CN107344104A - A kind of hydrocracking catalyst for producing high-quality ethylene raw material and its preparation method and application - Google Patents

A kind of hydrocracking catalyst for producing high-quality ethylene raw material and its preparation method and application Download PDF

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CN107344104A
CN107344104A CN201610288625.1A CN201610288625A CN107344104A CN 107344104 A CN107344104 A CN 107344104A CN 201610288625 A CN201610288625 A CN 201610288625A CN 107344104 A CN107344104 A CN 107344104A
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molecular sieve
catalyst
preparation
hydrocracking catalyst
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CN107344104B (en
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秦波
杜艳泽
柳伟
高杭
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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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/60—Synthesis on support
    • B01J2229/62—Synthesis on support in or on other molecular sieves

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

Abstract

The present invention discloses a kind of hydrocracking catalyst for producing high-quality ethylene raw material and its preparation method and application.The preparation method includes following content：（1）Under agitation, in the pressure vessel for one or more of organic alkali solutions that Y type molecular sieve is added in the tetraethyl ammonium hydroxide, TPAOH or TBAH that are 0.05 ~ 0.35mol/L equipped with concentration, it is and system is closed, 0.2 ~ 1.0MPa is boosted to using compressed air, nitrogen or inert gas etc. is passed through into pressure vessel, then heat to 50 ~ 90 DEG C, constant temperature is handled 0.5 ~ 3 hour, is unloaded and is depressed into normal pressure；（2）White carbon and active metal component are added to step（1）It is well mixed in mixture, then fully rolls aftershaping, is then dried, is calcined, obtain hydrocracking catalyst.Hydrocracking catalyst prepared by this method has the characteristics of being hydrocracked property height and good product selectivity, can be used for producing high-quality ethylene cracking material.

Description

A kind of hydrocracking catalyst for producing high-quality ethylene raw material and preparation method thereof and Using
Technical field
The present invention relates to a kind of hydrocracking catalyst for being used to produce high-quality ethylene raw material and its preparation method and application.
Background technology
In hydrocracked product, heavy naphtha fraction low-sulfur, low nitrogen and high arene underwater content can be directly as high-quality Catalytic reforming raw material；And C2 ~ C4 light hydrocarbon components, light naphthar and unconverted tail oil fraction low-sulfur, low nitrogen and saturated hydrocarbon content Height, preferable preparing ethylene by steam cracking raw material can be used as.The characteristics of China's processing crude oil light component yield is low is limited by, is compared In ethylene cracking materials such as straight-run naphtha, lighter hydrocarbons, hydrocracking tail oil has cheap, triolefin high income, skill as feed ethylene The advantages that art maturation and production process clean, from the point of view of economy and operability, hydrocracking tail oil is former as ethylene unit Material has irreplaceability within considerable time.
The bifunctional catalyst that hydrocracking catalyst is made up of hydrogenating function and cracking function, wherein hydrogenating function are There is provided by hydrogenation active metals, improve the Hydrogenation of hydrocracking catalyst, be advantageous to the saturation of aromatic hydrocarbons；Cracking function be by What amorphous silicon aluminium or molecular sieve provided, it can crack the macromolecular of long-chain and make the further open loop of polycyclic aromatic hydrocarbon after saturation Conversion.At present, the cracking center in most of hydrocracking catalysts is provided by molecular sieve, therefore by improving the property of molecular sieve Can be a feasible approach to improve the performance of catalyst.Ke Ming etc.（The molecular sieve modified progress of MCM-22 [J], the present age Chemical industry, 2015,44（11）：2629~2634）By the knot that MCM-22 molecular sieves are carried out to molecular sieve after alkali process and hydro-thermal process Structure changes, it is found that molecular sieve is while original microcellular structure is maintained after alkali process, more meso-hole structures occur And macroporous structure.Cheng Shiwen etc.（Influence [J] of the Y molecular sieve modification to its structure and acidity, petrochemical technology and application, 2011,29 （5）：401~405）Result of study show modified by hydro-thermal process, hydro-thermal-oxalic acid treatment etc., Y molecular sieve can be formed greatly Secondary pore is measured, this explanation steam treatment can play a part of reaming, can further increase Jie after oxalic acid removing non-framework aluminum Hole pore volume can simultaneously be measured in the acids type of interior regulation Y molecular sieve and acid in a big way, and modified total acid content declines, after hydro-thermal process Strong L acid amount increase, and hydro-thermal-oxalic acid combination dealuminzation can improve strong B acid amount.Qin Zhen etc.（The small-grain Y molecule of different silica alumina ratios The physicochemical property of sieve and its performance [J] is hydrocracked, petrochemical industry chemical industry, 2013,42（10）：1080~1085）Result of study show The skeleton stability of small-grain Y molecular sieve increases with the increase of silica alumina ratio；Acid amount is reduced with the increase of silica alumina ratio, different silicon The small-grain Y molecular sieve of aluminum ratio has different acid site distributions；The pore structure of small-grain Y molecular sieve with silica alumina ratio change simultaneously It is not that small-grain Y molecular sieve has larger specific surface area it is obvious that compared with industrial Y molecular sieve, this has to heavy oil conversion Profit.The small-grain Y acidic zeolite that silica alumina ratio is 5.2 is moderate, and duct is flourishing, and skeleton stability is preferable, using its adding as carrier The activity of hydrogen Cracking catalyst is high, and light oil selectivity and industrial chemicals high income, are preferable light oil type hydrogen cracking catalysts Active component.Wang Yingjun etc.（Progress [J] molecular sieve modified super steady Y, silicate circular, 2015,34（11）：3243 ~3250）Describe the Dealumination, load sour modification, loading cation or oxide modifying and molecular sieve of super steady Y molecular sieves The methods of composite modified, show that super steady Y molecular sieves have good crystallinity, higher silica alumina ratio, larger by modified Hole size and pore volume, high specific surface area and hydrothermal stability, suitable acid amount and acid strength, so as to be used as carrier or acidity Component prepares catalyst and shows preferable catalytic performance.Think the study on the modification of ultra-steady Y molecular sieve is still to continue simultaneously, On the one hand the research in terms of acid centre, USY molecular sieves have B acid and L acid sites, how to prepare specific acid site Catalyst, it is the problem that needs are captured to reach best catalytic activity；On the other hand to improve and (or be changed with super steady Y molecular sieves Property super steady Y molecular sieves) catalyst for preparing recycles number, reduce production cost and improve production efficiency.Peng Chenghua Deng（The influence [J] of modified Y molecular sieve centering cut selective hydrogenation Cracking catalyst, petroleum journal（PETROLEUM PROCESSING）, 2006 （Supplementary issue）：171~173）Result of study show by modified Y molecular sieves there is relatively low total acid content and higher L acid ratio to have Beneficial to the middle cut selectivity for improving catalyst, and holding is preferably active；Product (<370 DEG C of distillates) conversion ratio be 60% When, pilot scale sizing catalyst HC-670 middle cut (150-370 DEG C of distillate) is selectively 68.3%, and similar Industrial Catalysis The middle cut of agent is selectively only 61.8%.Li Mingxiao etc.（The influence of hydro-thermal process and nitric acid treatment to modified Y molecular sieve performance [J], petrochemical industry, 2012,43（4）：412~419）Result of study show, with the rise of hydro-thermal process temperature, Y molecular sieve Dealuminzation amount increases, and specific surface area reduces, and total acid content reduces；With the increase of concentration of nitric acid, the non-framework aluminum in Y molecular sieve removes, Relative crystallinity, specific surface area and silica alumina ratio increase.The activity of the hydrocracking catalyst prepared with modified Y molecular sieve and Selectivity is improved, and what wherein Y molecular sieve was prepared after 680 DEG C of hydro-thermal process and 0.6mol/L nitric acid treatments, which be hydrocracked, urges Agent, on the premise of higher n-dodecane conversion ratio is kept, there is good middle oil（C4~8Hydrocarbon）Selectivity, middle oil yield are 51.07%.Wang Wenlan（Combination Modified Zeolite Y is hydrocracked performance [J], chemistry of fuel journal, and 2009,37（4）：454~ 458）Result of study show, during Y type molecular sieve oxalic acid dealuminzation, add CTAB can make Y type molecular sieve keep very High relative crystallinity, while improve SiO2/Al2O3Than reducing lattice constant.CTAB participates in the acid amount of modified Y type molecular sieve Significantly reduce, its reason is determined by the raising of silica alumina ratio and the amine poisoning of partially acidic position.CTAB participates in Modified Zeolite Y system Standby hydrocracking catalyst has higher activity and midbarrel oil yield, than the midbarrel oil type of current commercial Application VGO high conversion rates 2.42%, the high income of intermediate oil 4.20% of hydrocracking catalyst.Its reason is that CTAB participates in being modified Y type molecular sieve have more rich mesoporous, enable macromolecular in VGO more close to the acidic site of catalyst, simultaneously Crackate can quickly leave the active sites of catalyst and avoid secondary cracking, thus make catalyst have higher activity and Midbarrel oil yield.Patent 200610001864.0 describes a kind of method of modifying of Y type molecular sieve, and this method is used in acid The method that surfactant is added in dealumination process, has obtained the Y type molecular sieve of high silica alumina ratio（Mole of silica and aluminum oxide Silica alumina ratio 9 ~ 15）And higher crystallinity is maintained, the secondary pore of Modified Zeolite Y, which has, to be greatly improved, and sour structure also obtains Further improvement is arrived.Patent 200810104303.2 describes a kind of method of modifying of HY types molecular sieve, and this method uses HY types molecular sieve is impregnated to a certain amount of 5% ~ 10% Ludox, is then dried by 120 DEG C and 450 DEG C is calcined, finally used Certain density ammonium fluoride aqueous solution carries out dealumination treatment, has obtained micro--mesoporous remodeling molecular sieve.
Patent 200810105644.1 describes a kind of method of modifying of NaY types molecular sieve, and this method will be from using screen cloth Sub-exchange resin is kept apart with molecular sieve pulp, in the case of both are discontiguous, using concentration difference realize hydrogen ion with The exchange of sodium ion, the problem of alleviating subsequent wastewater treatment.The sodium oxide content of resulting remodeling molecular sieve can be reduced to Below 1wt%, crystallinity are maintained at more than 80%.Patent 201110331019.0 describes a kind of modification side of NaY types molecular sieve Method, this method is added in the mixed liquor of NaY molecular sieve, buffer solution and water using mixed acid to be beaten uniform, then and adjusts pH Value is 4.0 ~ 6.5, and the exchange reaction under the conditions of 70 ~ 95 DEG C, finally washs, and dries.No ammonium discharge is the method achieve, is alleviated The problem of subsequent wastewater treatment.The sodium oxide content of resulting remodeling molecular sieve can be reduced to below 0.5wt%, crystallinity It is maintained at more than 85%.Patent 201310114414.2 describes a kind of method of modifying of USY molecular sieve, and this method uses 0.10mol/L ~ 0.35mol/L citric acids are modified at 50 DEG C ~ 120 DEG C, and rise to design temperature in temperature as 60 DEG C ~ 90 DEG C Afterwards, ammonium fluosilicate solution is added with 0.1ml/min ~ 3.5ml/min speed, after reacting 1h ~ 6h after charging, washs, do It is dry to obtain being modified USY molecular sieve.Ratio surface, secondary pore pore volume and the middle strong acid ratio of molecular sieve significantly improve.Patent 201310240740.8 and 201410131823.8 describe the combination method of modifying rich in mesoporous ultra-steady Y molecular sieve, this method Using organic acid and inorganic salt solution mixed solution, under conditions of stirring, temperature reaction is carried out in closed container, reaction reaches Washed after to setting time, filter to neutrality, be dried to obtain modified molecular screen.Modified molecular sieve secondary pore content is notable Improve, silica alumina ratio increase, lattice constant reduces.Patent 201410131458.0 describes a kind of method of modifying of USY molecular sieve, This method is modified processing with ammonium fluosilicate and citric acid mixed solution at a temperature of 50 DEG C ~ 120 DEG C, finally obtains and is rich in The abundant modification USY molecular sieve of the high and middle strong acid of secondary pore structure, crystallinity.Patent 201510131458.0 describes one kind and changed Property Y molecular sieve and its method of modifying, this method are handled Y type molecular sieve using alkaline solution first, then take dealuminzation The method for mending silicon obtains the Y type molecular sieve of high silica alumina ratio.The modified molecular screen has that strong acid ratio is big, especially strong B acid ratio The characteristics of big.
Existing result of study shows, can change molecular sieve pore passage structure and regulation point by using different method of modifying The Acidity of son sieve, so as to effectively improve the stability and catalytic performance of molecular sieve.The raising of molecular sieve performance can be significantly Improve the reactivity and purpose product selectivity of catalyst.
The content of the invention
In view of the shortcomings of the prior art, the present invention provide a kind of hydrocracking catalyst for producing high-quality ethylene raw material and its Preparation method and application.Hydrocracking catalyst prepared by the inventive method has being hydrocracked property high good with product selectivity Feature, it can be used for producing high-quality ethylene cracking material.
The preparation method of catalyst of the present invention includes following content：
（1）Under agitation, Y type molecular sieve is added to equipped with the tetraethyl hydroxide that concentration is 0.05 ~ 0.35mol/L In the pressure vessel of one or more of organic alkali solutions in ammonium, TPAOH or TBAH, and will be Unite closed, boost to 0.2 ~ 1.0MPa using compressed air, nitrogen or inert gas etc. is passed through into pressure vessel, then heat up To 50 ~ 90 DEG C, constant temperature is handled 0.5 ~ 3 hour, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.
In the inventive method, step（1）Described modification USY molecular sieve has following property after roasting：Total hole body Product is 0.76 ~ 1.25ml/g, preferably 0.80 ~ 1.10ml/g；Its intermediary hole pore volume is 0.55 ~ 1.05ml/g, preferably 0.60 ~ 0.95ml/g, more preferably 0.68 ~ 0.90ml/g；Mesoporous pore volume accounts for the 65% ~ 90% of total pore volume, preferably 70% ~ 85%；Silica Mol ratio with aluminum oxide is 10 ~ 35, preferably 12 ~ 30；Specific surface area is 680 ~ 1050m2/ g, preferably 800 ~ 950m2/g。
In the inventive method, step（1）The Y type molecular sieve being added in organic alkali solution is Hydrogen, silica/alumina Mol ratio is 10 ~ 55, preferably 18 ~ 45；Specific surface area is 650 ~ 950m2/ g, preferably 750 ~ 900m2/g；The addition of Y type molecular sieve Amount is 1 with the water quality ratio in organic alkali solution:2~1:8, preferably 1:3~1:6.
In the inventive method, step（2）Described drying 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, each component in catalyst Content is：Modified USY molecular sieve is generally 20 ~ 70%, preferably 30 ~ 50%；Aluminum oxide is generally 30% ~ 70%, preferably 40 ~ 60%； Group vib metal（In terms of oxide）Generally 6% ~ 15%, preferably 8 ~ 12%；Group VIII metal（In terms of oxide）Generally 2% ~ 8%, preferably 3 ~ 6%.
For catalyst of the present invention when handling VGO, reaction condition is 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 following advantages that compared to prior art：Under elevated pressure conditions, use is organic for the inventive method Alkali carries out desiliconization aluminium processing to molecular sieve, and more and bigger secondary pore structures is formd in molecular sieve crystal.At organic base Reason molecular sieve can not introduce alkali metal ion（Such as sodium and potassium）Under conditions of molecular sieve is modified, and can profit White carbon is directly added into as peptizing agent prepare catalyst by the use of modified solution.Molecular sieve prepared by the inventive method has bigger Pore volume and specific surface area, active sites accessibility and diffusion are more preferable, improve catalyst reaction active site can The diffusion of proximity and molecular sieve.Method for preparing catalyst of the present invention is simple, and preparation process is few, reduces in preparation process The discharge of waste liquid.The hydrogenation open loop that catalyst preparation of the present invention is advantageous to improve cyclic hydrocarbon in raw material in hydrocracking process is anti- Should be with the generation that reduces excessive fragmentation reaction, ring-type hydrocarbon content declines to a great extent in the hydrocracking tail oil for making to finally give, can be with Improve the yield of triolefin in steam-cracking process.
Embodiment
The preparation process of the inventive method is further illustrated with reference to embodiment, but following examples are not formed to this hair The limitation of bright method.
Embodiment 1
（1）Under agitation, Y type molecular sieve is added to organic equipped with the TPAOH that concentration is 0.25mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.5MPa is boosted to using compressed air is passed through into pressure vessel, then 70 DEG C are warming up to, constant temperature is handled 2 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 2
（1）Under agitation, Y type molecular sieve is added to organic equipped with the tetraethyl ammonium hydroxide that concentration is 0.30mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.3MPa is boosted to using compressed nitrogen is passed through into pressure vessel, then 60 DEG C are warming up to, constant temperature is handled 2 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 3
（1）Under agitation, Y type molecular sieve is added to organic equipped with the TBAH that concentration is 0.26mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.8MPa is boosted to using compressed air is passed through into pressure vessel, then 55 DEG C are warming up to, constant temperature is handled 1.5 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 4
（1）Under agitation, Y type molecular sieve is added to organic equipped with the tetraethyl ammonium hydroxide that concentration is 0.33mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.45MPa is boosted to using compressed nitrogen is passed through into pressure vessel, so After be warming up to 70 DEG C, constant temperature is handled 1.5 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 5
（1）Under agitation, Y type molecular sieve is added to organic equipped with the TPAOH that concentration is 0.20mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.55MPa is boosted to using compressed air is passed through into pressure vessel, so After be warming up to 70 DEG C, constant temperature is handled 2 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 6
（1）Under agitation, Y type molecular sieve is added to organic equipped with the tetraethyl ammonium hydroxide that concentration is 0.30mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.35MPa is boosted to using compressed nitrogen is passed through into pressure vessel, so After be warming up to 65 DEG C, constant temperature is handled 2 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 7
（1）Under agitation, Y type molecular sieve is added to organic equipped with the TBAH that concentration is 0.40mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.45MPa is boosted to using compressed air is passed through into pressure vessel, so After be warming up to 55 DEG C, constant temperature is handled 1.0 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Embodiment 8
（1）Under agitation, Y type molecular sieve is added to organic equipped with the tetraethyl ammonium hydroxide that concentration is 0.35mol/L In the pressure vessel of aqueous slkali, and system is closed, 0.75MPa is boosted to using compressed nitrogen is passed through into pressure vessel, so After be warming up to 80 DEG C, constant temperature is handled 1.5 hours, is unloaded and is depressed into normal pressure；
（2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.Catalyst property such as table 1.
Comparative example 1
With embodiment 1, difference is that USY molecular sieve without modification, obtains hydrocracking catalyst catalyst performance Matter such as table 1.
Comparative example 2
With embodiment 1, difference is that USY molecular sieve modification process is carried out at ambient pressure, obtains hydrocracking catalyst Agent catalyst property such as table 1.
Catalytic performance test.
Evaluating apparatus is carried out using 200m1 small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Evaluation is urged The raw materials used oil nature of agent activity and reaction process condition are shown in Table 2 and table 3, and catalyst reaction performance comparison the results are shown in Table 4.Comment During valency catalyst, feedstock oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, passes through The organic nitrogen content in feedstock oil is controlled to be less than 20ppm during Hydrobon catalyst bed.
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 catalyst prepared by the inventive method is compared with comparative example catalyst, conversion ratio When identical, reaction temperature is low 4 ~ 6 DEG C, and the linear paraffin content of tail oil product is higher than comparative example, while two ring above Determination of Alkane Content It is lower than comparative example with the BMCI values of tail oil.Illustrate that catalyst prepared by the inventive method has hydrogenation activity high and is hydrogenated with The characteristics of open-loop performance is good.

Claims (10)

  1. A kind of 1. preparation method for being used to produce the hydrocracking catalyst of high-quality ethylene raw material, it is characterised in that：Including as follows Content：
    （1）Under agitation, Y type molecular sieve is added to equipped with the tetraethyl hydroxide that concentration is 0.05 ~ 0.35mol/L In the pressure vessel of one or more of organic alkali solutions in ammonium, TPAOH or TBAH, and will be Unite closed, boost to 0.2 ~ 1.0MPa using compressed air, nitrogen or inert gas etc. is passed through into pressure vessel, then heat up To 50 ~ 90 DEG C, constant temperature is handled 0.5 ~ 3 hour, is unloaded and is depressed into normal pressure；
    （2）White carbon and active metal component are added to step（1）In mixture be well mixed, after then fully rolling into Type, then dry, be calcined, obtain hydrocracking catalyst.
  2. 2. preparation method according to claim 1, it is characterised in that：Step（1）Described modification USY molecular sieve is by roasting There is following property after burning：Total pore volume is 0.76 ~ 1.25ml/g；Its intermediary hole pore volume is 0.55 ~ 1.05ml/g；Mesoporous hole Volume accounts for the 65% ~ 90% of total pore volume；The mol ratio of silica and aluminum oxide is 10 ~ 35；Specific surface area is 680 ~ 1050m2/g。
  3. 3. preparation method according to claim 2, it is characterised in that：Step（1）Described modification USY molecular sieve is by roasting There is following property after burning：Total pore volume is 0.80 ~ 1.10ml/g；Its intermediary hole pore volume is 0.60 ~ 0.95ml/g；Mesoporous hole Volume accounts for the 70% ~ 85% of total pore volume；The mol ratio of silica and aluminum oxide is 12 ~ 30；Specific surface area is 800 ~ 950m2/g。
  4. 4. preparation method according to claim 1, it is characterised in that：Step（1）The Y types point being added in organic alkali solution Son sieve is Hydrogen, and silica/alumina molar ratio is 10 ~ 55；Specific surface area is 650 ~ 950m2/g；The addition of Y type molecular sieve It is 1 with the water quality ratio in organic alkali solution:2~1:8.
  5. 5. preparation method according to claim 4, it is characterised in that：Silica/alumina molar ratio is 18 ~ 45；Compare table Area is 750 ~ 900m2/g；Water quality ratio in the addition and organic alkali solution of Y type molecular sieve is 1:3~1:6.
  6. 6. preparation method according to claim 1, it is characterised in that：Step（2）Described drying temperature is 50 ~ 150 DEG C, Drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
  7. 7. catalyst prepared by claim 1 to 6 either method, it is characterised in that：Based on catalyst weight percent, catalyst The content of middle each component is：Modified USY molecular sieve is 20 ~ 70%；Aluminum oxide is 30% ~ 70%；Group vib metal（In terms of oxide） For 6% ~ 15%；Group VIII metal（In terms of oxide）For 2% ~ 8%.
  8. 8. catalyst according to claim 7, it is characterised in that：Based on catalyst weight percent, each group in catalyst Point content be：Modified USY molecular sieve 30 ~ 50%；Aluminum oxide 40 ~ 60%；Group vib metal（In terms of oxide）8~12%；VIII Metal（In terms of oxide）3~6%.
  9. 9. any catalyst of claim 7 or 8 is used to handle VGO.
  10. 10. application according to claim 9, it is characterised in that：Reaction condition is under hydrogen existence condition, reaction pressure 10 ~ 20MPa, 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121849A (en) * 2020-10-12 2020-12-25 天长市润源催化剂有限公司 Preparation method of molecular sieve catalyst for power plant tail gas purification

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069427A (en) * 1991-08-16 1993-03-03 国际壳版研究有限公司 The carbon monoxide-olefin polymeric that contains modified zeolite of Y-type
CN1552818A (en) * 2003-05-30 2004-12-08 中国石油化工股份有限公司 Monox-alumina containnig hydrocracking catalyst
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof
CN104624227A (en) * 2013-11-15 2015-05-20 中国石油天然气股份有限公司 Mesoporous-microporous molecular sieve hydrocracking catalyst
CN104667968A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 A hydrocracking catalyst carrier and a preparing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069427A (en) * 1991-08-16 1993-03-03 国际壳版研究有限公司 The carbon monoxide-olefin polymeric that contains modified zeolite of Y-type
CN1552818A (en) * 2003-05-30 2004-12-08 中国石油化工股份有限公司 Monox-alumina containnig hydrocracking catalyst
CN103100417A (en) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 Hydrocracking catalyst and preparation method thereof
CN104624227A (en) * 2013-11-15 2015-05-20 中国石油天然气股份有限公司 Mesoporous-microporous molecular sieve hydrocracking catalyst
CN104667968A (en) * 2013-11-26 2015-06-03 中国石油化工股份有限公司 A hydrocracking catalyst carrier and a preparing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112121849A (en) * 2020-10-12 2020-12-25 天长市润源催化剂有限公司 Preparation method of molecular sieve catalyst for power plant tail gas purification

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