CN106669801A - Catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and preparation method thereof - Google Patents

Catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and preparation method thereof Download PDF

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CN106669801A
CN106669801A CN201510750228.7A CN201510750228A CN106669801A CN 106669801 A CN106669801 A CN 106669801A CN 201510750228 A CN201510750228 A CN 201510750228A CN 106669801 A CN106669801 A CN 106669801A
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molecular sieve
catalyst
roasting
pore volume
ammonium
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CN106669801B (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

Abstract

The invention discloses a catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and a preparation method thereof. The preparation method of the catalyst comprises the following steps: 1, uniformly mixing micro-porous alumina powder, modified USY molecular sieve and modified ZSM-48 molecular sieve powder, adding an acid solution, fully rolling the obtained mixture, molding the rolled mixture, drying the molded mixture, and roasting the dried mixture to obtain a catalyst carrier; and 2, impregnating the catalyst carrier obtained in step 1 in an impregnating solution containing active metal components, drying the impregnated carrier, and roasting the dried impregnated carrier to obtain the hydrocracking catalyst. The catalyst prepared through the method has the characteristics of high hydrogenation ring opening activity and good hydrogenation isomerism, and can be used for producing high-quality hydrocracking tail oil as lubricating oil base oil.

Description

Produce catalyst of low linear paraffin content hydrocracking tail oil and preparation method thereof
Technical field
The present invention relates to a kind of catalyst for producing low linear paraffin content hydrocracking tail oil and preparation method thereof, the characteristics of the invention catalyst has high hydrogenation open loop ability and strong hydroisomerizing ability, can be used to produce the hydrocracking tail oil of high-quality.
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, especially reduce by the two ring above naphthene contents and linear paraffin content in hydrocracking tail oil product so as to can be used as the lube base oil of high-quality.
The content of the invention
For the deficiencies in the prior art, present invention offer is a kind of can to produce catalyst of low linear paraffin content hydrocracking tail oil and preparation method thereof.The catalyst of the present invention has the features such as hydrogenation open loop activity is high, hydroisomerizing performance is good, can be used for producing the hydrocracking tail oil of high-quality as lube base oil.Simultaneously by the innovation of molecular sieve modified technology, so that catalyst cost is greatly reduced.
The preparation method of catalyst of the present invention, including following content：
（1）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, 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）Described 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 3 ~ 6nm；Aperture accounts for the 25 ~ 50% of USY molecular sieve total pore volume, preferably 30 ~ 40% for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is that between 7 ~ 35, 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 ~ 28, 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 USY molecular sieve is as follows：
Compound concentration is the inorganic base aqueous solution of 0.35 ~ 1.20mol/L, and tetraethylammonium bromide, tetrapropyl bromine ammonium or TBAB are added in inorganic base aqueous solution, the concentration of tetraethylammonium bromide, tetrapropyl bromine ammonium or TBAB is 0.08 ~ 0.20mol/L.USY molecular sieve is added in solution, the USY molecular sieve of addition is Hydrogen, and silica/alumina molar ratio is 7 ~ 45, and specific surface area is 650 ~ 880m2/ g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:3 ~ 20, process 0.5 ~ 3 hour first at 50 ~ 90 DEG C, it is washed out to pH value less than 10, will obtain USY molecular sieve carries out ammonium exchange, obtains modified USY molecular sieve.Ammonium exchange times are at least 2 times, 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 0.5 ~ 3mol/L, and preferred ammonium salt is ammonium nitrate, and preferred concentration is 1 ~ 2mol/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 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 of non-roasting template is added in the inorganic base aqueous solution of 0.15 ~ 0.80mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:3 ~ 20, constant temperature stir process 0.5 ~ 3 hour at 50 ~ 90 DEG C is washed out to pH value less than 10, finally the molecular sieve of modified ZSM-5-48 is 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 pore volume of described little porous aluminum oxide is 0.25 ~ 0.55ml/g, and preferably 0.3 ~ 0.48ml/g, specific surface is 180 ~ 420m2/ g, preferably 200 ~ 390 m2/g。
In the inventive method, step（1）Described acid solution, can be the organic acids such as the inorganic acids such as sulfuric 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 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：Roasting post-modification USY molecular sieve is generally 5 ~ 20%, preferably 8 ~ 15%；Roasting post-modification ZSM-48 molecular sieves are generally 20 ~ 50%, preferably 25 ~ 45%；Aluminum oxide is generally 5% ~ 30%, preferably 10 ~ 20%；Group vib metal（In terms of oxide）Generally 10% ~ 30%, preferably 18 ~ 25%；Group VIII metal（In terms of oxide）Generally 2% ~ 10%, preferably 3 ~ 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：This catalyst employs the higher modified USY molecular sieve of hydrogenation open loop ability and the more preferable molecular sieve of modified ZSM-5-48 of isomery performance in preparation process, enhance hydrogenation ring-opening reaction and the isomerization reaction of linear paraffin of raw material during the course of the reaction, two ring above cycloalkane and linear paraffin content in the hydrocracking tail oil for finally giving are made to decline to a great extent, the viscosity index (VI) of hydrocracking tail oil product is greatly improved.Therefore, the hydrocracking tail oil by the use of this Catalyst Production can be used as the lube base oil of high-quality.
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）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 8 hours under the conditions of 110 DEG C, last roasting 4 hours under the conditions of 550 DEG C, obtain catalyst carrier；
（2）Prepare the metal impregnation solution impregnation step of W and Ni（1）The catalyst carrier for obtaining, is then dried 8 hours under the conditions of 120 DEG C, and finally roasting 6 hours under the conditions of 480 DEG C, obtain hydrocracking catalyst.Catalyst property such as table 1.
Step（1）The preparation process of modified USY molecular sieve is as follows：Compound concentration is the sodium hydrate aqueous solution of 0.55mol/L, and is added thereto to 4-propyl bromide, and 4-propyl bromide concentration is 0.18mol/L, then adds silica/alumina molar ratio to be 35 in solution, and specific surface area is 780m2The Hydrogen USY molecular sieve of/g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:5, process 1.5 hours at 70 DEG C, wash to pH value less than 10, then the molecular sieve for obtaining is carried out into ammonium exchange, obtain modified USY molecular sieve.Ammonium exchange times are 2 times, and exchange temperature is 90 DEG C, ammonium salt used for 2.0mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 15, each swap time is 1.5 hours.Modified USY molecular sieve has following property after roasting：Aperture accounts for the 28% of USY molecular sieve total pore volume for the pore volume of 3 ~ 6nm；Aperture accounts for the 32% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is that specific surface area is 896m between 18 in molecular sieve2Between/g, pore volume is between 0.56ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 of non-roasting template is added in the sodium hydroxide solution of 0.5mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:5, constant temperature stir process 1.0 hours at 70 DEG C are washed out to pH value less than 10, and the molecular sieve of modified ZSM-5-48 is carried out into ammonium exchange.Ammonium exchange times are 1 time, and exchange temperature is 90 DEG C, ammonium salt used for 0.5mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 12, 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 55, and specific surface area is 270m2/ g, pore volume is 0.28cm3/ g, meleic acid acid amount is 0.22mmol/g.
Embodiment 2
（1）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 6 hours under the conditions of 100 DEG C, last roasting 10 hours under the conditions of 550 DEG C, obtain catalyst carrier；
（2）Prepare the metal impregnation solution impregnation step of W and Ni（1）The catalyst carrier for obtaining, is then dried 10 hours under the conditions of 110 DEG C, and finally roasting 4 hours under the conditions of 490 DEG C, obtain hydrocracking catalyst.Catalyst property such as table 1.
Step（1）The preparation process of modified USY molecular sieve is as follows：Compound concentration is the sodium hydroxide solution of 0.85mol/L, and is added thereto to tetraethylammonium bromide, and the concentration of tetraethylammonium bromide is 0.08 ~ 0.20mol/L, adds silica/alumina molar ratio to be 25 in solution, and specific surface area is 785m2The Hydrogen USY molecular sieve of/g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:8, process 2.0 hours at 60 DEG C, wash to pH value less than 10, then will obtain molecular sieve carries out ammonium exchange, obtains modified USY molecular sieve.Ammonium exchange times are 2 times, and exchange temperature is 95 DEG C, ammonium salt used for 1.5mol/L ammonium chloride solution, the liquid-solid ratio of exchange process（ml/g）For 12, each swap time is 1.0 hours.Modified USY molecular sieve has following property after roasting：Aperture accounts for the 28% of USY molecular sieve total pore volume for the pore volume of 3 ~ 6nm；Aperture accounts for the 40% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is 15 in molecular sieve, and specific surface area is 924m2/ g, pore volume is 0.66ml/g.
Step（1）The preparation process of the molecular sieve of modified ZSM-5-48 is as follows：The ZSM-48 of non-roasting template is added in the sodium hydroxide solution of 0.30mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:10, constant temperature stir process 1.0 hours at 80 DEG C are washed out to pH value less than 10, finally the molecular sieve of modified ZSM-5-48 are carried out into ammonium exchange.Ammonium exchange times are 1 time, and exchange temperature is 95 DEG C, ammonium salt used for 1.0mol/L ammonium nitrate 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 255m2/ g, pore volume is 0.24cm3/ g, meleic acid acid amount is 0.20mmol/g.
Embodiment 3
（1）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 8 hours under the conditions of 110 DEG C, last roasting 6 hours under the conditions of 540 DEG C, obtain catalyst carrier；
（2）Prepare the metal impregnation solution impregnation step of Mo and Co（1）The catalyst carrier for obtaining, is then dried 6 hours under the conditions of 100 DEG C, and finally roasting 4 hours under the conditions of 510 DEG C, obtain hydrocracking catalyst.Catalyst property such as table 1.
Step（1）The preparation process of modified USY molecular sieve is as follows：Compound concentration is the sodium hydroxide solution of 0.45mol/L, and is added thereto to TBAB, and the concentration of TBAB is 0.12mol/L.Silica/alumina molar ratio is added to be 18 in solution, specific surface area is 740m2The Hydrogen USY molecular sieve of/g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:18, process 1.5 hours at 65 DEG C, it is washed out to pH value less than 10, will obtain USY molecular sieve carries out ammonium exchange, obtains modified USY molecular sieve.Ammonium exchange times are 2 times, and exchange temperature is 100 DEG C, and ammonium salt used is, the ammonium chloride solution of 1.5mol/L, the liquid-solid ratio of exchange process（ml/g）For 18, each swap time is 1.5 hours.Modified USY molecular sieve has following property after roasting：Aperture accounts for the 25% of USY molecular sieve total pore volume for the pore volume of 3 ~ 6nm；Aperture accounts for the 38% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is 13 in molecular sieve, and specific surface area is 875m2/ 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 of non-roasting template is added in the sodium hydroxide solution of 0.25mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:16, constant temperature stir process 1.0 hours at 75 DEG C are washed out to pH value less than 10, finally the molecular sieve of modified ZSM-5-48 are carried out into ammonium exchange.Ammonium exchange times are 1 time, and exchange temperature is 85 DEG C, ammonium salt used for 0.8mol/L ammonium sulfate, the liquid-solid ratio of exchange process（ml/g）For 14, 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 65, and specific surface area is 210m2/ g, pore volume is 0.22cm3/ g, meleic acid acid amount is 0.18mmol/g.
Embodiment 4
（1）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, aftershaping is fully rolled, is then dried 8 hours under the conditions of 100 DEG C, last roasting 8 hours under the conditions of 600 DEG C, obtain catalyst carrier；
（2）Prepare the metal impregnation solution impregnation step of Mo and Co（1）The catalyst carrier for obtaining, is then dried 6 hours under the conditions of 120 DEG C, and finally roasting 6 hours under the conditions of 470 DEG C, obtain hydrocracking catalyst.Catalyst property such as table 1.
Step（1）The preparation process of modified USY molecular sieve is as follows：Compound concentration is the sodium hydroxide solution of 0.92mol/L, and is added thereto to tetrapropyl bromine ammonium, and the concentration of tetrapropyl bromine ammonium is 0.16mol/L.Silica/alumina molar ratio is added to be 29 in solution, specific surface area is 716m2The Hydrogen USY molecular sieve of/g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:6, process 1.0 hours at 70 DEG C, it is washed out to pH value less than 10, will obtain USY molecular sieve carries out ammonium exchange, obtains modified USY molecular sieve.Ammonium exchange times are 2 times, and exchange temperature is 92 DEG C, ammonium salt used for 1.8mol/L ammonium nitrate solution, the liquid-solid ratio of exchange process（ml/g）For 17, each swap time is 1.5 hours.Modified USY molecular sieve has following property after roasting：Aperture accounts for the 31% of USY molecular sieve total pore volume for the pore volume of 3 ~ 6nm；Aperture accounts for the 32% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is 15 in molecular sieve, and specific surface area is 864m2/ 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 of non-roasting template is added in the sodium hydrate aqueous solution of 0.72mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:8, constant temperature stir process 1.5 hours at 55 DEG C are washed out to pH value less than 10, finally the molecular sieve of modified ZSM-5-48 are carried out into ammonium exchange.Ammonium exchange times are 1 time, and exchange temperature is 90 DEG C, ammonium salt used for 0.6mol/L ammonium nitrate 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 35, and specific surface area is 272m2/ g, pore volume is 0.26cm3/ g, meleic acid acid amount is 0.24mmol/g.
Comparative example
With embodiment 1, difference is that USY molecular sieve is 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, 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 of the catalyst of table 1
Sequence number USY molecular sieve (wt%) ZSM-48 molecular sieves (wt%) Nickel oxide (wt%) Cobalt oxide (wt %) Tungsten oxide (wt %) Molybdenum oxide (wt %)
Embodiment 1 8.4 28.0 4.8 --- 21.5 ---
Embodiment 2 14.0 42.0 4.5 --- 23.6 ---
Embodiment 3 11.2 35.0 --- 5.6 --- 18.9
Embodiment 4 10.5 42.0 --- 6.2 --- 21.6
Comparative example 8.4 28.0 5.0 --- 20.9 ---
Roasting post-modification USY molecular sieve is generally 5 ~ 20%, preferably 8 ~ 15%；Roasting post-modification ZSM-48 molecular sieves are generally 20 ~ 50%, preferably 25 ~ 45%.
The process conditions of table 2
Pressure/MPa 14.7
Air speed (R1/R2)/h-1 1.2/1.8
Hydrogen to oil volume ratio 1200
Conversion ratio/wt% 70
The feedstock property of table 3
Density（20℃）, g/cm3 0.9159
Boiling range/DEG C
IBP/10% 328/376
30%/50% 400/430
70%/90% 455/499
95%/FBP 514/536
Condensation point/DEG C 32
Carbon residue, wt% 0.32
S, wt% 1.60
N, wt% 0.1575
The catalyst reaction performance of table 4
Catalyst Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example
Reaction temperature, DEG C 379 375 377 378 381
Tail oil viscosity index (VI) 138 133 134 142 128
Tail oil normal paraffin content, wt% 11.1 10.5 12.2 11.3 15.8
The ring above Determination of Alkane Content of tail oil two, wt% 20.2 18.3 19.9 18.6 22.3
BMCI values 9.6 8.9 9.6 9.2 11.2
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 2 ~ 6 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 (21)

1. a kind of preparation method of the catalyst for producing low linear paraffin content hydrocracking tail oil, it is characterised in that：Including following content：
（1）Aperture alumina powder, modified USY molecular sieve and the molecular sieve powder of modified ZSM-5-48 are well mixed, acid solution is subsequently adding, 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）Described 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 3 ~ 6nm；Aperture accounts for the 25 ~ 50% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is that between 7 ~ 35, 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：Described modified USY molecular sieve has following property after roasting：Aperture accounts for the 25 ~ 35% of USY molecular sieve total pore volume for the pore volume of 3 ~ 6nm；Aperture accounts for the 30 ~ 40% of USY molecular sieve total pore volume for the pore volume of 7 ~ 11nm；Silica/alumina molar ratio is that between 12 ~ 28, 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 USY molecular sieve is as follows：First, compound concentration is the inorganic base aqueous solution of 0.35 ~ 1.20mol/L, and tetraethylammonium bromide, tetrapropyl bromine ammonium or TBAB are added in inorganic base aqueous solution, the concentration of tetraethylammonium bromide, tetrapropyl bromine ammonium or TBAB is 0.08 ~ 0.20mol/L；Then to solution in add USY molecular sieve, the USY molecular sieve of addition is Hydrogen, and silica/alumina molar ratio is 7 ~ 45, and specific surface area is 650 ~ 880m2/ g, the addition of USY molecular sieve is 1 with the mass ratio of water in solution:3~20；It is last to process 0.5 ~ 3 hour at 50 ~ 90 DEG C, wash to pH value and less than 10 and carry out ammonium exchange, obtain modified USY molecular sieve.
5. method according to claim 4, it is characterised in that：Ammonium exchange times are at least 2 times, and exchange temperature is 60 ~ 110 DEG C.
6. method according to claim 4, it is characterised in that：Ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.5 ~ 3mol/L.
7. method according to claim 4, 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.
8. 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.
9. method according to claim 8, 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.
10. 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 of non-roasting template is added in the inorganic base aqueous solution of 0.15 ~ 0.80mol/L, the addition of ZSM-48 molecular sieves is 1 with the mass ratio of water in solution:3 ~ 20, constant temperature stir process 0.5 ~ 3 hour at 50 ~ 90 DEG C is washed out to pH value less than 10, finally the molecular sieve of modified ZSM-5-48 is carried out into ammonium exchange.
11. methods according to claim 10, it is characterised in that：Ammonium exchange times are at least 1 time, and exchange temperature is 60 ~ 110 DEG C.
12. methods according to claim 11, 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.
13. methods according to claim 11, 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.
14. methods according to claim 1, it is characterised in that：Step（1）The pore volume of described little porous aluminum oxide is 0.25 ~ 0.55ml/g, and specific surface is 180 ~ 420m2/g。
15. methods according to claim 1, it is characterised in that：Step（1）Described acid is one or more in sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid；Acid solutions are 2wt% ~ 10wt%.
16. 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.
17. 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）.
18. 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 19. claim 1 to 18 either method, it is characterised in that：Based on catalyst weight percent, the content of each component is in catalyst：Roasting post-modification USY molecular sieve is 5 ~ 20%；Roasting post-modification ZSM-48 molecular sieves are 20 ~ 50%；Aluminum oxide is 5% ~ 30%；Group vib metal is calculated as 10% ~ 30% with oxide；Group VIII metal is calculated as 2% ~ 10% with oxide.
20. catalyst according to claim 19, it is characterised in that：Roasting post-modification USY molecular sieve is 8 ~ 15%；Roasting post-modification ZSM-48 molecular sieves are 25 ~ 45%；Aluminum oxide is 10 ~ 20%；Group vib metal is calculated as 18 ~ 25% with oxide；Group VIII metal is calculated as 3 ~ 8% with oxide.
Application of the catalyst described in 21. claims 19 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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