hours at 490 DEG C, obtains hydrocracking catalyst.Catalyst performance
Matter such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 75%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 19；Specific surface area is 656m2/g；Hole
Volume is 0.29ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted 6 under the conditions of 450 DEG C
Hour, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in nitrogen atmosphere, roasts 3 under the conditions of 550 DEG C
Hour carries out roasting carbon deposit reaction, then carries out Y type molecular sieve surface desiliconization processing, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, is aged 3 hours at 140 DEG C in confined conditions,
White carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions at 160 DEG C
Crystallization 4 days, finally cooling, washing was 16 hours dry under the conditions of 80 DEG C, then roasted 4 hours under the conditions of 550 DEG C, and adopt
It is exchanged 2 times under the conditions of 90 DEG C with the ammonium nitrate solution of 1.0mol/L, the liquid-solid ratio (ml/g) of exchange process is 10, is handed over every time
Changing the time is 2.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 2
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 6 hours dry under the conditions of 110 DEG C, it is then roasted under the conditions of 550 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of W and Ni, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 8 hours at 110 DEG C.Then it is roasted 6 hours at 500 DEG C, obtains hydrocracking catalyst.Catalyst performance
Matter such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 65%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 18；Specific surface area is 710m2/g；Hole
Volume is 0.31ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted 6 under the conditions of 450 DEG C
Hour, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in argon atmosphere, roasts 3 under the conditions of 520 DEG C
Hour carries out roasting carbon deposit reaction, then carries out Y type molecular sieve surface desiliconization processing, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, is aged 3.0 hours at 90 DEG C in confined conditions,
White carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions at 170 DEG C
Crystallization 4 days, finally cooling, washing was 16 hours dry under the conditions of 90 DEG C, then roasted 4 hours under the conditions of 480 DEG C, and adopt
It is exchanged 2 times under the conditions of 100 DEG C with the ammonium nitrate solution of 2.0mol/L, the liquid-solid ratio (ml/g) of exchange process is 8, is handed over every time
Changing the time is 1.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 3
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 8 hours dry under the conditions of 120 DEG C, it is then roasted under the conditions of 490 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of preparation Mo and Ni, impregnation steps (1) resulting carrier of hydrocracking catalyst, then
Filtering, freeze-day with constant temperature 8 hours at 110 DEG C.Then it is roasted 10 hours at 550 DEG C, obtains hydrocracking catalyst.Catalyst
Property such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 55%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 22；Specific surface area is 610m2/g；Hole
Volume is 0.28ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted 2 under the conditions of 550 DEG C
Hour, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in nitrogen atmosphere, roasts 3 under the conditions of 480 DEG C
Hour carries out roasting carbon deposit reaction, then carries out Y type molecular sieve surface desiliconization processing, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, and ageing 3.0 is small at 110 DEG C in confined conditions
When, white carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions in 160
Crystallization 2 days at DEG C, finally cooling, washing is 12 hours dry under the conditions of 90 DEG C, then roasts 3 hours under the conditions of 490 DEG C,
And using the ammonium nitrate solution of 0.5mol/L, under the conditions of 90 DEG C, exchange 2 times, the liquid-solid ratio (ml/g) of exchange process is 12, often
Secondary swap time is 2.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 4
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 8 hours dry under the conditions of 80 DEG C, it is then roasted under the conditions of 620 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of preparation Mo and Co, impregnation steps (1) resulting carrier of hydrocracking catalyst, then
Filtering, freeze-day with constant temperature 11 hours at 100 DEG C.Then it is roasted 8 hours at 520 DEG C, obtains hydrocracking catalyst.Catalyst
Property such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 60%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 16；Specific surface area is 630m2/g；Hole
Volume is 0.31ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted 6 under the conditions of 500 DEG C
Hour, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in helium atmosphere, roasts 4 under the conditions of 580 DEG C
Hour carries out roasting carbon deposit reaction, then carries out Y type molecular sieve surface desiliconization processing, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, and ageing 3.0 is small at 120 DEG C in confined conditions
When, white carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions in 160
Crystallization 4 days at DEG C, finally cooling, washing is 12 hours dry under the conditions of 110 DEG C, then roasts 5 hours under the conditions of 530 DEG C,
And using the ammonium nitrate solution of 0.8mol/L, under the conditions of 90 DEG C, exchange 2 times, the liquid-solid ratio (ml/g) of exchange process is 9, often
Secondary swap time is 2.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 5
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 8 hours dry under the conditions of 95 DEG C, it is then roasted under the conditions of 550 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of W and Co, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 8 hours at 110 DEG C.Then it is roasted 6 hours at 520 DEG C, obtains hydrocracking catalyst.Catalyst performance
Matter such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 55%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 23；Specific surface area is 580m2/g；Hole
Volume is 0.28ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted under the conditions of 520 DEG C
10 hours, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in nitrogen atmosphere, is roasted under the conditions of 510 DEG C
Roasting carbon deposit reaction is carried out within 4 hours, Y type molecular sieve surface desiliconization processing is then carried out, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, and ageing 3.0 is small at 110 DEG C in confined conditions
When, white carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions in 170
Crystallization 2 days at DEG C, finally cooling, washing is 16 hours dry under the conditions of 90 DEG C, then roasts 2 hours under the conditions of 530 DEG C,
And using the ammonium nitrate solution of 1.5mol/L, under the conditions of 90 DEG C, exchange 2 times, the liquid-solid ratio (ml/g) of exchange process is 10, often
Secondary swap time is 2.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 6
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 6 hours dry under the conditions of 120 DEG C, it is then roasted under the conditions of 510 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of preparation Mo and Co, impregnation steps (1) resulting carrier of hydrocracking catalyst, then
Filtering, freeze-day with constant temperature 10 hours at 110 DEG C.Then it is roasted 8 hours at 540 DEG C, obtains hydrocracking catalyst.Catalyst
Property such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 85%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 15；Specific surface area is 740m2/g；Hole
Volume is 0.34ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: Y type molecular sieve is roasted 2 under the conditions of 580 DEG C
Hour, unsaturated olefin is contacted with the Y type molecular sieve after roasting then, in nitrogen atmosphere, roasts 6 under the conditions of 510 DEG C
Hour carries out roasting carbon deposit reaction, then carries out Y type molecular sieve surface desiliconization processing, obtains Modified Zeolite Y；It will modified Y
Type molecular sieve powder is added in the solution containing sodium hydroxide and template, and ageing 3.0 is small at 130 DEG C in confined conditions
When, white carbon black is added, continues to be uniformly mixing to obtain reaction mixture gel system, reaction mixture is in confined conditions in 170
Crystallization 4 days at DEG C, finally cooling, washing is 16 hours dry under the conditions of 90 DEG C, then roasts 3 hours under the conditions of 560 DEG C,
And using the ammonium nitrate solution of 1.5mol/L, under the conditions of 110 DEG C, exchanging 2 times, the liquid-solid ratio (ml/g) of exchange process is 12,
Each swap time is 1.0 hours, finally obtains modified Y/ZSM-48 composite molecular screen.
Embodiment 7
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 12 hours dry under the conditions of 80 DEG C, it is then roasted under the conditions of 610 DEG C, obtains catalyst carrier；
(2) the metal impregnation solution of W and Co, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 8 hours at 110 DEG C.Then it is roasted 8 hours at 550 DEG C, obtains hydrocracking catalyst.Catalyst performance
Matter such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 70%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 17；Specific surface area is 710m2/g；Hole
Volume is 0.32ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: by Y type molecular sieve under the conditions of 350 ~ 650 DEG C
Then roasting 1 ~ 12 hour contacts unsaturated olefin with the Y type molecular sieve after roasting, lazy in nitrogen, helium and argon gas etc.
Property gas atmosphere in, roasted under the conditions of 450 ~ 650 DEG C carry out within 1 ~ 8 hour roasting carbon deposit reaction, then carry out Y type molecular sieve table
The processing of emaciated face silicon, obtains Modified Zeolite Y；Modified Zeolite Y powder is added molten containing sodium hydroxide and template
It in liquid, is aged 1.0 ~ 6 hours at 80 ~ 160 DEG C in confined conditions, white carbon black is added, continued to be uniformly mixing to obtain and react mixed
Close object gel rubber system, reaction mixture crystallization 2 ~ 5 days at 150 ~ 180 DEG C in confined conditions are finally cooling, wash, 50 ~
It is 8 ~ 24 hours dry under the conditions of 120 DEG C, it is then roasted 1 ~ 6 hour under the conditions of 450 ~ 650 DEG C, and using 0.5 ~ 3.0mol/L's
Ammonium nitrate solution exchanges 1 ~ 2 time under the conditions of 80 ~ 120 DEG C, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 15, every time when exchange
Between be 1.0 ~ 3.0 hours, finally obtain modified Y/ZSM-48 composite molecular screen.
Embodiment 8
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 6 ~ 12 hours dry under the conditions of 50 ~ 150 DEG C, it then roasts, is urged under the conditions of 450 ~ 650 DEG C
Agent carrier；
(2) the metal impregnation solution of W and Ni, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 6 ~ 12 hours at 50 ~ 150 DEG C.Then it is roasted 2 ~ 12 hours at 450 ~ 650 DEG C, obtains being hydrocracked and urge
Agent C1.Catalyst property such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 50% ~ 85%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 15 ~ 25；Specific surface area is 550
~750m2/g；Pore volume is 0.28 ~ 0.34ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: by Y type molecular sieve under the conditions of 350 ~ 650 DEG C
Then roasting 1 ~ 12 hour contacts unsaturated olefin with the Y type molecular sieve after roasting, lazy in nitrogen, helium and argon gas etc.
Property gas atmosphere in, roasted under the conditions of 450 ~ 650 DEG C carry out within 1 ~ 8 hour roasting carbon deposit reaction, then carry out Y type molecular sieve table
The processing of emaciated face silicon, obtains Modified Zeolite Y；Modified Zeolite Y powder is added molten containing sodium hydroxide and template
It in liquid, is aged 1.0 ~ 6 hours at 80 ~ 160 DEG C in confined conditions, white carbon black is added, continued to be uniformly mixing to obtain and react mixed
Close object gel rubber system, reaction mixture crystallization 2 ~ 5 days at 150 ~ 180 DEG C in confined conditions are finally cooling, wash, 50 ~
It is 8 ~ 24 hours dry under the conditions of 120 DEG C, it is then roasted 1 ~ 6 hour under the conditions of 450 ~ 650 DEG C, and using 0.5 ~ 3.0mol/L's
Ammonium nitrate solution exchanges 1 ~ 2 time under the conditions of 80 ~ 120 DEG C, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 15, every time when exchange
Between be 1.0 ~ 3.0 hours, finally obtain modified Y/ZSM-48 composite molecular screen.
Embodiment 9
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution are then added, sufficiently
It is formed after rolling, it is then 6 ~ 12 hours dry under the conditions of 50 ~ 150 DEG C, it then roasts, is urged under the conditions of 450 ~ 650 DEG C
Agent carrier；
(2) the metal impregnation solution of W and Ni, impregnation steps (1) resulting carrier of hydrocracking catalyst, then mistake are prepared
Filter, freeze-day with constant temperature 6 ~ 12 hours at 50 ~ 150 DEG C.Then it is roasted 2 ~ 12 hours at 450 ~ 650 DEG C, obtains being hydrocracked and urge
Agent C1.Catalyst property such as table 1.
The modified Y/ZSM-48 composite molecular screen of step (1) has the property that with Y/ZSM-48 composite molecular screen weight
On the basis of, Y type molecular sieve content is 50% ~ 85%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 15 ~ 25；Specific surface area is 550
~750m2/g；Pore volume is 0.28 ~ 0.34ml/g.
The preparation step of the modified Y/ZSM-48 molecular sieve of step (1) is as follows: by Y type molecular sieve under the conditions of 350 ~ 650 DEG C
Then roasting 1 ~ 12 hour contacts unsaturated olefin with the Y type molecular sieve after roasting, lazy in nitrogen, helium and argon gas etc.
Property gas atmosphere in, roasted under the conditions of 450 ~ 650 DEG C carry out within 1 ~ 8 hour roasting carbon deposit reaction, then carry out Y type molecular sieve table
The processing of emaciated face silicon, obtains Modified Zeolite Y；Modified Zeolite Y powder is added molten containing sodium hydroxide and template
It in liquid, is aged 1.0 ~ 6 hours at 80 ~ 160 DEG C in confined conditions, white carbon black is added, continued to be uniformly mixing to obtain and react mixed
Close object gel rubber system, reaction mixture crystallization 2 ~ 5 days at 150 ~ 180 DEG C in confined conditions are finally cooling, wash, 50 ~
It is 8 ~ 24 hours dry under the conditions of 120 DEG C, it is then roasted 1 ~ 6 hour under the conditions of 450 ~ 650 DEG C, and using 0.5 ~ 3.0mol/L's
Ammonium nitrate solution exchanges 1 ~ 2 time under the conditions of 80 ~ 120 DEG C, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 15, every time when exchange
Between be 1.0 ~ 3.0 hours, finally obtain modified Y/ZSM-48 composite molecular screen.
Comparative example
It is mixed using Y type molecular sieve and ZSM-48 molecular sieve, remaining preparation condition is obtained being hydrocracked and be urged with embodiment 2
Agent BC1.Catalyst property such as table 1.
Catalytic performance test.
Evaluating apparatus is carried out using 200m1 small hydrogenation device, carries out presulfurization to catalyst before activity rating.Evaluation is urged
The raw materials used oil nature of agent activity and reaction process condition are shown in Table 2 and table 3, and catalyst reaction performance comparing result is shown in Table 4.It comments
When valence catalyst, feedstock oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, passes through
The organic nitrogen content controlled in feedstock oil when Hydrobon catalyst bed is lower than 20ppm.
The composition of 1 catalyst of table
2 process conditions of table
3 feedstock property of table
4 catalyst reaction performance of table
Hydrocracking reaction the result shows that, catalyst of the invention is compared with comparative example catalyst, when conversion ratio is identical, instead
Answer temperature 4 ~ 8 DEG C low, the BMCI value of the viscosity index (VI) of tail oil product, the normal paraffin content in tail oil and tail oil is than comparison
Example wants low.Illustrating the catalyst of the method for the present invention preparation has the characteristics that add that hydrogen open-loop performance is good, hydroisomerization ability is strong.
Claims (18)
1. a kind of preparation method for the catalyst for producing high-quality hydrocracking tail oil, it is characterised in that: including following content:
(1) alumina powder and modified Y/ZSM-48 composite molecular screen powder are uniformly mixed, acid solution is then added, sufficiently rolls
After form, it is then dry, roast, obtain catalyst carrier；
(2) catalyst carrier obtained with the dipping solution impregnation steps (1) containing active metal component, then dry, roasting,
Obtain hydrocracking catalyst；
Wherein, the preparation step of modification Y/ZSM-48 composite molecular screen described in step (1) is as follows:
(1) Y type molecular sieve is roasted under the conditions of 350 ~ 650 DEG C 1 ~ 12 hour, then by the Y after unsaturated olefin and roasting
The contact of type molecular sieve roasts under the conditions of 450 ~ 650 DEG C in an inert gas atmosphere and carries out within 1 ~ 8 hour roasting carbon deposit reaction, so
Y type molecular sieve surface desiliconization processing is carried out afterwards, obtains Modified Zeolite Y；
(2) Modified Zeolite Y powder is added in the solution containing sodium hydroxide and template, in confined conditions in 50 ~
It is aged 0.5 ~ 12 hour at 180 DEG C, white carbon black is added, continue to be uniformly mixing to obtain reaction mixture gel system, reaction mixing
Object in confined conditions wash by crystallization 2 ~ 5 days at 150 ~ 180 DEG C, finally cooling, and dry 8 ~ 24 is small under the conditions of 50 ~ 120 DEG C
When, it is then roasted 1 ~ 6 hour under the conditions of 450 ~ 650 DEG C, and using the ammonium nitrate solution of 0.5 ~ 3.0mol/L, at 80 ~ 120 DEG C
Under the conditions of, it exchanges 1 ~ 2 time, the liquid-solid ratio of exchange process is calculated as 5 ~ 15 with ml/g, and each swap time is 1.0 ~ 3.0 hours, most
After obtain modified Y/ZSM-48 composite molecular screen.
2. according to the method described in claim 1, it is characterized by: modification Y/ZSM-48 composite molecular screen described in step (1),
It has the property that on the basis of Y/ZSM-48 composite molecular screen weight, Y type molecular sieve content is 40% ~ 90%；Y/ZSM-48 is multiple
The silica alumina ratio for closing molecular sieve is 8 ~ 35；Specific surface area is 450 ~ 880m2/g；Pore volume is 0.24 ~ 0.35ml/g.
3. according to the method described in claim 2, it is characterized by: Y type divides on the basis of Y/ZSM-48 composite molecular screen weight
Son sieve content is 50% ~ 85%；The silica alumina ratio of Y/ZSM-48 composite molecular screen is 15 ~ 25；Specific surface area is 550 ~ 750m2/g；Hole
Volume is 0.28 ~ 0.34ml/g.
4. according to the method described in claim 1, it is characterized by: the Y type molecular sieve have the property that silica/
Alumina molar ratio is between 4.8 ~ 20, and specific surface area is 650 ~ 860m20.33 ~ 55ml/g of/g, Kong Rongwei.
5. according to the method described in claim 1, it is characterized by: it is 2 ~ 10 just that the unsaturated olefin, which is carbon atom number,
Structure or isomeric olefine.
6. according to the method described in claim 1, it is characterized by: the alkene and molecular sieve come into full contact with and refer to unsaturation
Alkene diffuses into inside molecular sieve；When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve contact conditions
Are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecule
Sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 hour, molecular sieve answered thorough impregnation in liquefied olefines.
7. according to the method described in claim 1, it is characterized by: the alkene and molecular sieve come into full contact at normal temperature into
Row, the unsaturated hydrocarbons state phase is phase under room temperature.
8. according to the method described in claim 1, it is characterized by: the desiliconization treatment process is will be after carbon distribution reacts
Y type molecular sieve be added in the sodium hydroxide solution of 0.35 ~ 1.20mol/L, then handled 0.5 ~ 3 hour at 50 ~ 90 DEG C,
It is washed out to pH value less than 10.
9. according to the method described in claim 8, it is characterized by: in the additional amount and solution of Y type molecular sieve water mass ratio
For 1:3 ~ 20；The molar ratio of the reaction mixture gel system is calculated as with following substance: 1.1 ~ 1.4Na2O:21~25SiO2:
0.4 ~ 0.6 template: 350 ~ 450H2O。
10. according to the method described in claim 9, it is characterized by: the template is hexamethylene bromide and/or chlorination six
The double ammoniums of first；On the basis of reaction mixture gel weight, the additional amount of Modified Zeolite Y accounts for reaction mixture gel system
5wt% ~ 20wt%.
11. according to the method described in claim 1, it is characterized by: the specific surface area of alumina powder described in step (1) is
400~820m20.55 ~ 1.55 ml/g of/g, Kong Rongwei.
12. according to the method described in claim 1, it is characterized by: the specific surface area of alumina powder described in step (1) is
450~750 m20.75 ~ 1.05 ml/g of/g, Kong Rongwei.
13. according to the method described in claim 1, it is characterized by: drying temperature described in step (1) be 50 ~ 150 DEG C, do
The dry time is 6 ~ 12 hours；Maturing temperature is 450 ~ 650 DEG C, and calcining time is 2 ~ 12 hours.
14. according to the method described in claim 1, it is characterized by: active metal component described in step (2) is group vib gold
Category and group VIII metal；Group vib tungsten (W) and molybdenum (Mo), group VIII metal cobalt (Co) and nickel (Ni).
15. according to the method described in claim 1, it is characterized by: drying temperature described in step (2) be 50 ~ 150 DEG C, do
The dry time is 6 ~ 12 hours；Maturing temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
16. the catalyst of claim 1 to 15 either method preparation, it is characterised in that: based on catalyst weight percent, catalysis
The content of each component in agent are as follows: modified Y/ZSM-48 composite molecular screen group is divided into 6 ~ 35%；Aluminium oxide is 40% ~ 75%；Group vib gold
Belong to and is calculated as 10% ~ 30% with oxide；Group VIII metal is calculated as 3% ~ 10% with oxide.
17. catalyst according to claim 16, it is characterised in that: each in catalyst based on catalyst weight percent
The content of component are as follows: modified Y/ZSM-48 composite molecular screen component 10 ~ 30%；Aluminium oxide 50 ~ 70%；Group vib metal is with oxide
Meter 14 ~ 24%；Group VIII metal in terms of oxide 3 ~ 8%.
18. the application of the catalyst treatment VGO of claim 16 or 17, it is characterised in that: reaction condition exists in hydrogen
Under the conditions of, 10 ~ 20MPa of reaction pressure, 350 ~ 430 DEG C of reaction temperature, hydrogen to oil volume ratio 500 ~ 1800, volume space velocity 0.5 when liquid ~
5.0h-1。
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