CN107303493B - A kind of preparation method of Catalyst For Single-stage Hydrocracking - Google Patents

A kind of preparation method of Catalyst For Single-stage Hydrocracking Download PDF

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CN107303493B
CN107303493B CN201610252799.2A CN201610252799A CN107303493B CN 107303493 B CN107303493 B CN 107303493B CN 201610252799 A CN201610252799 A CN 201610252799A CN 107303493 B CN107303493 B CN 107303493B
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molecular sieve
catalyst
ammonium
modified
hours
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CN107303493A (en
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柳伟
杜艳泽
秦波
高杭
阮彩安
董立廷
贝耀明
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • 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
    • 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

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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)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of preparation methods of Catalyst For Single-stage Hydrocracking, including following content: 1, being uniformly mixed modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide, dust technology is added, rear extruded moulding is slurried, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Mass percent of the modified Y molecular sieve in silica-alumina supports is 1% ~ 13%, preferably 2% ~ 10%, and surplus is amorphous silica-alumina and/or aluminium oxide；2, it is impregnated using carrier of the maceration extract containing active metal to step (1), the carrier after dipping obtains hydrocracking catalyst through drying, roasting；The Catalyst For Single-stage Hydrocracking of the method for the present invention preparation has good reactivity and anti-nitrogen ability in single-stage hydrocracking technique.

Description

A kind of preparation method of Catalyst For Single-stage Hydrocracking
Technical field
The present invention relates to a kind of preparation methods of Catalyst For Single-stage Hydrocracking.
Background technique
Hydrocracking technology is strong with adaptability to raw material, products scheme is flexible, purpose product selectivity is high, good product quality And added value is high, can directly produce the features such as a variety of high-quality oil products and industrial chemicals.Therefore, which has become reasonable benefit With limited crude resources, cleaning oil product and the optimum oil Refining Technologies of high-quality industrial chemicals are produced to greatest extent.Add hydrogen Cracking technology can be mainly divided into three kinds by processing flow: one-stage serial hydrocracking process flow, single-stage hydrocracking technique Process and two-stage reforming process flow.Wherein one-stage serial process flow setting purification and two reactors of cracking, purification Organonitrogen removal in raw material to 10 ~ 20ppm or less is added with meeting cracker using Hydrobon catalyst in reactor After the requirement of hydrogen Cracking catalyst, finishing reactor effluent is directly entered cracker.Two-stage process process equally uses Two reactors, use hydrogenation catalyst in first reactor, and second reactor uses hydrocracking catalyst, but the The effluent of one reactor carries out the operation such as gas-liquid separation, and liquid phase enters second two reactor.Compared to one-stage serial With two-stage reforming technology, single-stage hydrocracking technology is not provided with finishing reactor, using resistance to raw material impurity (sulphur, nitrogen etc.) energy The stronger hydrocracking catalyst of power, raw material directly carry out hydrocracking process without hydrofinishing, simple with process, Operation be easy, small investment the features such as, be suitable for maximum production intermediate oil.
In terms of Catalyst For Single-stage Hydrocracking, external more representational technology supplier mainly has Chevron public Department and Uop Inc..The single hop senior middle school oil hydrocracking catalyst of Chevron company mainly has ICR-106, ICR-120, ICR- 126, ICR-142, ICR-150, ICR-155, ICR-162 etc..It is matched excellent between hydrogenation component and carrier component by carrying out Change, and the further modification to molecular sieve, the activity of the ICR-142 catalyst of Chevron company exploitation is apparently higher than ICR-106 amorphous catalyst, and intermediate oil selectivity is suitable with it.The single hop senior middle school oil of Uop Inc.'s exploitation adds hydrogen Cracking catalyst mainly has HC-102, HC-22, DHC-8, DHC-32, DHC-100, HC-110, HC-115, HC-215 etc..
Single-stage hydrocracking technology requires hydrocracking catalyst to have the stronger energy of resistance to nitrogen due to its own process characteristic Power, therefore, the hydrocracking catalyst that industrial application process uses generally use amorphous silica-alumina or containing a small amount of high silica alumina ratios Modified Y or beta-molecular sieve are as its acidic components.Although catalyst has stronger resistance to nitrogen ability, catalyst activity in this way Poor, reaction temperature is usually more than 400 DEG C.Since reaction temperature is excessively high, limited by aromatic hydrogenation saturation thermodynamical equilibrium, it is excessively high Reaction temperature it is unfavorable to aromatic hydrogenation saturated reaction, product property is poor.And higher reaction temperature also accelerates catalyst product Carbon, inactivation affect the cycle of operation of hydrocracking unit.
CN200710158784.0 discloses a kind of hydrocracking catalyst and preparation method thereof containing Y molecular sieve, the hair Bright middle Y type molecular sieve is obtained with after the mixed aqueous solution of aluminium salt and acid processing hydro-thermal process, and catalyst activity obtained is higher, But resistance to nitrogen ability is poor.
CN98114489.6 discloses a kind of hydrocracking catalyst of nitrogen-resistant type multiferous middle oil, is used for heavy distillate one Section serial hydrocracking produces a large amount of intermediate oils, and cracking zone feeds nitrogen content up to 100 μ g/g, but the catalyst activity It is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of Catalyst For Single-stage Hydrocracking, the present invention The Catalyst For Single-stage Hydrocracking of method preparation has good reactivity and anti-nitrogen ability in single-stage hydrocracking technique.
The preparation method of Catalyst For Single-stage Hydrocracking of the invention, including following content: by modified Y molecular sieve, without fixed Type sial and/or aluminium oxide are uniformly mixed, and dust technology are added, rear extruded moulding is slurried, dry, roasting is obtained containing modified Y molecular sieve Silica-alumina supports；Mass percent of the modified Y molecular sieve in silica-alumina supports is 1% ~ 13%, preferably 2% ~ 10%, surplus For amorphous silica-alumina and/or aluminium oxide；Then the silica-alumina supports containing modified Y molecular sieve are impregnated with the maceration extract containing active metal, Carrier after dipping obtains hydrocracking catalyst through drying, roasting；
The wherein preparation method of the modified Y molecular sieve, including following content:
(1) Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by original powder of NaY zeolite；
(2) hydro-thermal process is carried out to the Y molecular sieve after ammonium obtained in step (1) exchange；
(3) Y molecular sieve after step (2) hydro-thermal process is handled with aluminum salt solution；
(4) the resulting Y molecular sieve of step (3) is dried；
(5) Y molecular sieve that liquid or gaseous unsaturated olefin are dried with step (4) is come into full contact with, is then existed Carbon deposit reaction is carried out in oxygen-containing atmosphere；
(6) the carbon deposit Y molecular sieve quick high-temp calcination process for preparing step (5)；
(7) molecular sieve for obtaining step (6) carries out dealumination complement silicon processing；
(8) treated after Y molecular sieve filtered, dried through dealumination complement silicon for step (7), carries out processing of making charcoal, is changed Property Y molecular sieve.
Ammonium Salt Ionic exchange process described in step (1) is as follows: it is raw material in ammonium salt aqueous solution using NaY zeolite, 60 ~ It at 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O contains Amount is less than 3.0%；The wherein SiO of NaY zeolite raw material2/Al2O3Molar ratio is 3 ~ 6, sodium oxide molybdena mass percentage 6% ~ 7%；Ammonium salt It is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, 0.3 ~ 6.0mol/ of ammonium salt aqueous solution concentration L, preferably 1.0 ~ 3.0 mol/L.
Step (2) described hydrothermal treatment process is the hydro-thermal process item in itself vapor or under conditions of be passed through vapor Part are as follows: temperature is 530 ~ 650 DEG C, and pressure is 0.01 ~ 0.5MPa, and the processing time is 1.0 ~ 6.0 hours.
Aluminium salt used in aluminium salt treatment process described in step (3) can be aluminium chloride, aluminum sulfate, aluminum nitrate etc..Aluminium salt Concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the processing time is 0.5 ~ 3 hour.
Drying temperature described in step (4) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
Unsaturated olefin described in step (5) is the positive structure or isomeric olefine, alkadienes that charcoal atomicity is 2 ~ 10；Wherein institute The alkene and molecular sieve stated, which come into full contact with, refers to that unsaturated olefin diffuses into inside molecular sieve；When use gaseous state unsaturated olefin When, gaseous state unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.1 ~ 2 hour；When use liquid When state unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 are small When, molecular sieve answers thorough impregnation in liquefied olefines.The alkene comes into full contact with molecular sieve and generally carries out at normal temperature, institute The unsaturated hydrocarbons state phase stated is phase under room temperature.
Oxygen-containing atmosphere described in step (5) is the mixing of air, the mixture of oxygen and nitrogen or oxygen and inert gas One of object, the volume fraction of oxygen in the gas phase are 10% ~ 100%, preferably air；Carbon deposit reaction condition are as follows: reaction temperature 50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.
Quick high-temp roasting condition described in step (6) are as follows: maturing temperature is 400 ~ 600 DEG C, and calcining time is 2 ~ 50 points Clock, preferably 5 ~ 20 minutes；General treatment process is that the Y molecular sieve of carbon deposit is directly added into the horse for being warming up to maturing temperature in advance Not roasted in furnace or other heating equipments.
The processing of dealumination complement silicon described in step (7) is method well known to those skilled in the art, can be using conventional fluorine The Y molecular sieve that step (6) obtains first is added water to be made into the water sample mixing of liquid-solid ratio 3 ~ 6 by ammonium silicate dealumination complement silicon method, then, It is that 1.0 ~ 3.0mol/L ammonium fluosilicate aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C that concentration, which is added, and ammonium fluosilicate treatment process can Repeat 1 ~ 3 time as needed.Other are such as SiCl4The methods of gas phase dealumination complement silicon is also suitable.
It makes charcoal described in step (8) treatment conditions are as follows: roast 2 ~ 4 hours, remove remaining on molecular sieve at 400 ~ 600 DEG C Carbon deposit.
The modified Y molecular sieve have the property that lattice constant be 2.425 ~ 2.440, body phase silica alumina ratio be 20 ~ 40, wherein surface layer silica alumina ratio 50 ~ 120, surface layer silica alumina ratio are higher than body phase silica alumina ratio 10 ~ 80；Wherein the superficial layer refers to molecule Sieve 10 ~ 200nm of outer surface to inside, preferably 50 ~ 190nm；Sodium oxide molybdena mass percentage is less than 1.0%, and preferably smaller than 0.5%； 650 ~ 900m of modified Y molecular sieve specific surface area2/ g, Kong Rong 0.30 ~ 0.50ml/g, infrared 0.1 ~ 0.8mmol/g of acid content, preferably 0.2 ~ 0.6mmol/g, relative crystallinity 80% ~ 110%.
The Catalyst For Single-stage Hydrocracking of the method for the present invention preparation, including the silica-alumina supports 30% ~ 80% containing modified Y molecular sieve With active metal 20% ~ 70%, wherein active metal is in terms of metal oxide；The active metal is in the periodic table of elements Group VIII and/or vib metals element, group VIII active metal can be Ni and/or Co, group VIB active metal It can be W and/or Mo, group VIII active metallic content is 3% ~ 15%, and group VIB active metallic content is 10% ~ 40%, with gold Belong to oxide meter.The specific surface area of the catalyst is 100 ~ 300m20.2 ~ 0.5ml/g of/g, Kong Rongwei.
The hydrocracking catalyst of the method for the present invention preparation can be applied to single-stage hydrocracking technological reaction process, general to grasp Make condition are as follows: 6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, 0.3 ~ 3.0h of feed volume air speed-1, hydrogen oil volume Than for 500:1 ~ 2000:1.
In the method for the present invention, silica alumina ratio is the molar ratio of silica and aluminium oxide.
In the method for the present invention, body phase silica alumina ratio refers to the silica alumina ratio of modified molecular screen entirety.
In the method for the present invention, body phase silica alumina ratio is measured using chemical analysis.Surface layer silica alumina ratio is using transmission Electronic Speculum X-ray electronic spectroscopy measures.
In the method for the present invention, specially treated is carried out to the Y molecular sieve that Catalyst For Single-stage Hydrocracking uses, i.e., first in sky Make the unsaturated hydrocarbons such as the alkene being adsorbed on Y molecular sieve, alkadienes sufficiently long-pending inside and outside molecular sieve in gas atmosphere, under heating condition Then charcoal burns up the charcoal deposited on molecular sieve surface by the method that quick high-temp roasts, the aluminium position quilt inside such molecular sieve Therefore carbon deposit covering protection in subsequent ammonium fluosilicate dealumination complement silicon treatment process, mainly carries out, ammonium fluosilicate on the outer surface After processed, then the carbon deposit of molecular sieve internal residual is removed in high-temperature roasting, restores the acid point inside molecular sieve.Side of the present invention Method carries out dealumination complement silicon, the selective sial for improving Y molecular sieve outer surface to Y molecular sieve outer surface by selectivity Than compared to the hydrocracking catalyst of conventional method modified molecular screen preparation, hydrocracking catalyst of the present invention is used for single hop Higher anti-nitrogen ability is shown during hydrocracking process, there is preferably activity, stability.
Specific embodiment
Below by embodiment, the present invention is further described, but is not so limited the present invention.Involved in embodiment Percentage is mass percent (except relative crystallinity), and the liquid-solid ratio is that liquid consolidates mass ratio.
Hydrocracking catalyst of the invention specific the preparation method is as follows:
1, modified Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are uniformly mixed according to a certain ratio, dust technology is added Rear extruded moulding is slurried, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Wherein the concentration of dust technology be 3wt% ~ 30wt%；The drying condition are as follows: 1 ~ 5 hour dry at 80 ~ 120 DEG C；Roasting condition are as follows: at 400 ~ 700 DEG C roast 1 ~ 5 hours；
2, it is impregnated using carrier of the maceration extract containing active metal to step 1, the carrier after dipping is through drying, roasting It burns, obtains hydrocracking catalyst；The liquid-solid ratio wherein impregnated is 1.5:1 ~ 3:1, using saturation dipping well known in the art Mode carries out, and the content of group vib metallic compound is calculated as 20 ~ 60g/100ml, group VIII gold by corresponding oxide in maceration extract The content for belonging to compound is calculated as 3 ~ 20g/100ml by corresponding oxide, and the concentration of metallic compound can be according to production in maceration extract Product needs adjust accordingly；The wherein drying condition are as follows: 2 ~ 8 hours dry at 90 ~ 150 DEG C；Roasting condition are as follows: It is roasted 1 ~ 5 hour at 400 ~ 700 DEG C.
Embodiment 1
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.5mol/L with concentration is according to liquid-solid ratio 3:1 mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.5%；
(2) 570 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.2MPa；
(3) molecular sieve obtained by step (2) is stirred according to liquid-solid ratio 5:1 with distilled water, is then heated to 90 DEG C, is being stirred The aluminum sulfate solution 400ml of addition 1.2mol/L during mixing, isothermal reaction 3 hours.
(4) 150 DEG C of molecular sieve dry 8h obtained by step (3)；
(5) it takes step (4) resulting molecular sieve to be placed in the closed container full of butadiene atmosphere, controls pressure 0.3MPa comes into full contact with 20 minutes, then, heats 15 hours in air atmosphere at 200 DEG C；
(6) treated that molecular sieve is directly placed into the Muffle furnace for being previously heated to 450 DEG C for step (5), roasts 10 minutes；
(7) step (6) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with distilled water, and then, concentration, which is added, is The ammonium fluosilicate solution 100ml of 1.2mol/L, 90 DEG C are handled 1.5 hours, and treated that sample is filtered, done for an ammonium fluosilicate Repeat once after dry according to step (7) method；
(8) through step (7) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, 550 DEG C after roasting 2 hours, Obtain modified Y molecular sieve, number Y-1.
Y-1 molecular sieve transmission electron microscope EDAX results measure its outer surface to 80nm thickness, and superficial layer silica alumina ratio is 85, Molecular sieve phase silica alumina ratio is 37.XRD analysis the result shows that its lattice constant be 2.433, relative crystallinity 99%.Kong Rong 0.36ml/g, specific surface area 760m2/ g, it is 0.45mmol/g that infrared analysis result, which measures Y-1 meleic acid amount,.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 430g and nickel nitrate 440g to be dissolved in water Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 36g/100ml and 11g/100ml, molten Liquid number RY-1；
(2) it takes Y-1 4g to mix with 50g amorphous silicon aluminium and 46g macroporous aluminium oxide, 4g/100ml dust technology is added mixed Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-1 on banded extruder；
(3) T-1 60g is taken 120ml RY-1 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings It burns 3 hours, obtains hydrocracking catalyst, number Cat-1.
Embodiment 2
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder for taking laboratory to prepare, the ammonium nitrate for being 0.8mol/L with concentration is according to liquid-solid ratio 3:1 Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%.
(2) 570 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 1 hour under 0.1MPa；
(3) molecular sieve obtained by step (2) is stirred according to liquid-solid ratio 6:1 with distilled water, is then heated to 90 DEG C, is being stirred The aluminum sulfate solution 600ml of addition 1.5mol/L during mixing, isothermal reaction 2 hours.
(4) 200 DEG C of molecular sieve dry 4h obtained by step (3)；
(5) the resulting molecular sieve of heptene soaking step (4) is taken 2 hours, then, 250 DEG C of heating 20 are small in air atmosphere When；
(6) treated that molecular sieve is directly placed into the Muffle furnace for being previously heated to 500 DEG C for step (5), roasts 15 minutes；
(7) step (6) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with distilled water, and then, concentration, which is added, is The ammonium fluosilicate solution 200ml of 1.5mol/L, 95 DEG C are handled 3 hours；
(8) through step (7) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, 550 DEG C after roasting 2 hours, Obtain modified Y molecular sieve, number Y-2.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten Liquid number RY-2；
(2) it takes Y-2 4g to mix with 50g amorphous silicon aluminium and 46g macroporous aluminium oxide, 4g/100ml dust technology is added mixed Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-2 on banded extruder；
(3) T-2 60g is taken 120ml RY-2 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings It burns 3 hours, obtains hydrocracking catalyst, number Cat-2.
Y-2 molecular sieve transmission electron microscope EDAX results measure its outer surface to 150nm thickness, and superficial layer silica alumina ratio is 73, molecular sieve phase silica alumina ratio is 39.XRD analysis the result shows that its lattice constant be 2.431, relative crystallinity 96%.Kong Rong 0.37 ml/g, specific surface area 700m2/ g, it is 0.43mmol/g that infrared analysis result, which measures Y-2 meleic acid amount,.
Embodiment 3
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder for taking laboratory to prepare, the ammonium nitrate for being 0.8mol/L with concentration is according to liquid-solid ratio 3:1 Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%.
(2) 550 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.15MPa；
(3) molecular sieve obtained by step (2) is stirred according to liquid-solid ratio 6:1 with distilled water, is then heated to 90 DEG C, is being stirred The aluminum sulfate solution 600ml of addition 1.0mol/L during mixing, isothermal reaction 2 hours.
(4) 250 DEG C of molecular sieve dry 2h obtained by step (3)；
(5) the resulting molecular sieve of heptene soaking step (4) is taken 4 hours, then, 300 DEG C of heating 12 are small in air atmosphere When；
(6) treated that molecular sieve is directly placed into the Muffle furnace for being previously heated to 500 DEG C for step (5), roasts 12 minutes；
(7) step (6) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with distilled water, and then, it is 1.1 that concentration, which is added, The ammonium fluosilicate solution 200ml of mol/L, 80 DEG C are handled 2 hours；
(8) through step (7) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, 550 DEG C after roasting 2 hours, Obtain modified Y molecular sieve, number Y-3.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, molten Liquid number RY-3；
(2) it takes Y-3 8g to mix with 40g amorphous silicon aluminium and 52g macroporous aluminium oxide, 4g/100ml dust technology is added mixed Mixing is rolled to extrudable shape in clutch, and extruded moulding obtains carrier T-3 on banded extruder；
(3) T-3 60g is taken 120ml RY-3 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings It burns 3 hours, obtains hydrocracking catalyst, number Cat-3.
Y-3 molecular sieve transmission electron microscope EDAX results measure its outer surface to 100nm thickness, and superficial layer silica alumina ratio is 55, molecular sieve phase silica alumina ratio is 25.XRD analysis the result shows that its lattice constant be 2.436, relative crystallinity 96%.Kong Rong 0.35ml/g, specific surface area 680m2/ g, it is 0.54mmol/g that infrared analysis result, which measures Y-3 meleic acid amount,.
Embodiment 4
Molecular sieve modified treatment process:
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 0.6mol/L with concentration is according to liquid-solid ratio 3:1 mixing, 80 DEG C exchange 3 hours, repeat this process 3 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%；
(2) 600 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.2MPa；
(3) molecular sieve obtained by step (2) is stirred according to liquid-solid ratio 5:1 with distilled water, is then heated to 80 DEG C, is being stirred The aluminum sulfate solution 400ml of addition 1.2mol/L during mixing, isothermal reaction 2 hours.
(4) 100 DEG C of molecular sieve dry 9h obtained by step (3)；
(5) the resulting molecular sieve of hexadiene soaking step (4) is taken 3 hours, then, 150 DEG C of heating 25 in air atmosphere Hour；
(6) treated that molecular sieve is directly placed into the Muffle furnace for being previously heated to 400 DEG C for step (5), roasts 8 minutes；
(7) step (6) resulting molecular sieve is mixed according to liquid-solid ratio 5:1 with distilled water, and then, concentration, which is added, is The ammonium fluosilicate solution 100ml of 1.0mol/L, 80 DEG C are handled 2 hours；
(8) through step (7) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, 550 DEG C after roasting 2 hours, Obtain modified Y molecular sieve, number Y-4.
Y-4 molecular sieve transmission electron microscope EDAX results measure its outer surface to 70nm thickness, and superficial layer silica alumina ratio is 46, Molecular sieve phase silica alumina ratio is 29.XRD analysis the result shows that its lattice constant be 2.435, relative crystallinity 98%.Kong Rong 0.39ml/g, specific surface area 640m2/ g, it is 0.49mmol/g that infrared analysis result, which measures Y-4 meleic acid amount,.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: configuring 1000ml leaching after taking ammonium metatungstate 430g and nickel nitrate 440g to be dissolved in water Stain solution, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 36g/100ml and 11g/100ml, molten Liquid number RY-4；
(2) Y-4 5g is taken to mix with 95g macroporous aluminium oxide, be added 4g/100ml dust technology mix in a mixer roll to Extrudable shape, extruded moulding obtains carrier T-4 on banded extruder；
(3) T-4 60g is taken 120ml RY-4 maceration extract dipping to be added 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings It burns 3 hours, obtains hydrocracking catalyst, number Cat-4.
Comparative example 1
Using a kind of widely applied hydrocracking catalyst of industry, it is counted as BCat-1, modified Y is removed in catalyst formulation Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 1, the Y molecular sieve that catalyst BCat-1 is used Matter is as follows: molecular sieve SiO2/Al2O3 Molar ratio is 50.XRD analysis the result shows that its lattice constant be 2.429, relative crystallinity 92%, Kong Rong 0.33ml/g, specific surface area 700m2/ g, meleic acid amount are 0.32 mmol/g.
Comparative example 2
Using a kind of widely applied hydrocracking catalyst of industry, it is counted as BCat-2, modified Y is removed in catalyst formulation Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 3, the Y molecular sieve that catalyst BCat-2 is used Matter is as follows: molecular sieve SiO2/Al2O3 Molar ratio is 30.XRD analysis the result shows that its lattice constant be 2.437, relative crystallinity 98%, Kong Rong 0.35ml/g, specific surface area 690m2/ g, meleic acid amount are 0.50 mmol/g.
Embodiment 5
In order to investigate the reactivity worth that Examples and Comparative Examples prepare catalyst, catalyst is carried out on midget plant Evaluation test, evaluating apparatus use single-stage hydrocracking process flow, are loaded respectively according to embodiment 1 ~ 4 and compared in reactor Hydrocracking catalyst prepared by example 1 ~ 2, feedstock property, evaluation condition and evaluation result are listed in 1 ~ table of table 5.
1 raw material oil nature of table.
Figure 733181DEST_PATH_IMAGE002
2 evaluation condition of table.
Figure 650322DEST_PATH_IMAGE004
3 evaluation result of table.
Figure 430059DEST_PATH_IMAGE006
4 embodiment 1 of table and 1 catalyst stability comparative test of comparative example.
5 embodiment 3 of table and 2 catalyst stability comparative test of comparative example.
Figure 108482DEST_PATH_IMAGE010
Embodiment 1,3 shows with comparative test of 1 ~ 2 catalyst of comparative example on evaluating apparatus using the method for the present invention system Standby catalyst is compared with comparative example catalyst, and operation process reactivity and stable product quality are more preferably.

Claims (10)

1. a kind of preparation method of Catalyst For Single-stage Hydrocracking, it is characterised in that including following content: by modified Y molecular sieve with Amorphous silicon aluminium and/or aluminium oxide are uniformly mixed, and dust technology are added, rear extruded moulding is slurried, dry, roasting is obtained containing modified Y points The silica-alumina supports of son sieve；Mass percent of the modified Y molecular sieve in silica-alumina supports is 1% ~ 13%, and surplus is amorphous Sial and/or aluminium oxide；Silica-alumina supports containing modified Y molecular sieve are impregnated using the maceration extract containing active metal, the load after dipping Body obtains hydrocracking catalyst through drying, roasting；
The wherein preparation method of the modified Y molecular sieve, including following content: (1) water-soluble in ammonium salt by original powder of NaY zeolite Ammonium Salt Ionic exchange is carried out in liquid；(2) hydro-thermal process is carried out to the Y molecular sieve after ammonium obtained in step (1) exchange；(3) right Y molecular sieve after step (2) hydro-thermal process is handled with aluminum salt solution；(4) the resulting Y molecular sieve of step (3) is dried； (5) Y molecular sieve that liquid or gaseous unsaturated olefin are dried with step (4) is come into full contact with, then in oxygen-containing atmosphere Middle progress carbon deposit reaction；(6) the carbon deposit Y molecular sieve quick high-temp calcination process for preparing step (5)；(7) step (6) is obtained Molecular sieve carry out dealumination complement silicon processing；(8) treated after Y molecular sieve filtered, dried through dealumination complement silicon for step (7), into Capable processing of making charcoal, obtains modified Y molecular sieve；Unsaturated olefin described in step (5) is the positive structure or different that carbon atom number is 2 ~ 10 Structure alkene, alkadienes；Wherein the alkene and molecular sieve, which come into full contact with, refers to that unsaturated olefin diffuses into inside molecular sieve； When using gaseous state unsaturated olefin, gaseous state unsaturated olefin and molecular sieve contact conditions are as follows: 0.1 ~ 1.0MPa of pressure, when contact Between 0.1 ~ 2 hour；When using liquid unsaturated hydrocarbons, liquid unsaturated olefin and molecular sieve contact conditions are as follows: pressure 0.1 ~ 1.0MPa, time of contact 0.5 ~ 4 hour, molecular sieve answered thorough impregnation in liquefied olefines；Oxygen-containing atmosphere described in step (5) is Air；Carbon deposit reaction condition are as follows: 150 ~ 300 DEG C of reaction temperature, the reaction time is 12 ~ 25 hours；Quick height described in step (6) Warm roasting condition are as follows: maturing temperature is 400 ~ 600 DEG C, and calcining time is 2 ~ 50 minutes.
2. according to the method for claim 1, it is characterised in that: Ammonium Salt Ionic exchange process described in step (1) is as follows: with NaY zeolite is raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, is exchanged 1 ~ 3 hour, and exchange times are 1 ~ 4 time, after obtaining exchange NaY zeolite, Na2O content is less than 3.0%；The wherein SiO of NaY zeolite raw material2/Al2O3Molar ratio is 3 ~ 6, sodium oxide molybdena quality hundred Divide content 6% ~ 7%；Ammonium salt is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, and ammonium salt is water-soluble 0.3 ~ 6.0mol/L of liquid concentration.
3. according to the method for claim 1, it is characterised in that: step (2) described hydrothermal treatment process is steamed in itself water Gas is passed through under conditions of vapor, hydrothermal conditions are as follows: temperature is 530 ~ 650 DEG C, and pressure is 0.01 ~ 0.5MPa, processing Time is 1.0 ~ 6.0 hours.
4. according to the method for claim 1, it is characterised in that: aluminium salt used in aluminium salt treatment process described in step (3) It is aluminium chloride, aluminum sulfate, aluminum nitrate；Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the processing time is 0.5 ~ 3 hours.
5. according to the method for claim 1, it is characterised in that: drying temperature described in step (4) is 90 ~ 300 DEG C, dry Time is 2 ~ 10 hours.
6. according to the method for claim 1, it is characterised in that: the processing of dealumination complement silicon described in step (7) is using conventional The Y molecular sieve that step (6) obtains first is added water to be made into the water sample mixing of liquid-solid ratio 3 ~ 6, so by ammonium fluosilicate dealumination complement silicon method Afterwards, it is that 1.0 ~ 3.0mol/L ammonium fluosilicate aqueous solution is handled 1 ~ 4 hour in 70 ~ 100 DEG C that concentration, which is added,.
7. according to the method for claim 1, it is characterised in that: treatment conditions of making charcoal described in step (8) are as follows: 400 ~ 600 It is roasted 2 ~ 4 hours at DEG C, removes remaining carbon deposit on molecular sieve.
8. according to the method for claim 1, it is characterised in that: the modified Y molecular sieve has the property that structure cell is normal Number is 2.425 ~ 2.440, and body phase silica alumina ratio is 20 ~ 40, wherein surface layer silica alumina ratio 50 ~ 120, and surface layer silica alumina ratio is higher than body phase sial Than 10 ~ 80；Wherein the superficial layer refers to molecular sieve outer surface to 10 ~ 200nm of inside；Sodium oxide molybdena mass percentage is less than 1.0%；650 ~ 900m of modified Y molecular sieve specific surface area2/ g, Kong Rong 0.30 ~ 0.50ml/g, infrared 0.1 ~ 0.8mmol/ of acid content G, relative crystallinity 80% ~ 110%.
9. according to Catalyst For Single-stage Hydrocracking prepared by method described in claim 1 ~ 8 any claim, feature exists In: including silica-alumina supports 30% ~ 80% and active metal 20% ~ 70% containing modified Y molecular sieve, wherein active metal is aoxidized with metal Object meter；Group VIII and/or vib metals element of the active metal in the periodic table of elements, group VIII are living Property metal be Ni and/or Co, group VIB active metal is W and/or Mo, and group VIII active metallic content is 3% ~ 15%, the Group vib active metallic content is 10% ~ 40%, in terms of metal oxide.
10. adding according to Catalyst For Single-stage Hydrocracking prepared by method described in claim 1 ~ 8 any claim in single hop Application in hydrogen process reaction process, operating condition are as follows: 6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, 0.3 ~ 3.0h of feed volume air speed-1, hydrogen to oil volume ratio is 500 ~ 2000:1.
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CN104826651A (en) * 2014-02-08 2015-08-12 中国石油化工股份有限公司 Preparation method for hydrocracking catalyst
CN104826653A (en) * 2014-02-08 2015-08-12 中国石油化工股份有限公司 Preparation method for hydrocracking catalyst
CN104826652A (en) * 2014-02-08 2015-08-12 中国石油化工股份有限公司 Preparation method for hydrocracking catalyst

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CN1073617C (en) * 1998-11-18 2001-10-24 中国石油化工集团公司 Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil
CN1289821A (en) * 1999-09-29 2001-04-04 中国石油化工集团公司 Hydrotransforming catalyst for residual oil and its preparing process
CN1508226A (en) * 2002-12-19 2004-06-30 中国石油化工股份有限公司 Medium oil type hydrocracking catalyst
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