CN105618119B - A kind of method for preparing hydrocracking catalyst - Google Patents

Abstract

The invention discloses a kind of method for preparing hydrocracking catalyst, including following content：First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology into extruded moulding after slurry, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；2nd, the carrier of step 1 is impregnated using the maceration extract containing active metal, the carrier after dipping obtains hydrocracking catalyst through drying, roasting；Wherein described modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Molecular sieve body phase silica alumina ratio is 10 ~ 70, and superficial layer silica alumina ratio 7 ~ 30, superficial layer silica alumina ratio is less than body phase silica alumina ratio.Hydrocracking catalyst prepared by the inventive method has good temperature raising sensitiveness and operating flexibility, is had broad application prospects during hydrocracking reaction.

Description

A kind of method for preparing hydrocracking catalyst

Technical field

The present invention relates to a kind of method for preparing hydrocracking catalyst.

Background technology

Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc. Feature, various heavy inferiors can be fed to high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and petro chemical industry are most important heavy One of oily deep processing technique, at home and abroad obtains increasingly extensive application.The core of hydrocracking process is to be hydrocracked to urge Agent.Hydrocracking catalyst is typical bifunctional catalyst, has hydrogenation and cracking dual-use function.Wherein hydrogenating function leads to The sulphided state form for often having W, Mo, Ni isoreactivity metal is provided, and cracking function is then provided by molecular sieve.It is hydrocracked in China Technology is because its raw material adapts to the characteristics of strong, product adjustability is big, therefore, is usually come by oil refining enterprise as a kind of regulating measure Adapt to the changes in demand in market, when distillate is in great demand between Ru Dang cities field alignment, can some voluminous midbarrels, and market When in great demand to heavy naphtha then can voluminous heavy naphtha, therefore, the operating condition such as air speed, pressure on hydrocracking unit In the case of being relatively fixed, the temperature raising sensitiveness of hydrocracking catalyst is particularly important for device flexible operating, in addition, for Setter, because hydrogen supply is relatively fixed, therefore, hydrogen gas consumption should be reduced as far as possible during device temperature raising Fluctuation so as to be more beneficial for device even running while flexible operating, these are all carried for the research and development of hydrocracking catalyst Higher requirement is gone out.

At present, it is modified Y molecular sieve that hydrocracking process is the most widely used, inside and outside conventional processing method molecular sieve Distribution of silicon and aluminium is uniform, and acid centre is uniformly distributed, and when reducing Y molecular sieve silica alumina ratio, improves Y molecular sieve acid site density, Temperature raising sensitiveness is improved, but simultaneously, second pyrolysis is also significantly increased, and hydrogen consumption is substantially improved.It is and deep when being carried out to Y molecular sieve Degree processing, when sour density is too low, catalyst temperature raising sensitiveness is again poor.

CN200710158784.0 discloses a kind of hydrocracking catalyst containing Y molecular sieve and preparation method thereof, 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 obtained catalyst temperature raising is sensitive Property it is higher, but simultaneously, temperature raising process second pyrolysis substantially increases, and hydrogen consumption significantly rises, and is unfavorable for industrial hydrocracking unit Temperature raising process apparatus even running.

CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, prepared by the invention Hydrocracking catalyst temperature raising sensitiveness is poor.

The content of the invention

In view of the shortcomings of the prior art, the present invention puies forward a kind of method for preparing hydrocracking catalyst, the inventive method system Standby hydrocracking catalyst has good temperature raising sensitiveness and operating flexibility, has during hydrocracking reaction wide Application prospect.

The method for preparing hydrocracking catalyst of the present invention, including following content：

First, modified Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed according to a certain ratio, add dust technology Extruded moulding after into slurry, dry, roasting obtains the silica-alumina supports containing modified Y molecular sieve；Wherein the concentration of dust technology be 3wt% ~ 30wt%；Described drying condition is：Dried 1 ~ 5 hour at 80 ~ 120 DEG C；Roasting condition is：At 400 ~ 700 DEG C roasting 1 ~ 5 hours；

2nd, the carrier of step 1 is impregnated using the maceration extract containing active metal, the carrier after dipping is through drying, roasting Burn, obtain hydrocracking catalyst；Group VIII and/or vib gold of the described active metal in the periodic table of elements Belong to element, group VIII active metal can be Ni and/or Co, and vib active metal can be W and/or Mo；Wherein impregnate Liquid-solid ratio be 1.5：1~3：1, carried out by the way of saturation well known in the art dipping, group vib metal compound in maceration extract The content of thing is calculated as 20 ~ 60g/100ml by corresponding oxide, and the content of group VIII metallic compound is calculated as by corresponding oxide 3 ~ 20g/100ml, the concentration of metallic compound can need adjust accordingly according to product in maceration extract；Wherein described is dry Dry condition is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C；

Mass percent of the wherein described modified Y molecular sieve in silica-alumina supports is 15% ~ 90%, preferably 30% ~ 70%, remaining Measure as amorphous silica-alumina and/or aluminum oxide；Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm；Body phase silica alumina ratio（Wen Zhong Described silica alumina ratio is SiO₂/Al₂O₃Mol ratio）For 10 ~ 70, preferably 20 ~ 50, superficial layer silica alumina ratio 7 ~ 30, preferably 9 ~ 20, table Surface layer silica alumina ratio is less than body phase silica alumina ratio 5 ~ 40, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness Degree scope, more preferably preferably 10 ~ 200nm, 50 ~ 190nm, superficial layer are primary in Y molecular sieve crystal grain before modified；Sodium oxide molybdena quality Percentage composition is less than 1.0%, preferably smaller than 0.5%；650 ~ 900m of modified Y molecular sieve specific surface area²/g；0.30 ~ 0.50ml/ of pore volume g；Infrared 0.3 ~ 1.2mmol/g of acid content, preferably 0.4 ~ 1.0mmol/g；Relative crystallinity 80 ~ 120%.

The preparation method of described modified Y molecular sieve, including following content：

（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；

（2）To step（1）In obtained ammonium exchange after Y molecular sieve carry out hydro-thermal process；

（3）To step（2）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution；

（4）To step（3）The Y molecular sieve drying process of gained；

（5）By liquid or gaseous unsaturated olefin and step（4）Y molecular sieve after drying process fully contacts, then Carbon deposit reaction is carried out in oxygen-containing atmosphere；

（6）By step（5）The carbon deposit Y molecular sieve quick high-temp calcination process of preparation；

（7）By step（6）Obtained molecular sieve carries out alkali desiliconization processing；

（8）Step（7）Through alkali desiliconization processing after Y molecular sieve it is filtered, dry after, carry out processing of making charcoal, obtain pre- place The Y molecular sieve of reason.

Step（1）Described in Ammonium Salt Ionic exchange process it is as follows：It is raw material in ammonium salt aqueous solution using NaY zeolite, 60 ~ At 120 DEG C, at preferably 60 ~ 90 DEG C, exchange 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/Al₂O₃Mol ratio is 3 ~ 6, sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt It is the one or more in 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）The hydrothermal treatment process is the hydro-thermal process bar in itself vapor or under conditions of being passed through vapor Part is：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and processing time is 1.0 ~ 6.0 hours.

Step（3）Aluminium salt used in described aluminium salt processing procedure 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 processing time is 0.5 ~ 3 hour.

Step（4）Described drying process process：90 ~ 300 DEG C of dryings 2 ~ 10 hours.

Step（5）Described unsaturated olefin is the positive structure or isomeric olefine that charcoal atomicity is 2 ~ 10, alkadienes；Wherein institute The alkene stated fully contacts with molecular sieve refers to that unsaturated olefin is diffused into inside molecular sieve；When use gaseous state unsaturated olefin When, gaseous state unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact；When using liquid During state unsaturated hydrocarbons, liquid unsaturated olefin is with molecular sieve contact conditions：0.1 ~ 1.0MPa of pressure, time of contact 0.5 ~ 4 are small When, molecular sieve answers thorough impregnation in liquefied olefines.Described alkene fully contacts with molecular sieve typically to be carried out at normal temperatures, institute The unsaturated hydrocarbons state phase stated is phase under normal temperature.

Step（5）Described oxygen-containing atmosphere is the mixing of air, the mixture of oxygen and nitrogen or oxygen and inert gas One kind in thing, the volume fraction of oxygen in the gas phase are 10% ~ 100%, preferably air；Carbon deposit reaction condition is：Reaction temperature 50 ~ 500 DEG C of degree, preferably 100 ~ 400 DEG C, the reaction time is 1 ~ 50 hour, preferably 2 ~ 40 hours.

Step（6）Described quick high-temp calcination process condition is：Sintering temperature is 400 ~ 600 DEG C, roasting time 2 ~ 50 Minute, preferably 5 ~ 20 minutes.In general roasting process is：The Y molecular sieve of carbon deposit is directly added into and is warming up to sintering temperature in advance Muffle kiln roasting.

Step（7）Described in the alkali lye that uses of alkali desiliconization processing procedure be sodium hydroxide or the aqueous solution of potassium hydroxide, Wherein the concentration of alkali lye is 0.1wt% ~ 2wt%.50 ~ 100 DEG C of base extraction temperature, processing time are 0.5 ~ 4 hour, alkali lye/point The solid mass ratio of son sieve liquid is 5:1~10:1.

Step（8）Described treatment conditions of making charcoal are：It is calcined 2 ~ 4 hours at 400 ~ 600 DEG C, removes what is remained on molecular sieve Carbon deposit.

The present invention carries out microsection component analyzing come measure and calculation molecular sieve surface using transmission electron microscope X ray electronic spectroscopy Layer and body phase silica alumina ratio.

Hydrocracking catalyst of the present invention can be applied to flexibly production industrial chemicals or intermediate oil etc. it is different plus Hydrogen cracking reaction process, general operational requirement(GOR) are：6.0 ~ 20.0MPa of reaction pressure, 350 ~ 420 DEG C of reaction temperature, feed volume 0.1 ~ 2.0h of air speed^-1, hydrogen to oil volume ratio 500：1~2000：1.

In the inventive method, the Y molecular sieve used hydrocracking catalyst carries out specially treated, i.e., first in air gas Make to be adsorbed in unsaturated hydrocarbons abundant carbon deposits inside and outside molecular sieve such as alkene on Y molecular sieve, alkadienes in atmosphere, under heating condition, Then, the method being calcined by quick high-temp burns up the charcoal deposited on molecular sieve surface, is covered inside such molecular sieve by carbon deposit Protection, therefore, in follow-up alkali liquor desiliconization processing procedure, is mainly carried out, after alkali-treated, then high-temperature roasting is removed on the outer surface The carbon deposit of molecular sieve internal residual, recover the acid sites position inside molecular sieve.The inventive method is by selectivity to Y molecular sieve Outer surface carries out alkali desiliconization processing, and while high silica alumina ratio inside molecular sieve is retained, selective reduces outside Y molecular sieves The silica alumina ratio on surface, the acid centre of molecular sieve outer surface is improved, the hydrogenation prepared compared to conventional method modified molecular screen Cracking catalyst can significantly improve temperature raising sensitiveness, the operating flexibility of catalyst, and device liquid is received and changed under same conversion Hydrogen consumption is learned all to make moderate progress.

Brief description of the drawings

Fig. 1 is the transmission electron microscope of modified Y molecular sieve prepared by embodiment 1（TEM）Photo.

Embodiment

Below by embodiment, the present invention is further described, but is not so limited the present invention.

Embodiment 1

Molecular sieve modified processing procedure：

（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 contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.5%；

（2）To step（1）570 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 is stirred with distilled water, then heats to 80 DEG C, is stirring 0.6mol/L aluminum sulfate solution 400ml, isothermal reaction 2 hours are added during mixing.

（4）Step（3）The drying 4 hours of 150 DEG C of gained molecular sieve；

（5）Take step（4）The molecular sieve of gained is positioned in the closed container full of butadiene atmosphere, control pressure 0.3MPa is fully contacted 20 minutes, then, is heated 15 hours at 200 DEG C in air atmosphere；

（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 450 DEG C of Muffle furnace, is calcined 10 minutes；

（7）Step（6）The Y molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with 0.7% sodium hydroxide solution, at 90 DEG C Reason 2 hours；

（8）Through step（7）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed Property Y molecular sieve, numbering Y-1.

Y-1 molecular sieve transmission electron microscope EDAX results determine its outer surface to 70nm thickness, and superficial layer silica alumina ratio is 14, Molecular sieve body phase silica alumina ratio is 26.XRD analysis result shows that its lattice constant is 2.436nm, relative crystallinity 88%.Pore volume 0.44ml/g, specific surface area 700m²/ g, infrared analysis result measure Y-1 meleic acids amount is 0.68mmol/g.

Hydrocracking catalyst preparation process：

（1）Configure W-Ni dipping solutions：Ammonium metatungstate 430g and nickel nitrate 440g is taken to configure 1000ml leachings after being dissolved in water Stain solution, active metal is with WO in gained dipping solution₃It is respectively 36g/100ml and 11g/100ml with NiO cubages, it is molten Liquid numbering RY-1；

（2）Y-1 55g are taken to be mixed with 45g macroporous aluminium oxides, addition 4g/100ml dust technologies mix in a mixer to roll To extrudable shape, extruded moulding obtains carrier T-1 on banded extruder；

（3）Take T-1 60g to add 120ml RY-1 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast Burn 3 hours, obtain hydrocracking catalyst, numbering Cat-1.

Embodiment 2

Molecular sieve modified processing procedure：

（1）The NaY molecular sieve original powder for taking laboratory to prepare, with the ammonium nitrate that concentration is 0.8mol/L according to liquid-solid ratio 3:1 Mixing, 70 DEG C exchange 3 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.0%.

（2）To step（1）590 DEG C of obtained Y molecular sieve, hydro-thermal process 3 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 6:1 is stirred with distilled water, then heats to 90 DEG C, is stirring 0.8mol/L aluminum sulfate solution 600ml, isothermal reaction 2 hours are added during mixing.

（4）Step（3）The drying 2 hours of 250 DEG C of gained molecular sieve；

（5）Take heptene soaking step（4）The molecular sieve of gained 4 hours, then, 250 DEG C of heating 10 are small in air atmosphere When；

（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 20 minutes；

（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with 1.2% sodium hydroxide solution, 80 DEG C of processing 3 hours；

（8）Through step（7）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed Property Y molecular sieve, numbering Y-2.

Hydrocracking catalyst preparation process：

（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml leachings after being dissolved in water Stain solution, active metal is with WO in gained dipping solution₃It is respectively 40g/100ml and 12g/100ml with NiO cubages, it is molten Liquid numbering RY-2；

（2）Y-2 45g are taken to be mixed with 55g macroporous aluminium oxides, addition 4g/100ml dust technologies mix in a mixer to roll To extrudable shape, extruded moulding obtains carrier T-2 on banded extruder；

（3）Take T-2 60g to add 120ml RY-2 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast Burn 3 hours, obtain hydrocracking catalyst, numbering Cat-2.

Y-2 molecular sieve transmission electron microscope EDAX results determine its outer surface to 130nm thickness, the silica alumina ratio of superficial layer 8, molecular sieve body phase silica alumina ratio is 35.XRD analysis result shows that its lattice constant is 2.430nm, relative crystallinity 84%.Pore volume 0.47, specific surface area 690m²/ g, infrared analysis result measure Y-2 meleic acids amount is 0.58mmol/g.

Embodiment 3

Molecular sieve modified processing procedure：

（1）The NaY molecular sieve original powder for taking laboratory to prepare, with the ammonium nitrate that concentration is 0.6mol/L according to liquid-solid ratio 3:1 Mixing, 80 DEG C exchange 2 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.3%.

（2）To step（1）590 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 6:1 is stirred with distilled water, then heats to 85 DEG C, is stirring 0.6mol/L aluminum sulfate solution 600ml, isothermal reaction 2 hours are added during mixing.

（4）Step（3）The drying 4 hours of 150 DEG C of gained molecular sieve；

（5）Take hexadiene soaking step（4）The molecular sieve of gained 3 hours, then, 180 DEG C of heating 20 in air atmosphere Hour；

（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 500 DEG C of Muffle furnace, is calcined 30 minutes；

（7）Step（6）The molecular sieve of gained is according to liquid-solid ratio 6:1 mixes with 1.0% sodium hydroxide solution, 75 DEG C of processing 2 hours；

（8）Through step（7）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed Property Y molecular sieve, numbering Y-3.

Hydrocracking catalyst preparation process：

（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml leachings after being dissolved in water Stain solution, active metal is with WO in gained dipping solution₃It is respectively 40g/100ml and 12g/100ml with NiO cubages, it is molten Liquid numbering RY-3；

（2）Y-3 45g are taken to be mixed with 55g macroporous aluminium oxides, addition 4g/100ml dust technologies mix in a mixer to roll To extrudable shape, extruded moulding obtains carrier T-3 on banded extruder；

（3）Take T-3 60g to add 120ml RY-3 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast Burn 3 hours, obtain hydrocracking catalyst, numbering Cat-3.

Y-3 molecular sieve transmission electron microscope EDAX results determine its outer surface to 190nm thickness, the silica alumina ratio of superficial layer 9, molecular sieve body phase silica alumina ratio is 34.XRD analysis result shows that its lattice constant is 2.431nm, relative crystallinity 85%.Pore volume 0.46, specific surface area 695m²/ g, infrared analysis result measure Y-3 meleic acids amount is 0.59mmol/g.

Embodiment 4

Molecular sieve modified processing procedure：

（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, 70 DEG C exchange 2 hours, repeat this process 3 times, and Na contents are with Na in the Y molecular sieve after exchange₂O is calculated as 2.6%；

（2）To step（1）560 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.1MPa；

（3）Step（2）Gained molecular sieve is according to liquid-solid ratio 5:1 is stirred with distilled water, then heats to 80 DEG C, is stirring 0.9mol/L aluminum sulfate solution 300ml, isothermal reaction 1.5 hours are added during mixing.

（4）Step（3）The drying 4 hours of 150 DEG C of gained molecular sieve；

（5）Take step（4）The molecular sieve of gained is positioned in the closed container full of propylene atmosphere, control pressure 0.2MPa Fully contact 25 minutes, then, heated 12 hours at 250 DEG C in air atmosphere；

（6）Step（5）Molecular sieve after processing, which is directly placed into, to be previously heated in 470 DEG C of Muffle furnace, is calcined 12 minutes；

（7）Step（6）The Y molecular sieve of gained is according to liquid-solid ratio 5:1 mixes with 0.6% sodium hydroxide solution, at 95 DEG C Reason 2 hours；

（8）Through step（7）Y molecular sieve after alkali process, 120 DEG C of dryings 2 hours, after 550 DEG C of roastings 2 hours, changed Property Y molecular sieve, numbering Y-4.

Y-4 molecular sieve transmission electron microscope EDAX results determine its outer surface to 100nm thickness, superficial layer silica alumina ratio 13, molecular sieve body phase silica alumina ratio is 25.XRD analysis result shows that its lattice constant is 2.437nm, relative crystallinity 90%.Pore volume 0.44ml/g, specific surface area 710m²/ g, infrared analysis result measure Y-1 meleic acids amount is 0.70mmol/g.

Hydrocracking catalyst preparation process：

（1）Configure W-Ni dipping solutions：Ammonium metatungstate 430g and nickel nitrate 440g is taken to configure 1000ml leachings after being dissolved in water Stain solution, active metal is with WO in gained dipping solution₃It is respectively 36g/100ml and 11g/100ml with NiO cubages, it is molten Liquid numbering RY-4；

（2）Y-4 55g are taken to be mixed with 45g macroporous aluminium oxides, addition 4g/100ml dust technologies mix in a mixer to roll To extrudable shape, extruded moulding obtains carrier T-4 on banded extruder；

（3）Take T-4 60g to add 120ml RY-4 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C roast Burn 3 hours, obtain hydrocracking catalyst, numbering Cat-4.

Comparative example 1

Using a kind of wide variety of hydrocracking catalyst of industry, BCat-1 is counted as, except modified Y in its 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 Mol ratio is 23.XRD analysis result shows that its lattice constant is 2.440nm, relative crystallization Degree 95%, pore volume 0.33ml/g, specific surface area 720m²/ g, meleic acid amount are 0.73 mmol/g.

Comparative example 2

Using a kind of wide variety of hydrocracking catalyst of industry, BCat-2 is counted as, except modified Y in its catalyst formulation Outside molecular sieve, remaining composition and method for preparing catalyst are same as Example 2, the Y molecular sieves that catalyst BCat-2 is used Matter is as follows：Molecular sieve SiO₂/Al₂O₃ Mol ratio is 32.XRD analysis result shows that its lattice constant is 2.426nm, relative crystallization Degree 90%, pore volume 0.38ml/g, specific surface area 690m²/ g, meleic acid amount are 0.54 mmol/g.

Embodiment 5

The reactivity worth of catalyst is prepared in order to investigate embodiment 1 ~ 4 and comparative example 1 ~ 2, to catalyst on midget plant Evaluation test is carried out, evaluating apparatus uses single hop to connect once by flow, and an anti-filling regular refiner catalyst, two instead divide The hydrocracking catalyst according to embodiment 1 ~ 4 and the preparation of the method for comparative example 1 ~ 2 is not loaded, and evaluation result is listed in 1 ~ table of table 4.

The raw material oil nature of table 1.

The appreciation condition of table 2.

The evaluation result of table 3.

The embodiment 1 of table 4 is investigated with the catalyst differential responses temperature of comparative example 1 to be tested.

The embodiment 2 of table 5 is investigated with the catalyst differential responses temperature of comparative example 2 to be tested.

Show by using contrast test of the embodiment 1 with the catalyst of comparative example 1 on evaluating apparatus, using present invention side Catalyst prepared by method has more preferable operating flexibility, and product changes in distribution amplitude is larger during temperature raising, can switch progress Voluminous naphtha and the less operation of production naphtha both of which, simultaneously as the present invention uses specific process modified Y molecular sieve, While improving acid centre outside molecular sieve, the high silica alumina ratio inside molecular sieve is remained, acid centre is less, temperature raising process Caused by secondary cracking significantly reduce, accordingly, with respect to the catalyst of comparative example 1, the catalyst of embodiment 1 during temperature raising hydrogen consume Increase and liquid receipts fall are smaller, are more beneficial for the quiet run of device.Embodiment 2 is with the catalyst of comparative example 2 to having a competition Test, show, the catalyst of embodiment 2 causes the catalyst of embodiment 2 to have more due to the higher acid site quantity of molecular sieve outer surface Good temperature raising sensitiveness, 350 DEG C of cut conversion ratios raisings are more than during reaction temperature is improved to 380 DEG C from 372 DEG C about 16 percentage points, and comparative example 2 only improves 6 percentage points, compared to the catalyst of comparative example 2, the catalyst of embodiment 2 shows bigger Product distribution flexibility.Therefore, all in all catalyst of the present invention shows good temperature raising sensitiveness, device operation flexibly Property and higher liquid yield.

Claims (16)

1. A kind of 1. method for preparing hydrocracking catalyst, it is characterised in that including following content：First, by modified Y molecular sieve, nothing Sizing sial and/or aluminum oxide are well mixed according to a certain ratio, are added dust technology into extruded moulding after slurry, are dried, are calcined To the silica-alumina supports containing modified Y molecular sieve；2nd, the carrier of step 1 is impregnated using the maceration extract containing active metal, soaked Carrier after stain obtains hydrocracking catalyst through drying, roasting；Modified Y molecular sieve lattice constant wherein described in step 1 For 2.425 ~ 2.455nm；Molecular sieve body phase silica alumina ratio is 10 ~ 60, and superficial layer silica alumina ratio 7 ~ 30, superficial layer silica alumina ratio is less than body phase Silica alumina ratio 5 ~ 40, wherein described superficial layer refers to molecular sieve outer surface to 5 ~ 400nm of inside thickness range, superficial layer it is primary in Y molecular sieve crystal grain before modified；650 ~ 900m of modified Y molecular sieve specific surface area²/g；0.30 ~ 0.50ml/g of pore volume；Meleic acid contains Measure 0.3 ~ 1.2mmol/g；Relative crystallinity 80 ~ 120%；Quality percentage of the wherein described modified Y molecular sieve in silica-alumina supports Than for 15% ~ 90%；Described silica alumina ratio is SiO₂/Al₂O₃Mol ratio.
2. 2. in accordance with the method for claim 1, it is characterised in that：Drying condition described in step 1 is：At 80 ~ 120 DEG C Dry 1 ~ 5 hour；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
3. 3. in accordance with the method for claim 1, it is characterised in that：Active metal described in step 2 is in the periodic table of elements Group VIII and/or vib metals element；Group VIII active metal is Ni and/or Co, and vib active metal is W And/or Mo；The liquid-solid ratio wherein impregnated is 1.5：1~3：1, the content of group vib metallic compound presses corresponding oxide in maceration extract 20 ~ 60g/100ml is calculated as, the content of group VIII metallic compound is calculated as 3 ~ 20g/100ml by corresponding oxide.
4. 4. in accordance with the method for claim 1, it is characterised in that：Drying condition described in step 2 is：At 90 ~ 150 DEG C Dry 2 ~ 8 hours；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
5. 5. in accordance with the method for claim 1, it is characterised in that：The preparation method of described modified Y molecular sieve, including it is as follows Content：（1）Ammonium Salt Ionic exchange is carried out in ammonium salt aqueous solution by former powder of NaY zeolite；（2）To step（1）In obtained ammonium Y molecular sieve after exchange carries out hydro-thermal process；（3）To step（2）Y molecular sieve after hydro-thermal process is handled with aluminum salt solution；（4） To step（3）The Y molecular sieve drying process of gained；（5）By liquid or gaseous unsaturated olefin and step（4）Drying process Y molecular sieve is fully contacted, and carbon deposit reaction is then carried out in oxygen-containing atmosphere；（6）By step（5）The carbon deposit Y molecular sieve of preparation is fast Fast high-temperature roasting processing；（7）By step（6）Obtained molecular sieve carries out alkali desiliconization processing；（8）Step（7）Handled through alkali desiliconization Rear Y molecular sieve is filtered, dry after, carry out processing of making charcoal, obtain modified Y molecular sieve；Step（6）Described quick high-temp roasting Burning condition is：Sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes.
6. 6. in accordance with the method for claim 5, it is characterised in that：Step（2）The hydrothermal treatment process is steamed in itself water Gas is passed through under conditions of vapor, and hydrothermal conditions are：Temperature is 500 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, processing Time is 1.0 ~ 6.0 hours.
7. 7. in accordance with the method for claim 5, it is characterised in that：Step（3）Aluminium salt used in described aluminium salt processing procedure It is the one or more in aluminium chloride, aluminum sulfate or aluminum nitrate；Aluminium salt concentration is 0.05 ~ 2mol/L；Treatment temperature is 50 ~ 120 DEG C, processing time is 0.5 ~ 3 hour.
8. 8. in accordance with the method for claim 5, it is characterised in that：Step（4）Described drying process process：90 ~ 300 DEG C dry Dry 2 ~ 10 hours.
9. 9. in accordance with the method for claim 5, it is characterised in that：Step（5）Described unsaturated olefin is that carbon number is 2 ~ 10 positive structure or isomeric olefine, alkadienes.
10. 10. according to the method described in claim 5 or 9, it is characterised in that：Step（5）Described gaseous state unsaturated olefin is with dividing Son sieves contact conditions：0.1 ~ 1.0MPa of pressure, 0.1 ~ 2 hour time of contact.
11. 11. according to the method described in claim 5 or 9, it is characterised in that：Step（5）Described liquid unsaturated olefin is with dividing Son sieves contact conditions：0.1 ~ 1.0MPa of pressure, 0.5 ~ 4 hour time of contact, molecular sieve thorough impregnation is in liquefied olefines.
12. 12. in accordance with the method for claim 5, it is characterised in that：Step（5）Described oxygen-containing atmosphere be air, oxygen with One kind in the mixture or oxygen of nitrogen and the mixture of inert gas, the volume fraction of oxygen in the gas phase be 10% ~ 100%。
13. 13. in accordance with the method for claim 5, it is characterised in that：Step（5）Described carbon deposit reaction condition is：Reaction temperature 50 ~ 500 DEG C of degree, reaction time are 1 ~ 50 hour.
14. 14. in accordance with the method for claim 5, it is characterised in that：Step（7）Described in alkali desiliconization processing procedure use Alkali lye is the aqueous solution of sodium hydroxide or potassium hydroxide, and the wherein concentration of alkali lye is 0.1wt% ~ 2wt%；Base extraction temperature 50 ~ 100 DEG C, processing time is 0.5 ~ 4 hour；The solid mass ratio of alkali lye/molecular sieve liquid is 5:1~10:1.
15. 15. in accordance with the method for claim 5, it is characterised in that：Step（8）Described treatment conditions of making charcoal are：400~600 It is calcined 2 ~ 4 hours at DEG C.
16. 16. according to hydrocracking catalyst prepared by claim 1 ~ 5 any claim methods described in flexibly production chemical industry Application during the hydrocracking reaction of raw material or intermediate oil, it is characterised in that operating condition is：Reaction pressure 6.0 ~ 20.0MPa, 350 ~ 420 DEG C of reaction temperature, 0.1 ~ 2.0h of feed volume air speed^-1, hydrogen to oil volume ratio 500：1~2000：1.