CN106669802A - Catalyst for producing high-quality hydrocracked tail oil and preparation method for catalyst - Google Patents

Catalyst for producing high-quality hydrocracked tail oil and preparation method for catalyst Download PDF

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CN106669802A
CN106669802A CN201510750237.6A CN201510750237A CN106669802A CN 106669802 A CN106669802 A CN 106669802A CN 201510750237 A CN201510750237 A CN 201510750237A CN 106669802 A CN106669802 A CN 106669802A
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molecular sieve
catalyst
pore volume
roasting
modified
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CN106669802B (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
    • B01J29/7861—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

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalyst for producing high-quality hydrocracked tail oil and a preparation method for the catalyst. The preparation method for the catalyst comprises the following steps: (1) preparing an organic-base aqueous solution with the concentration of 0.15mol/L to 0.80mol/L, adding USY molecular sieves into the solution, carrying out treatment for 0.5 to 3 hours at the temperature of 50 DEG C to 90 DEG C so as to prepare modified USY molecular sieves, then, adding fumed silica and modified ZSM-48 molecular sieve powder into the modified USY molecular sieves, carrying out thorough milling, then, carrying out shaping, and then, carrying out drying and roasting, so as to obtain a catalyst support; (2) dipping the catalyst support obtained in the step (1) with a dipping solution containing active metal components, and then, carrying out drying and roasting, thereby obtaining the hydrocracking catalyst. The prepared hydrocracked tail oil has the characteristics of low straight-chain paraffin content, high isohydrocarbon content and high viscosity index and can serve as high-quality lubricating-oil base oil.

Description

Catalyst of production high-quality hydrocracking tail oil and preparation method thereof
Technical field
The present invention relates to a kind of catalyst for producing high viscosity index (HVI) hydrocracking tail oil and preparation method thereof, the characteristics of invention catalyst has high hydrogenation open loop ability and strong hydroisomerizing ability, the hydrocracking tail oil linear paraffin content of production is low, viscosity index (VI) is high, can be used as lube base oil.
Background technology
The features such as hydrocracking technology has big strong adaptability to raw material, production operation and products scheme flexibility, 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 naphtha 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 macromolecular 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 polycyclic 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 polycyclic 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 polycyclic 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, present invention offer is a kind of to produce catalyst of hydrocracking tail oil of high-quality and preparation method thereof.The catalyst hydrogenation open loop activity of the present invention is high, hydroisomerizing performance is good, the characteristics of the hydrocracking tail oil of production has low linear paraffin content, high isomery hydrocarbon content and high viscosity index (VI), can be used as the lube base oil of high-quality.Simultaneously by the reduction of molecular sieve modified step, the cost of molecular sieve is greatly reduced, so as to reduce the cost of catalyst.
The preparation method of hydrocracking catalyst of the present invention includes following content：
（1）Compound concentration is organic aqueous alkali of 0.15 ~ 0.80mol/L, organic base is tetraethyl ammonium hydroxide, TPAOH or TBAH, USY molecular sieve is added in solution, process at 50 ~ 90 DEG C and modified USY molecular sieve is obtained within 0.5 ~ 3 hour, it is subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, aftershaping is fully rolled, 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）The modified USY molecular sieve has following property after roasting：Aperture accounts for the 15 ~ 40% of USY molecular sieve total pore volume, preferably 25 ~ 35% for the pore volume of 2 ~ 6nm；Aperture accounts for the 25 ~ 50% of USY molecular sieve total pore volume, preferably 30 ~ 40% for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is that between 7 ~ 45, 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 9 ~ 33, specific surface area is 750 ~ 950m2Between/g, pore volume is between 0.45 ~ 0.71ml/g.
In the inventive method, step（1）The USY molecular sieve of the addition is Hydrogen, and silica/alumina molar ratio is 8 ~ 50, and specific surface area is 650 ~ 840m2/ g, the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali:5~20.
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 for not deviating from template are carried out into ammonium exchange.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 of described aerosil is 50 ~ 300m2/ g, preferably 100 ~ 200m2/g。
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 using supersaturation dipping.
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：Modified USY molecular sieve component is generally 8 ~ 35%, preferably 11 ~ 25%；The molecular sieve of modified ZSM-5-48 is generally 25 ~ 60%, preferably 35 ~ 55%；Silica is generally 6% ~ 35%, preferably 8 ~ 25%；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：Using the inorganic base in its modified solution in USY molecular sieve modifying process, both the effect for serving filling molecular sieve pore passage serves the effect of binding agent with the silica for adding simultaneously, so that the preparation process of catalyst is simple, step shortens, and cost is occurred in that and is greatly reduced.Simultaneously template is always held in the skeleton structure of molecular sieve in the preparation process of molecular sieve modified process and carrier; therefore reduce modifying process to destroy the structure of molecular sieve; the active sites for protecting molecular sieve and the accessibility that improve molecular sieve active sites; the formation of pore passage structure in carrier forming process is also beneficial to simultaneously, considerably increases the diffusion of carrier.Therefore, catalyst of the present invention enhances hydrogenation ring-opening reaction and the isomerization reaction of VGO feedstock during the course of the reaction, makes the linear paraffin content in the product for finally giving decline to a great extent, and the viscosity index (VI) of hydrocracking tail oil product is greatly improved.
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）Compound concentration is the TPAOH aqueous solution of 0.45mol/L, and USY molecular sieve is added in solution, and the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali:5.Process at 70 DEG C and modified USY molecular sieve is obtained within 2.0 hours, be subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, fully roll aftershaping, then freeze-day with constant temperature 6 hours at 100 DEG C.Then roasting 5 hours at 550 DEG C, 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 100 DEG C.Then roasting 4 hours at 490 DEG C, obtain hydrocracking catalyst C1.Catalyst property such as table 1.
Step（1）Modified USY molecular sieve has following property after roasting：Aperture accounts for the 30% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 35% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is 21 in molecular sieve, and specific surface area is 869m2/ g, pore volume is 0.62ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves for not deviating from template are carried out into 1 ammonium to exchange, exchange temperature is 85 DEG C, ammonium salt used for 0.9mol/L ammonium chloride 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 76, and specific surface area is 276m2/ g, pore volume is 0.28cm3/ g, meleic acid acid amount is 0.18mmol/g.
Embodiment 2
（1）Compound concentration is the tetraethyl ammonium hydroxide aqueous solution of 0.55mol/L, and USY molecular sieve is added in solution, and the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali: 20.Process 1.5 hours first at 60 DEG C, be subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, fully roll aftershaping, then freeze-day with constant temperature 4 hours at 110 DEG C.Then roasting 6 hours at 600 DEG C, 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 5 hours at 110 DEG C.Then roasting 6 hours at 550 DEG C, obtain hydrocracking catalyst C2.Catalyst property such as table 1.
Step（1）Modified USY molecular sieve has following property after roasting：Aperture accounts for the 27% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 37% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is 15 in molecular sieve, and specific surface area is 902m2/ g, pore volume is 0.65ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves for not deviating from template are carried out into 1 ammonium to exchange, exchange temperature is 80 DEG C, ammonium salt used for 0.2mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 18, 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 56, and specific surface area is 250m2/ g, pore volume is 0.25cm3/ g, meleic acid acid amount is 0.21mmol/g.
Embodiment 3
（1）Compound concentration is the TPAOH aqueous solution of 0.20mol/L, and USY molecular sieve is then added in solution, and the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali:10.Process 1.0 hours first at 80 DEG C, be subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, fully roll aftershaping, then freeze-day with constant temperature 6 hours at 120 DEG C.Then roasting 3 hours at 580 DEG C, 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 6 hours at 120 DEG C.Then roasting 6 hours at 480 DEG C, obtain hydrocracking catalyst C3.Catalyst property such as table 1.
Step（1）Modified USY molecular sieve has following property after roasting：Aperture accounts for the 34% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 32% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is 25 in molecular sieve, and specific surface area is 812m2/ 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 for not deviating from template are carried out into 1 ammonium to exchange, exchange temperature is 90 DEG C, ammonium salt used for 1.5mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 15, 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 40, and specific surface area is 210m2/ g, pore volume is 0.23cm3/ g, meleic acid acid amount is 0.26mmol/g.
Embodiment 4
（1）Compound concentration is the tetraethyl ammonium hydroxide aqueous solution of 0.64mol/L, and USY molecular sieve is added in solution, and the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali:15.Process 1.5 hours first at 65 DEG C, be subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, fully roll aftershaping, then freeze-day with constant temperature 10 hours at 110 DEG C.Then roasting 6 hours at 480 DEG C, 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 4 hours at 120 DEG C.Then roasting 3 hours at 510 DEG C, obtain hydrocracking catalyst C4.Catalyst property such as table 1.
Step（1）Modified USY molecular sieve has following property after roasting：Aperture accounts for the 35% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 30% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is 10 in molecular sieve, and specific surface area is 850m2/ g, pore volume is 0.70ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 molecular sieves for not deviating from template are carried out into 1 ammonium to exchange, exchange temperature is 98 DEG C, ammonium salt used for 1.2mol/L ammonium chloride solution, the liquid-solid ratio of exchange process（ml/g）For 15, 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 28, and specific surface area is 198m2/ g, pore volume is 0.22cm3/ g, meleic acid acid amount is 0.28mmol/g.
Comparative example
It is well mixed using conventional USY molecular sieve, silica, the molecular sieve of modified ZSM-5-48, is subsequently adding acid solution, fully roll aftershaping, remaining preparation condition obtains hydrocracking catalyst BC1 with embodiment 3.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, feedstock 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 feedstock oil is less than 10ppm.
The composition and pore structure property 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, the catalyst of the present invention is compared with comparative example catalyst, when conversion ratio is identical, reaction temperature is low 3 ~ 13 DEG C, and the BMCI values of n-alkane and two ring above Determination of Alkane Content and tail oil in viscosity index (VI), the tail oil of tail oil product are lower than comparative example.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 preparation method of the catalyst for producing high-quality hydrocracking tail oil, it is characterised in that：Including following content：
（1）Compound concentration is organic aqueous alkali of 0.15 ~ 0.80mol/L, organic base is tetraethyl ammonium hydroxide, TPAOH or TBAH, USY molecular sieve is added in solution, process at 50 ~ 90 DEG C and modified USY molecular sieve is obtained within 0.5 ~ 3 hour, it is subsequently adding aerosil and the molecular sieve powder of modified ZSM-5-48, aftershaping is fully rolled, 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）The modified USY molecular sieve has following property after roasting：Aperture accounts for the 15 ~ 40% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 25 ~ 50% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is that between 7 ~ 45, 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 ~ 35% of USY molecular sieve total pore volume for the pore volume of 2 ~ 6nm；Aperture accounts for the 30 ~ 40% of USY molecular sieve total pore volume for the pore volume of 7 ~ 10nm；Silica/alumina molar ratio is that between 9 ~ 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 USY molecular sieve of the addition is Hydrogen, and silica/alumina molar ratio is 8 ~ 50, and specific surface area is 650 ~ 840m2/ g, the addition of USY molecular sieve is 1 with the water quality ratio in organic aqueous alkali:5~20.
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：Step（1）The described molecular sieve of modified ZSM-5-48 has following property after roasting：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 for not deviating from template are carried out into ammonium exchange.
8. method according to claim 7, it is characterised in that：Ammonium exchange times are at least 1 time, and exchange temperature is 60 ~ 110 DEG C.
9. method according to claim 7, it is characterised in that：Ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.1 ~ 2mol/L.
10. method according to claim 7, it is characterised in that：The liquid-solid ratio of exchange process（ml/g）For 5 ~ 30；Every time swap time is 0.5 ~ 2.0 hour.
11. methods according to claim 1, it is characterised in that：Step（1）The specific surface of described aerosil is 50 ~ 300m2/g。
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/or 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）.
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 15. claim 1 to 15 either method, it is characterised in that：Based on catalyst weight percent, the content of each component is in catalyst：Modified USY molecular sieve component is 8 ~ 35%；The molecular sieve of modified ZSM-5-48 is 25 ~ 60%；Silica is 6% ~ 35%；Group vib metal is calculated as 10% ~ 35% with oxide；Group VIII metal is calculated as 2% ~ 10% with oxide.
16. catalyst according to claim 15, it is characterised in that：Modified USY molecular sieve component is 11 ~ 25%；The molecular sieve of modified ZSM-5-48 is 35 ~ 55%；Silica is 8 ~ 25%；Group vib metal is calculated as 18 ~ 28% with oxide；Group VIII metal is calculated as 4 ~ 8% with oxide.
Application of the catalyst described in 17. claims 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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CN101837299A (en) * 2009-03-18 2010-09-22 中国石油天然气股份有限公司 Catalyst used in hydrogenation modification of catalytic gasoline and preparation method thereof
CN102309975A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing hydrocracking catalyst
US20120080357A1 (en) * 2010-09-30 2012-04-05 Exxonmobil Research And Engineering Company Hydrocracking process selective for improved distillate and improved lube yield and properties
CN103055922A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Preparation method of bulk phase hydrocracking catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101837299A (en) * 2009-03-18 2010-09-22 中国石油天然气股份有限公司 Catalyst used in hydrogenation modification of catalytic gasoline and preparation method thereof
CN102309975A (en) * 2010-07-07 2012-01-11 中国石油化工股份有限公司 Method for preparing hydrocracking catalyst
US20120080357A1 (en) * 2010-09-30 2012-04-05 Exxonmobil Research And Engineering Company Hydrocracking process selective for improved distillate and improved lube yield and properties
CN103055922A (en) * 2011-10-21 2013-04-24 中国石油化工股份有限公司 Preparation method of bulk phase hydrocracking catalyst

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