CN106669807A - Preparation method of catalyst for improving viscosity index of hydrocracking tail oil - Google Patents

Preparation method of catalyst for improving viscosity index of hydrocracking tail oil Download PDF

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CN106669807A
CN106669807A CN201510750880.9A CN201510750880A CN106669807A CN 106669807 A CN106669807 A CN 106669807A CN 201510750880 A CN201510750880 A CN 201510750880A CN 106669807 A CN106669807 A CN 106669807A
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catalyst
modified
composite molecular
pore volume
molecular sieve
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CN106669807B (en
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秦波
杜艳泽
柳伟
张晓萍
王凤来
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • 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
    • B01J29/7815—Zeolite Beta
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10G2300/70—Catalyst aspects
    • 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

Abstract

The invention discloses a preparation method of a catalyst for producing a high viscosity index of hydrocracking tail oil. The preparation method comprises: (1) uniformly mixing macroporous alumina powder, a modified Y-beta composite molecular sieve and modified ZSM-48 molecular sieve powder, adding an acid solution, completely rolling, molding, drying, and calcining to obtain a catalyst carrier; and (2) impregnating the catalyst carrier obtained in the step (1) with an active metal component-containing impregnation solution, drying, and calcining to obtain the hydrocracking catalyst. According to the present invention, the prepared catalyst uses the novel modified molecular sieve, such that the catalyst has the characteristics of high hydrogenation ring opening activity and good isomerization performance, and the obtained hydrocracking tail oil has the characteristics of extremely low straight chain alkane content and high viscosity index, and can be adopted as the high quality lubricating oil base oil.

Description

A kind of method for preparing catalyst for improving hydrocracking tail oil viscosity index (VI)
Technical field
The present invention relates to a kind of method for preparing catalyst for producing high viscosity index (HVI) hydrocracking tail oil, catalyst prepared by the method has the characteristics of hydrogenation open loop activity is high, isomery performance is good, can be used to produce the hydrocracking tail oil of high viscosity index (HVI).
Background technology
The features such as hydrocracking technology has big strong adaptability to raw material, production operation and products scheme motility, good product quality, the charging of various heavy inferiors can be converted into high-quality jet fuel, diesel oil, lube basestocks and the chemical industry Petroleum and tail oil preparing ethylene by steam cracking raw material of market in urgent need, become one of modern oil refining and the most important heavy oil deep processing technique of petro chemical industry, at home and abroad obtain increasingly extensive application.
The bifunctional catalyst that hydrocracking catalyst is made up of hydrogenating function and cracking function, wherein hydrogenating function are provided by hydrogenation active metals, improve the Hydrogenation of hydrocracking catalyst, are conducive to the saturation of aromatic hydrocarbons；Cracking function is provided by amorphous silicon aluminium or molecular sieve, it can crack the macromole of long-chain and make the further open loop conversion of polycyclic aromatic hydrocarbon after saturation, this not only contributes to process more heavy, Hydrocracking Raw Oil inferior, improve liquid product yield and produce high-quality hydrocracked product, the ability of the anti-organic nitrogen poisoning of catalyst can also further be improved, green coke, carbon deposit are reduced, extends the service life of catalyst.
In the production process of lube base oil, oil body index has close relationship with the composition and structure of its hydrocarbon-containifirst.The viscosity index (VI) of different hydrocarbons is quite different.Even if hydrocarbon system constitutes by identical, viscosity index (VI) also has difference, and this difference has in structure difference and causes by hydro carbons of the same clan.In the hydro carbons contained by lubricating oil with the viscosity temperature characteristic of alkane preferably, the such as viscosity index (VI) of n-alkane is up to more than 180.The viscosity index (VI) of isoparaffin is lower than n-alkane, and branch degree more high viscosity refers to lower, chain index with side chain is lower, the viscosity index (VI) of the cycloalkane with side chain and aromatic hydrocarbon is then relevant with its structural group composition, when moieties are dominant in molecule, its viscosity temperature characteristic is good, there is higher viscosity index (VI).Monocyclic hydro carbons with carbon number in molecule increase, viscosity index (VI) increase, bicyclic and multi-ring hydro carbons, its viscosity index (VI) also increases with the number of side chain and the increase of length, and the viscosity temperature characteristic of multi-ring short-side chain cyclic hydrocarbon is worst.
For linear paraffin, although with very high viscosity index (VI), the low temperature flow of lubricating oil when there are a lot, ought can be affected, therefore, should be removed.The cyclic hydrocarbon of multi-ring short-side chain, is to make lubricating oil lose the key component of excellent viscosity temperature characteristic, therefore also should be removed.
Different types of modified molecular screen can provide different reactivity worth for hydrocracking catalyst, the hydrogenation ring-opening reaction and hydroisomerizing reaction in hydrocracking process can be strengthened using the strong modified molecular screen of some new isomerism abilities, the raising of this reactivity worth can effectively improve the property of hydrocracked product, can produce the lube base oil product of high-quality.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of method for preparing catalyst for producing high viscosity index (HVI) hydrocracking tail oil.Catalyst prepared by the present invention causes catalyst to have the characteristics of hydrogenation open loop activity is high, isomery performance is good using new modified molecular screen, the hydrocracking tail oil for obtaining has linear paraffin content few and the characteristics of high viscosity index (VI), can be used as the lube base oil of high-quality.
A kind of method for preparing catalyst for producing high viscosity index (HVI) hydrocracking tail oil of the present invention, including following content：
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, fully rolls aftershaping, then dry, roasting, obtains catalyst carrier；
（2）With the dipping solution impregnation steps containing active metal component（1）The catalyst carrier for obtaining, then dry, roasting, obtains hydrocracking catalyst.
In the inventive method, step（1）Described modified Y- β composite molecular screens have following property after roasting：Aperture accounts for 15 ~ 50%, preferably the 25 ~ 46% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for 25 ~ 50%, preferably the 30 ~ 40% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is that between 7 ~ 40, specific surface area is 680 ~ 980m in molecular sieve2Between/g, pore volume is between 0.42 ~ 0.75ml/g；It is preferred that silica/alumina molar ratio is between 12 ~ 33, specific surface area is 750 ~ 950m2Between/g, pore volume is between 0.45 ~ 0.71ml/g.
In the inventive method, step（1）The preparation process of described modified Y- β composite molecular screens is as follows：
Compound concentration is organic aqueous alkali of 0.15 ~ 0.80mol/L, and organic base is tetraethyl ammonium hydroxide, TPAOH or TBAH.Y- β composite molecular screens are added in solution, the Y- β composite molecular screens of addition are Hydrogen, and silica/alumina molar ratio is 7 ~ 45, and specific surface area is 650 ~ 880m2The addition of/g, Y- β composite molecular screens is 1 with the mass ratio of water in solution:5 ~ 20, process 0.5 ~ 3 hour first at 50 ~ 90 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.
In the inventive method, step（1）The described molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 25 ~ 100；Specific surface area is 150 ~ 350m2/ g, preferably 180 ~ 280m2/g；Pore volume is 0.20 ~ 0.35cm3/ g, preferably 0.22 ~ 0.30cm3/g；Meleic acid acid amount is 0.10 ~ 0.35mmol/g, and preferred meleic acid acid amount is 0.18 ~ 0.28mmol/g.
In the inventive method, step（1）The preparation process of the described molecular sieve of modified ZSM-5-48 is as follows：
The ZSM-48 molecular sieves ammonium for not deviating from template is exchanged.Ammonium exchange times are at least 1 time, and exchange temperature is 60 ~ 110 DEG C, preferably 80 ~ 100 DEG C.Ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.1 ~ 2mol/L, and preferred ammonium salt is ammonium nitrate, and preferred concentration is 0.2 ~ 1.5mol/L.The liquid-solid ratio of exchange process（ml/g）For 5 ~ 30, preferably 10 ~ 20；Every time swap time is 0.5 ~ 2.0 hour, preferably 1 ~ 1.5 hour.
In the inventive method, step（1）The specific surface area of described macroporous aluminium oxide powder is 400 ~ 820m2/ g, preferably 450 ~ 750 m2/ g, pore volume is 0.55 ~ 1.55 Ml/g, preferably 0.75 ~ 1.05 ml/g；The particle diameter of macroporous aluminium oxide between 5 ~ 100nm, preferably 10 ~ 50nm.
In the inventive method, step（1）Described acid solution, can be the organic acid such as the mineral acids such as sulphuric acid, hydrochloric acid and nitric acid, or acetic acid and citric acid, preferred salpeter solution；Acid solutions are 2wt% ~ 10wt%, preferred 3wt% ~ 6wt%.
In the inventive method, step（1）Described baking temperature is 50 ~ 150 DEG C, and preferably 100 ~ 120 DEG C, drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and roasting time is 2 ~ 12 hours.
In the inventive method, step（2）Described is group vib metal and group VIII metal containing active metal component；The preferred tungsten of group vib metal（W）And molybdenum（Mo）, the preferred cobalt of group VIII metal（Co）And nickel（Ni）, dipping solution be formulated as those skilled in the art know；Dipping method is impregnated using supersaturation.
In the inventive method, step（2）Described baking temperature is 50 ~ 150 DEG C, and preferably 100 ~ 120 DEG C, drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
Hydrocracking catalyst prepared by the inventive method, based on catalyst weight percent, the content of each component is in catalyst：Roasting post-modification Y- β composite molecular screen components are generally 6 ~ 25%, preferably 10 ~ 15%；Roasting post-modification ZSM-48 molecular sieves are generally 25 ~ 50%, preferably 30 ~ 45%；Aluminium oxide is generally 6% ~ 25%, preferably 10 ~ 20%；Group vib metal（In terms of oxide）Generally 10% ~ 35%, preferably 18 ~ 28%；Group VIII metal（In terms of oxide）Generally 2% ~ 10%, preferably 4 ~ 8%.
Catalyst of the present invention process VGO when, reaction condition under hydrogen existence condition, 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 during liquid-1。
The inventive method has the advantage that compared to prior art：Template is always held in the framing structure of molecular sieve in modified Y- β composite molecular screen preparation process and in the modifying process of ZSM-48 molecular sieves, reduce structural deterioration of the modifying process to molecular sieve, the active sites for farthest remaining molecular sieve and the accessibility that improve active sites, the step of reducing molecular sieve modified process simultaneously, reduces the cost of molecular sieve.Catalyst in preparation process due to adopting the hydrogenation open-loop performance preferably strong molecular sieve of modified ZSM-5-48 of modified Y- β composite molecular screens and hydroisomerizing ability, enhance hydrogenation ring-opening reaction and the isomerization reaction of linear paraffin of VGO feedstock during the course of the reaction, the linear paraffin content in product is set to decline to a great extent, the viscosity index (VI) of hydrocracking tail oil product is greatly improved.Therefore, catalyst of the present invention has good hydrogenation open loop ability and isomerization performance, can greatly improve the viscosity index (VI) of hydrocracking tail oil.
Specific embodiment
The preparation process of the present invention is further illustrated with reference to embodiment, but following examples do not constitute the restriction to the inventive method.
Embodiment 1
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 8 hours at a temperature of 1000 DEG C, it is last in 550 DEG C of roasting temperatures 3 hours, obtain catalyst carrier；
（2）Prepare the metal impregnation solution of W and Ni, impregnation steps（1）The carrier of hydrocracking catalyst of gained, then filters, freeze-day with constant temperature 12 hours at a temperature of 100 DEG C, and finally constant temperature calcining 3 hours at a temperature of 500 DEG C, obtain hydrocracking catalyst C1.Catalyst property such as table 1.
Step（1）The preparation process of modified Y- β composite molecular screens is as follows：Compound concentration is the tetraethyl ammonium hydroxide solution of 0.55mol/L, adds silica/alumina molar ratio to be 35 in solution, and specific surface area is 765m2The Hydrogen Y- β composite molecular screens of/g, the addition of Y- β composite molecular screens is 1 with the mass ratio of water in solution:18, then process 1.5 hours at 60 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.Modified Y- β composite molecular screens have following property after roasting：Aperture accounts for the 26% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 38% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is 19 in molecular sieve, and specific surface area is 904m2/ g, pore volume is 0.69ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves ammonium for not deviating from template is exchanged 1 time, exchange temperature is 90 DEG C, ammonium salt used for 1.0mol/L ammonium chloride solution, the liquid-solid ratio of exchange process（ml/g）For 16, swap time is 1.0 hours.The molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 45, and specific surface area is 253m2/ g, pore volume is 0.24cm3/ g, meleic acid acid amount is 0.22mmol/g.
Embodiment 2
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 12 hours at a temperature of 110 DEG C, it is last in 550 DEG C of roasting temperatures 4 hours, obtain catalyst carrier；
（2）Prepare the metal impregnation solution of Mo and Co, impregnation steps（1）The carrier of hydrocracking catalyst of gained, then filters, freeze-day with constant temperature 12 hours at a temperature of 100 DEG C, and finally constant temperature calcining 6 hours at a temperature of 480 DEG C, obtain hydrocracking catalyst C2.Catalyst property such as table 1.
Step（1）The preparation process of modified Y- β composite molecular screens is as follows：Compound concentration is the TPAOH solution of 0.60mol/L, adds silica/alumina molar ratio to be 33 in solution, and specific surface area is 695m2The Hydrogen Y- β composite molecular screens of/g, the addition of Y- β composite molecular screens is 1 with the mass ratio of water in solution:8, then process 1.0 hours at 80 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.Modified Y- β composite molecular screens have following property after roasting：Aperture accounts for the 42% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 31% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is 15 in molecular sieve, and specific surface area is 882m2/ g, pore volume is 62ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves ammonium for not deviating from template is exchanged 1 time, exchange temperature is 85 DEG C, ammonium salt used for 1.2mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 11, swap time is 1.0 hours.The molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 75, and specific surface area is 275m2/ g, pore volume is 0.28cm3/ g, meleic acid acid amount is 0.19mmol/g.
Embodiment 3
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 6 hours at a temperature of 120 DEG C, it is last in 580 DEG C of roasting temperatures 3 hours, obtain catalyst carrier；
（2）Prepare the metal impregnation solution of W and Ni, impregnation steps（1）The carrier of hydrocracking catalyst of gained, then filters, freeze-day with constant temperature 8 hours at a temperature of 110 DEG C, and finally constant temperature calcining 5 hours at a temperature of 510 DEG C, obtain hydrocracking catalyst C3.Catalyst property such as table 1.
Step（1）The preparation process of modified Y- β composite molecular screens is as follows：Compound concentration is the TBAH solution of 0.35mol/L, adds silica/alumina molar ratio to be 18 in solution, and specific surface area is 780m2The Hydrogen Y- β composite molecular screens of/g, the addition of Y- β composite molecular screens is 1 with the mass ratio of water in solution:10, then process 1.5 hours at 70 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.Modified Y- β composite molecular screens have following property after roasting：Aperture accounts for the 35% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 34% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is 13 in molecular sieve, and specific surface area is 912m2/ g, pore volume is 0.68ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves ammonium for not deviating from template is exchanged 1 time, exchange temperature is 95 DEG C, ammonium salt used for 0.6mol/L ammonium chloride solution, the liquid-solid ratio of exchange process（ml/g）For 11, swap time is 1.5 hours.The molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 31, and specific surface area is 198m2/ g, pore volume is 0.23cm3/ g, meleic acid acid amount is 0.26mmol/g.
Embodiment 4
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 12 hours at a temperature of 100 DEG C, it is last in 480 DEG C of roasting temperatures 5 hours, obtain catalyst carrier；
（2）Prepare the metal impregnation solution of Mo and Co, impregnation steps（1）The carrier of hydrocracking catalyst of gained, then filters, freeze-day with constant temperature 10 hours at a temperature of 110 DEG C, and finally constant temperature calcining 4 hours at a temperature of 490 DEG C, obtain hydrocracking catalyst C4.Catalyst property such as table 1.
Step（1）The preparation process of modified Y- β composite molecular screens is as follows：Compound concentration is the tetraethyl ammonium hydroxide solution of 0.45mol/L, adds silica/alumina molar ratio to be 15 in solution, and specific surface area is 720m2The Hydrogen Y- β composite molecular screens of/g, the addition of Y- β composite molecular screens is 1 with the mass ratio of water in solution:12, then process 2.0 hours at 65 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.Modified Y- β composite molecular screens have following property after roasting：Aperture accounts for the 42% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 33% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is 12 in molecular sieve, and specific surface area is 850m2/ g, pore volume is 0.52ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves ammonium for not deviating from template is exchanged 1 time, exchange temperature is 92 DEG C, ammonium salt used for 0.4mol/L ammonium sulfate, the liquid-solid ratio of exchange process（ml/g）For 18, swap time is 1.5 hours.The molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 55, and specific surface area is 230m2/ g, pore volume is 0.25cm3/ g, meleic acid acid amount is 0.21mmol/g.
Comparative example
With embodiment 1, difference is that Y- β composite molecular screens are not modified process, obtains hydrocracking catalyst.Catalyst property such as table 1.
Catalytic performance test.
Evaluating apparatus are carried out using 200m1 small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Evaluate the raw materials used oil nature of catalyst activity and reaction process condition is shown in Table 2 and table 3, catalyst reaction performance comparison the results are shown in Table 4.When evaluating catalyst, raw oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, and the organic nitrogen content controlled when Hydrobon catalyst bed in raw oil is less than 10ppm.
The composition of the catalyst of table 1
The process conditions of table 2
The feedstock property of table 3
The catalyst reaction performance of table 4
Hydrocracking reaction result shows that compared with comparative example catalyst, when conversion ratio is identical, reaction temperature is low 3 ~ 10 DEG C, and the normal paraffin content in the viscosity index (VI) and tail oil of tail oil product is lower than comparative example for the catalyst of the present invention.Illustrate that catalyst prepared by the inventive method has the characteristics of hydrogenation open-loop performance is good, hydroisomerization ability is strong.

Claims (17)

1. a kind of method for preparing catalyst for producing high viscosity index (HVI) hydrocracking tail oil, it is characterised in that：Including following content：
（1）By macroporous aluminium oxide powder, modified Y- β composite molecular screens and the molecular sieve powder mix homogeneously of modified ZSM-5-48, acid solution is subsequently adding, fully rolls aftershaping, then dry, roasting, obtains catalyst carrier；
（2）With the dipping solution impregnation steps containing active metal component（1）The catalyst carrier for obtaining, then dry, roasting, obtains hydrocracking catalyst.
2. method according to claim 1, it is characterised in that：Step（1）Described modified Y- β composite molecular screens have following property after roasting：Aperture accounts for the 15 ~ 50% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 25 ~ 50% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is that between 7 ~ 40, specific surface area is 680 ~ 980m in molecular sieve2Between/g, pore volume is between 0.42 ~ 0.75ml/g.
3. method according to claim 2, it is characterised in that：Aperture accounts for the 25 ~ 46% of modified Y- β composite molecular screen total pore volumes for the pore volume of 2 ~ 6nm；Aperture accounts for the 30 ~ 40% of modified Y- β composite molecular screen total pore volumes for the pore volume of 6 ~ 10nm；Silica/alumina molar ratio is that between 12 ~ 33, specific surface area is 750 ~ 950m in molecular sieve2Between/g, pore volume is between 0.45 ~ 0.71ml/g.
4. method according to claim 1, it is characterised in that：Step（1）The preparation process of described modified Y- β composite molecular screens is as follows：Compound concentration is organic aqueous alkali of 0.15 ~ 0.80mol/L, organic base is tetraethyl ammonium hydroxide, TPAOH or TBAH, Y- β composite molecular screens are added in solution, the Y- β composite molecular screens of addition are Hydrogen, silica/alumina molar ratio is 7 ~ 45, and specific surface area is 650 ~ 880m2The addition of/g, Y- β composite molecular screens is 1 with the mass ratio of water in solution:5 ~ 20, process 0.5 ~ 3 hour first at 50 ~ 90 DEG C, it is washed out to pH value less than 10, finally obtain modified Y- β composite molecular screens.
5. method according to claim 1, it is characterised in that：Step（1）The described molecular sieve of modified ZSM-5-48 has following property after roasting：Molecular sieve silica/alumina molar ratio is 25 ~ 100；Specific surface area is 150 ~ 350m2/g；Pore volume is 0.20 ~ 0.35cm3/g；Meleic acid acid amount is 0.10 ~ 0.35mmol/g.
6. method according to claim 5, it is characterised in that：Specific surface area is 180 ~ 280m2/g；Pore volume is 0.22 ~ 0.30cm3/g；Meleic acid acid amount is 0.18 ~ 0.28mmol/g.
7. method according to claim 1, it is characterised in that：Step（1）The preparation process of the described molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves ammonium that template will not deviate from is exchanged, and ammonium exchange times are at least 1 time, and exchange temperature is 60 ~ 110 DEG C, and ammonium salt used be ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.1 ~ 2mol/L, the liquid-solid ratio of exchange process（ml/g）For 5 ~ 30；Every time swap time is 0.5 ~ 2.0 hour.
8. method according to claim 7, it is characterised in that：Exchange temperature is 80 ~ 100 DEG C, and ammonium salt is ammonium nitrate, and concentration is 0.2 ~ 1.5mol/L, the liquid-solid ratio of exchange process（ml/g）For 10 ~ 20；Every time swap time is 1 ~ 1.5 hour.
9. method according to claim 1, it is characterised in that：Step（1）The specific surface area of described macroporous aluminium oxide powder is 400 ~ 820m2/ g, pore volume is 0.55 ~ 1.55 ml/g, and the particle diameter of macroporous aluminium oxide is between 5 ~ 100nm.
10. method according to claim 1, it is characterised in that：Step（1）The specific surface area of described macroporous aluminium oxide powder is 450 ~ 750 m2/ g, pore volume is 0.75 ~ 1.05 ml/g；The particle diameter of macroporous aluminium oxide is in 10 ~ 50nm.
11. methods according to claim 1, it is characterised in that：Step（1）Described acid solutions are 2wt% ~ 10wt%.
12. methods according to claim 1, it is characterised in that：Step（1）Described baking temperature is 50 ~ 150 DEG C, and drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and roasting time is 2 ~ 12 hours.
13. methods according to claim 1, it is characterised in that：Step（2）Described is group vib metal and group VIII metal containing active metal component；The preferred tungsten of group vib metal（W）And molybdenum（Mo）, the preferred cobalt of group VIII metal（Co）And nickel（Ni）, dipping solution be formulated as those skilled in the art know；Dipping method is impregnated using supersaturation.
14. methods according to claim 1, it is characterised in that：Step（2）Described baking temperature is 50 ~ 150 DEG C, and drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
Catalyst prepared by a kind of 15. claim 1 to 14 either method, it is characterised in that：Based on catalyst weight percent, the content of each component is in catalyst：Roasting post-modification Y- β composite molecular screens component is 6 ~ 25%；Roasting post-modification ZSM-48 molecular sieves are 25 ~ 50%；Aluminium oxide is 6% ~ 25%；Group vib metal（In terms of oxide）For 10% ~ 35%；Group VIII metal（In terms of oxide）For 2% ~ 10%.
16. catalyst according to claim 15, it is characterised in that：Based on catalyst weight percent, the content of each component is in catalyst：Roasting post-modification Y- β composite molecular screens component is 10 ~ 15%；Roasting post-modification ZSM-48 molecular sieves are 30 ~ 45%；Aluminium oxide is 10 ~ 20%；Group vib metal（In terms of oxide）For 18 ~ 28%；Group VIII metal（In terms of oxide）For 4 ~ 8%.
Application of the catalyst described in 17. claim 15 when VGO is processed, it is characterised in that：Reaction condition under hydrogen existence condition, 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 during liquid-1。
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