CN104826648B - A kind of preparation method of catalytic hydro-dearomatization catalyst - Google Patents

Abstract

The invention discloses the preparation method of a kind of catalytic hydro-dearomatization catalyst.Silica alumina ratio is higher, degree of crystallinity is high, the NaY type Molecular sieve raw material of good stability in the method employing, after sequentially passing through alkali cleaning, ammonium exchange, dealumination complement silicon, hydro-thermal process and processing with the mixed solution of acid and ammonium salt, obtains small crystal grain Y-shaped molecular sieve.Using this small crystal grain Y-shaped molecular sieve as acidic components, match with amorphous silica-alumina and active component and adjuvant component, there is higher hydrogenation aromatics-removing activity, be particularly suitable for hydrogenation aromatics-removing and the decolorization of the cycloalkyl high viscosity white oil containing heavy aromatics and solvent naphtha.

Description

A kind of preparation method of catalytic hydro-dearomatization catalyst

Technical field

The present invention relates to the preparation method of a kind of Hydrobon catalyst, particularly relate to the preparation of catalytic hydro-dearomatization catalyst Method.This catalyst is suitable for the hydrogenation process of aromatic hydrocarbons, is particularly suitable for the hydrogenation aromatics-removing mistake of naphthene base crude oil containing heavy aromatics Journey.

Background technology

Under aerobic conditions, hydrotreating generates oil (such as top-grade lubricating oil, food-level white oil etc.) to daylight, ultraviolet spoke Penetrating very sensitive, being exposed in daylight and air and cause oil product appearance property unstable, oil product color can be deepened, and it is heavy to produce when serious Form sediment.This type of oil requires that viscosity is low, and flash-point and boiling point are high, and volatility is little.Colorless and odorless, arene content is low, and non-corrosiveness is good Thermostability and oxidation stability, be difficult to cause gel, and biological property is good, meets environmental requirement.

The problems referred to above to be solved, it is saturated that most efficient method carries out deep hydrogenation aromatic hydrocarbons to it exactly.Use conventional adding Hydrogen catalyst for refining, owing to the fault of construction of catalyst and cycloalkyl viscous crude cut have, viscosity is big, molecular weight is high, condensed ring knot The many features of structure, cause the polycyclic aromatic hydrocarbon in big molecular fraction to be difficult to sufficiently to be hydrogenated with saturated, it requires that catalyst must Must have higher deep removal aromatic hydrocarbons, the particularly catalysis activity of polycyclic aromatic hydrocarbon, meet product aromatic hydrocarbons and be less than 0.05%, color (Sai Shi)+30, readily carbonizable substance (100 DEG C) by being less than the requirement of the indexs such as 0.1cm with ultraviolet absorptivity (260nm-420nm). Catalyst also should have preferable selectivity simultaneously, makes the index such as viscosity, pour point and flash-point of hydrofinishing product change not Greatly.And the Y type molecular sieves that use in this type of catalyst, such as lube oil hydrogenation essences such as CN1317368C, CN201010197869.1. more Catalyst processed, carrier is made up of Y type molecular sieve and amorphous silica-alumina, and active component is mainly Pd and Pt.Y type molecular sieve performance Quality, directly affects performance and the product quality of catalyst.

Conventional Y molecular sieve, crystal grain is generally about 1000nm, and its crystal grain is relatively big, and duct is relatively long, and diffusional resistance is big, Big molecule is difficult to enter and reacts inside duct, and afterproduct is also more difficult diffuses out, so its catalytic performance receives in reaction Restriction.Compared with conventional Y type molecular sieve, small crystal grain Y-shaped molecular sieve has bigger external surface area and more outer surface activated centre, Be conducive to improving big molecule hydrocarbon cracking capability, thus there is more superior catalytic perfomance.Meanwhile, Y type molecular sieve is reduced Crystallite dimension can also improve inner surface active sites utilization rate.In general, reactant molecule is in molecular sieve endoporus duct Diffusion is referred to as micropore diffusion.Molecular sieve inner surface to be made all is used for catalyzed conversion, it is necessary to make micropore diffusion speed big In endoporus catalyzed conversion speed.Shortening diffusion path is the best way.The effective way overcoming micropore diffusion to limit is Reduce zeolite crystal size.This not only can increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously. Small crystal grain NaY molecular sieve and big crystal NaY molecular sieve are compared by EP0204236, and result shows, the former is to heavy-oil catalytic Cracking has higher activity and preferable selectivity.

Small crystal grain NaY molecular sieve is not possess acidity, needs to be modified processing, to meet the performance of Cracking catalyst Require.CNl382632A discloses a kind of super stabilizing method of small-grain Y-type zeolite, and the method is with the dry gas of silicon tetrachloride Body and fine grain NaY zeolitic contact, obtain after washing, owing to heat and the hydrothermal stability of its raw material self are just poor, simultaneously This inventive method is that the mode using gas phase dealumination complement silicon processes molecular sieve, and this makes the heat of product and hydrothermal stability worse, Activity is low.Especially to the fine grain NaY zeolite that heat endurance and hydrothermal stability are poor, the sial skeleton structure in molecular sieve Less stable, easily causes the removing of framework aluminum in modifying process, simultaneously also some framework silicon also with removing, Cause part skeleton that the phenomenon caved in occurs so that the crystallization reservation degree of product is relatively low, and the activity of molecular sieve is not high.

CN200910165116.X discloses a kind of small crystal grain Y-shaped molecular sieve and preparation method thereof.Handled by the method Raw material small crystal grain NaY molecular sieve is prepared by the method disclosed in CN101722023A, i.e. SiO₂/Al₂O₃Mol ratio is 4.0～ 6.0, average grain diameter, at 100～700nm, passes sequentially through successive modified i.e. ammonium exchange, at ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal The mixed aqueous solution process of reason, aluminium salt and acid, obtains small-grain Y molecular sieve.In the method, need first to raw material ammonium hexafluorosilicate After dealumination complement silicon is processed, then carrying out hydro-thermal process etc. and processing, so could reduce the caving in of skeleton structure of molecular sieve, raising divides The crystallization reservation degree of son sieve, but after the method is owing to first being processed by ammonium hexafluorosilicate dealumination complement silicon, owing to occurring the sial isomorphous to take In generation, molecular sieve silica constructed of aluminium ratio is more complete, then carries out hydro-thermal process, and the secondary pore of formation is few, and secondary pore proportion is low, no Being beneficial to the diffusion of product, aromatic hydrocarbons saturation degree is low.

At present, owing to the hydrothermal stability of small crystal grain NaY molecular sieve is poor, structural instability, through successive modified, it is impossible to Obtain structural integrity, degree of crystallinity height and the small crystal grain Y-shaped molecular sieve with more secondary pore.

Existing method fine grain NaY type molecular sieve is in preparation process, and silicon and aluminium are easy to run off, and silicon utilization rate is low, and silicon, Reuniting, easily occurs in aluminium distributing inhomogeneity, and therefore still cannot to prepare silica alumina ratio high for existing method, and heat endurance and hydro-thermal steady Qualitative fine grain NaY type molecular sieve good again.Through successive modified, it is impossible to obtain structural integrity, degree of crystallinity is high and has more The small crystal grain Y-shaped molecular sieve of secondary pore, is used for catalytic hydro-dearomatization catalyst, and aromatic hydrocarbons saturation degree is low.

Content of the invention

For overcoming weak point of the prior art, the invention provides the preparation side of a kind of catalytic hydro-dearomatization catalyst Method.This catalyst uses the small crystal grain Y-shaped molecular sieve conduct that a kind of dealumination depth is big, degree of crystallinity holding is good, secondary pore is flourishing Acidic components, have higher hydrogenation aromatics-removing activity, are particularly suitable for the cycloalkyl high viscosity white oil containing heavy aromatics and solvent The hydrogenation aromatics-removing of oil and decolorization.The preparation method of catalytic hydro-dearomatization catalyst of the present invention, comprises the steps:

By small crystal grain Y-shaped molecular sieve, amorphous silica-alumina and the adhesive mechanical mixture made by aluminum oxide, shaping, then It is dried and roasting, make catalyst carrier；Use infusion process in supported on carriers Pt and Pd, drying and roasting, be hydrogenated with Dearomatization catalyst.

The preparation method of described small crystal grain Y-shaped molecular sieve, comprises the steps:

(1) preparation of fine grain NaY type molecular sieve；

(2) by fine grain NaY with containing alkaline solution treatment；

(3) the fine grain NaY type molecular sieve that step (2) obtains is prepared as Na₂The little crystal grain of O content≤2.5wt% NH₄NaY；

(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtaining and pair Product separates；

(5) little crystal grain NH is obtained to step (4)₄NaY molecular sieve carries out hydro-thermal process；

(6) molecular sieve obtaining step (5) is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and be dried, obtain little Grain Y-molecular sieve.

Small crystal grain NaY molecular sieve described in step (1), its character is as follows: SiO₂/Al₂O₃Mol ratio is more than 6.0 and not Higher than 9.0, preferably 6.5～9.0, more preferably 7.0～8.0, average grain diameter is 200～700nm, preferably 300～ 500nm；Specific surface area is 800～1000 m²/ g, preferably 850～950 m²/ g, pore volume 0.30/～0.45mL/g, tie relatively Crystalline substance degree is 90%～130%, and cell parameter is 2.460～2.470nm, through relative crystallinity after roasting in 650 DEG C of air 3 hours It is more than 90%, generally 90%～110%, preferably 90% ~ 105%, after processing 2 hours through 700 DEG C of water vapour hydro-thermals relatively Degree of crystallinity is more than 90%, generally 90%～110%, preferably 90% ~ 105%.

The preparation method of fine grain NaY type molecular sieve in step (1) in the inventive method, comprising:

I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6～30) Na₂O:Al₂O₃: (6 ～30) SiO₂: (100～460) H₂Mixture, after stirring, is stirred ageing at 0～20 DEG C and prepares for 0.5～24 hour by O Directed agents；

II, use preparing amorphous silicon alumnium using carbonization predecessor, with the weight of the butt of amorphous silica-alumina predecessor as base Standard, the content that silicon is counted with silica as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes:

A, respectively preparation sodium aluminate solution and sodium silicate solution；

B, the part sodium silicate solution adding the preparation of step a in the sodium aluminate solution of step a preparation, then pass to CO₂ Gas, control reaction temperature is 10 ~ 40 DEG C, preferably 15～35 DEG C, and the pH value of control cemented into bundles is 8 ~ 11；Wherein when being passed through CO₂Gas flow accounts for the 60% ~ 100% of total intake, when preferably 80% ~ 100%, adds remainder sodium silicate solution, wherein In step b, remainder sodium silicate solution accounts for step b addition sodium silicate solution total amount in terms of silica in terms of silica 5wt% ~ 85wt%, preferably 30wt% ~ 70wt%；

C, at the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel

Press (0.5～6) Na₂O:Al₂O₃: (8～15) SiO₂: (100～460) H₂Total molar ratio of O, at 0～40 DEG C Add water, silicon source, directed agents and alkali source in the amorphous silica-alumina predecessor of step (2) gained under conditions of quick stirring, and Control ph is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel；Wherein directed agents addition accounts for the 1% of silica-alumina gel weight ～20%,

IV, the reactant mixture of step (3) gained are through two step dynamic crystallizations, then through filtering, wash, and are dried, obtain little crystalline substance Grain NaY molecular sieve.

In the present invention, in step I and III, silicon source, alkali source are respectively selected from sodium metasilicate and NaOH.In step I, aluminium source Selected from sodium metaaluminate.

In step II, the concentration of the sodium aluminate solution used by step a is preferably 15～55g Al₂O₃/ l, sodium silicate solution Concentration be 50～150 gSiO₂/ l, CO used by step b₂The concentration of gas is 30v% ~ 60v%.

In step III, control reaction temperature 0～40 DEG C, preferably 10 ~ 30 DEG C, pH value 9.5～12.0, preferable ph 10～ 11。

In step IV, the reactant mixture of gained carries out crystallization and uses two step dynamic crystallizations, and wherein the first step enters Mobile state The condition of crystallization is as follows: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；Second step carries out dynamic crystallization Condition is as follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours, after crystallization completes, then through filtering, washing, doing Dry, prepare product.Two step dynamic crystallization conditions are preferably as follows: the first step: temperature controls at 60～80 DEG C, and crystallization time is 1～ 10 hours；Second step: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.

In step (2), small crystal grain NaY molecular sieve is mixed with the aqueous solution making beating of alkali, and maintains 60～120 DEG C Stir process 1～4h under temperature conditions, filters, washes.Alkali wherein used is the mixture of NaOH, KOH or NaOH and KOH. The concentration of the aqueous solution of alkali is generally 0.1～3 mol/L, and the concentration of slurries Middle molecule sieve is 0.05～1.0g/mL.

In step (4), aqueous medium adds little crystal grain NH₄NaY(solid-liquid weight is than 1:4 ~ 1:8), stir and be warmed up to 90～120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, after dropping finishes, constant temperature stirs 1～2 hour, separates molecular sieve And accessory substance, and filter, be dried.The concentration 10 wt% ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate addition is little Crystal grain NH₄10 wt% of NaY molecular sieve ~ 50wt%.

In step (5), the condition that described hydro-thermal is processed is as follows: treatment temperature controls at 500～750 DEG C, preferably controls At 600～700 DEG C, pressure is 0.01～0.50MPa, preferably 0.05～0.30MPa, and the process time is 1.0～4.0 hours.

In step (6), by hydro-thermal process after molecular sieve with acid and contain NH₄ ⁺Salt composition mixed solution contact, exchange Na in molecular sieve⁺With the part non-framework aluminum in removing molecular sieve, acid therein can be hydrochloric acid, carbonic acid, nitric acid, in sulfuric acid One or more, contain NH₄ ⁺Salt be one or more in the ammonium salt containing above acid group；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺Concentration be 0.5～3.0mol/L, exchange temperature is 70～120 DEG C, exchange slurries Middle molecule sieve Concentration be 0.1～0.5g/mL, swap time is 0.5～3.0 hour, and exchange step may be repeated 1～4 time.Then remove Mother liquor, washes with water, is dried.

Other operating procedures in the modified Y molecular sieve preparation method of the present invention, as ammonium salt exchange can use this area normal The method of operating of rule and condition.Step (3) uses the method for ammonium salt exchange, specific as follows: with NaY molecular sieve as raw material, and using can The aqueous solution of undissolved ammonium salt, at 70～120 DEG C, exchanges 0.5～3.0 hour at preferably 80～100 DEG C, and Y molecular sieve is at exchange slurry Concentration in liquid is 0.05～0.50g/mL, repeated exchanged l～5 time, filters off mother liquor, washing, is dried.Ammonium salt such as ammonium chloride, carbon One or more in acid ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5 ～5.0mol/L.

Small crystal grain Y-shaped molecular sieve of the present invention, its character is as follows: SiO₂/ A1₂O₃Mol ratio is 40～120, crystal grain Average diameter is 200～700nm, preferably 300～500nm, relative crystallinity >=95%, preferably 95% ~ 120%, and lattice constant 2.425～2.435nm, specific surface area is 900～1200m²/ g, pore volume is 0.5～0.80mL/g, the secondary pore of 1.7～10nm Shared pore volume is more than the 50% of total pore volume, preferably 50% ~ 80%, more preferably 55% ~ 75%.

In described catalytic hydro-dearomatization catalyst, the content of Pt is 0.1wt%～0.5wt%, Pd content be 0.3wt%～ 0.8wt%。

In described catalytic hydro-dearomatization catalyst carrier, on the basis of the weight of carrier, its composition includes: small-grain Y-type The content of molecular sieve is 5wt%～40wt%, preferably 10wt%～25wt%, the content of amorphous silica-alumina be 20wt%～ 65wt%, preferably 30wt%～60wt%, the content of aluminum oxide is 10wt%～40wt%, preferably 15wt%～ 30wt%.

Adhesive therefor of the present invention is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3～0.5 mL/g, and specific surface area is 200～400m²/ g.

In catalyst carrier of the present invention, mixing amorphous silica-alumina used with small-grain Y molecular sieve and adhesive can be by altogether Prepared by the precipitation method or grafting copolymerization process, prepare by conventional method in document.SiO in the amorphous silica-alumina preparing₂Weight Content is 20%～60%, preferably 25%～40%, and the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, preferably 0.8～ 1.0 mL/g, specific surface area is 300～500 m²/ g, preferably 350～500 m²/g。

In method for preparing catalyst of the present invention, introduce Pt metal and the method for Pd uses infusion process.The present invention is by amorphous The compound of sial and Y type molecular sieve and adhesive kneading, shaping, drying and roasting obtain carrier, then use infusion process to bear After carrying Pt and Pd, drying and roasting, obtain catalytic hydro-dearomatization catalyst.Wherein, catalyst can become according to actual needs Type, shape can be cylindrical bars, clover etc..Described carrier strip through 80 ~ 150 DEG C of dryings 3 ~ 10 hours, 500 ~ 600 DEG C of roastings 3 ~ 6 hours.Described infusion process can use saturated dipping or the method for excessive dipping, and after impregnating metal Pt and Pd, catalyst is carried out It is dried and the condition of roasting is as follows: 100 ~ 150 DEG C of dryings 1 ~ 12 hour, roasting 3 ~ 6 hours at 450 ~ 550 DEG C.Above-mentioned urge Agent preparation process and condition are all well known to those skilled in the art.

Catalyst of the present invention is particularly suitable for the process of hydrogenation aromatics-removing, is particularly suitable for the cycloalkyl high viscosity containing heavy aromatics The hydrogenation aromatics-removing of white oil, solvent naphtha and hydrocracking tail oil and decolorization, it is possible to obtain good using effect.

Catalyst of the present invention is when processing naphthene base crude oil, and reaction condition is typically under hydrogen existence condition, and reaction pressure is 10 ~ 20MPa, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 7.0h during liquid^-1, reaction temperature 180 ~ 250 DEG C.

Catalytic hydro-dearomatization catalyst of the present invention due to use small crystal grain Y-shaped molecular sieve as acidic components, this molecular sieve Have that high silica alumina ratio, high-crystallinity, secondary pore be many, the feature of bigger serface, with amorphous silica-alumina and hydrogenation active metals group Divide Pt and Pd to match, not only promote the performance of aromatic hydrogenation saturated activity, be more beneficial for the selective opening of aromatic hydrocarbons, and Be conducive to the diffusion of product, hold charcoal ability and also greatly enhance, improve activity, selectivity and the stability of catalyst.This is urged Agent is especially suitable as cycloalkyl raw material, the hydrogenation dearomatization of the cycloalkyl raw material that especially viscosity is high, condensed-nuclei aromatics content is high In hydrocarbon reaction.

The preparation method that the present invention provides has the advantage that the silicon of the NaY type Molecular sieve raw material due to present invention process Aluminum ratio is higher, and degree of crystallinity is high, good stability, thus process through follow-up alkali cleaning, ammonium exchange, dealumination complement silicon, hydro-thermal and with sour and The mixed solution process of ammonium salt, is so conducive to improving the ratio shared by secondary pore of molecular sieve, and special due to raw material Property make molecular sieve process through hydro-thermal and remain in that good stability, and do not affect the stability of final molecular sieve.With this Small crystal grain Y-shaped molecular sieve prepared by the method that invention provides is obtaining higher SiO₂/A1₂O₃While mol ratio, secondary pore institute The ratio accounting for is higher, and maintains the stability of Y type molecular sieve, and molecular sieve has higher specific surface area and higher crystallization Degree.Use this small crystal grain Y-shaped molecular sieve and amorphous silica-alumina kneading and compacting, then dip loading active metal Pt and Pd again, more Be conducive to cooperating of catalyst hydrogenation activity component and carrier component, the activity of raising catalyst, stability, purpose product Selectivity.

Detailed description of the invention

In order to the present invention is better described, further illustrate the present invention below in conjunction with embodiment and comparative example.But this Bright scope is not limited solely to the scope of these embodiments.The present invention analyzes method: specific surface area, pore volume use low temperature liquid nitrogen physics Absorption method, relative crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio uses chemical method, and the crystal grain of molecular sieve is big The mode of little employing SEM (SEM) measures.Wt% is mass fraction.

Embodiment 1

The present embodiment is to prepare raw material fine grain NaY type molecular sieve

The preparation of NY-1

(1) preparation of directed agents: take 10 g sodium hydrate solids and be dissolved in 80g water, adds sodium metaaluminate 2g (Al₂O₃Contain Amount is 45wt%, Na₂O content is 41wt%), then add 36g waterglass (SiO₂Content is 28wt%, Na₂O content is 8 Wt%), 15 DEG C of stirring 4 hours prepared directed agents of ageing after mixing.

(2) preparation of amorphous silica-alumina predecessor

It is 40gAl that solid sodium aluminate is configured to concentration₂O₃/ L sodium aluminate working solution, takes containing SiO₂The silicic acid of 28wt% Sodium solution, then to be diluted to concentration be 100g SiO₂/ L sodium metasilicate working solution.Take 1L sodium aluminate working solution and be placed in plastic cans In, it is subsequently adding 0.2L sodium metasilicate working solution, control reaction temperature 20 DEG C, be passed through the CO that concentration is 50v%₂Gas, works as pH value Reach to stop when 10.0 logical CO₂, add 0.4L sodium metasilicate working solution, then ventilate and stablize 20 minutes.

(3) preparation of gel

Slurries obtained by step (2) add 100g SiO₂Prepared by/L sodium metasilicate working solution 1.5L and step (1) Directed agents 120g, the pH value of gel is 12, control reaction temperature 20 DEG C, uniform stirring 30 minutes, staticize 2 hours.

(4) crystallization

Pour the gel obtained by step (2) in stainless steel cauldron into, stir crystallization 4 hours at 70 DEG C, then heat up To 100 DEG C, stirring crystallization 8 hours, then filter, washing, dry NaY molecular sieve product NY-1, product property is shown in Table 1.

The preparation of NY-2

(1) preparation of directed agents: take 8 g sodium hydrate solids and be dissolved in 80g water, adds sodium metaaluminate 2.5 g (Al₂O₃ Content is 45wt%, Na₂O content is 41wt%).Then 40g waterglass (SiO is added₂Content is 28wt%, Na₂O content is 8 Wt%), 18 DEG C of stirring 4 hours prepared directed agents of ageing after mixing.

(2) preparation of amorphous silica-alumina predecessor

It is 30gAl that solid sodium aluminate is configured to concentration₂O₃/ L sodium aluminate working solution, takes containing SiO₂The silicic acid of 28wt% Sodium solution, then to be diluted to concentration be 70g SiO₂/ L sodium metasilicate working solution.Take 1L sodium aluminate working solution to be placed in plastic cans, It is subsequently adding 0.4L sodium metasilicate working solution, control reaction temperature 18 DEG C, be passed through the CO that concentration is 50v%₂Gas, when pH value reaches To the logical CO of stopping when 10.2₂, add 0.6L sodium metasilicate working solution, then ventilate and stablize 20 minutes.

(3) preparation of gel

Slurries obtained by step (2) add 70g SiO₂Prepared by/L sodium metasilicate working solution 1.5L and step (1) Directed agents 100g, the pH value of gel is 11.5, control reaction temperature 15 DEG C, uniform stirring 30 minutes, staticize 2.5 hours.

(4) crystallization

Pour the gel obtained by step (2) in stainless steel cauldron into, stir crystallization 5 hours at 75 DEG C, then heat up To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry NaY molecular sieve product NY-2, product property is shown in Table 1.

Embodiment 2

First alkali process is carried out to raw material small crystal grain NaY molecular sieve, be 1 mol/L by 1000 grams of NY-1 and 5L concentration NaOH solution making beating mixes, and maintains stir process 2h under the temperature conditions of 80 DEG C, filter, be washed to solution close in Property；Contacting the 0.5mol/L aqueous ammonium nitrate solution of filter cake and 10 liters, speed of agitator is 300rpm, constant temperature stirring at 90 DEG C L hour, then filtering molecular sieve, and stay sample, analyze Na₂O content；Repeat aforesaid operations, until Na in molecular sieve₂O content Reaching 2.5wt%, obtaining dried sample number into spectrum is NNY-1.

Embodiment 3

First alkali process is carried out to raw material small crystal grain NaY molecular sieve, be 0.8 mol/L by 1000 grams of NY-2 and 5L concentration KOH solution making beating mixes, and maintains stir process 2h under the temperature conditions of 80 DEG C, filters, is washed to solution close to neutrality； Contacting the 0.5mol/L aqueous ammonium nitrate solution of filter cake and 10 liters, speed of agitator is 300rpm, and at 95 DEG C, constant temperature stirring l is little When, then filtering molecular sieve, and stay sample, analyze Na₂O content；Repeat aforesaid operations, until Na in molecular sieve₂The content of O reaches To 2.5wt%, obtaining dried sample number into spectrum is NNY-2.

Embodiment 4

Take 100 grams of NNY-1 deionized water making beating, and under conditions of stirring, be brought rapidly up 95 DEG C, then with uniformly Speed in 2 hours, drip the aqueous solution being configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water, add rear slurry and exist 2 hours of constant temperature under 95 DEG C of stirring conditions, stand 10 minutes, through 3 washings and are dried after filtering, are placed in sample after drying In heat-treatment furnace, the heating rate of 500 DEG C/h of control, temperature is risen to 600 DEG C, the water vapor pressure of maintenance system is simultaneously 0.15MPa, is processed 2 hours, cooling, takes out sample；Filter cake is contained NH with 500mL₄ ⁺And H⁺Concentration be respectively 0.6mol/L and The mixed solution (ammonium chloride and hydrochloric acid) of 0.1mol/L is processed, and the non-framework aluminum in removing sample, dealuminzation condition is at 80 DEG C Manage 2 hours, and wash filter cake with hot deionized water, with the pH value of cleaning solution close to stopping washing, filter cake in an oven 120 after 7 DEG C drying 5 hours, obtains modified small-grain Y-1, and the physico-chemical property of Y-1 is shown in Table 1.

Embodiment 5

Take 100 grams of NNY-1 deionized water making beating, and under conditions of stirring, be brought rapidly up 90 DEG C, then with uniformly Speed in 2 hours, drip the aqueous solution being configured by 30 grams of ammonium hexafluorosilicate and 150m1 deionized water, add rear slurry and exist 2 hours of constant temperature under 90 DEG C of stirring conditions, stand 10 minutes, through 3 washings and are dried after filtering, are placed in sample after drying In heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 650 DEG C, maintain the steam partial pressure of system simultaneously 0.08MPa, is processed 2 hours, cooling, takes out sample；Filter cake is contained NH with 400mL₄ ⁺And H⁺Concentration be respectively 0.8mol/L and The mixed solution (ammonium nitrate and nitric acid) of 0.2mol/L is processed, and the non-framework aluminum in removing sample, dealuminzation condition is at 70 DEG C Process 3 hours, filter, and wash filter cake with hot deionized water, after 7, stop washing, filter cake in baking with the pH value of cleaning solution 120 DEG C of dryings 5 hours in case, obtain modified small-grain Y-2, and the physico-chemical property of Y-2 is shown in Table 1.

Embodiment 6

Take 100 grams of NNY-2 deionized water making beating, and under conditions of stirring, be brought rapidly up 100 DEG C, then with uniformly Speed in 2 hours, drip the aqueous solution being configured by 20 grams of ammonium hexafluorosilicate and 150m1 deionized water, add rear slurry and exist 2 hours of constant temperature under 100 DEG C of stirring conditions, stand 10 minutes, through 3 washings and are dried after filtering, put sample after drying In water heat-treatment furnace, control the heating rate of 400 DEG C/h, temperature is risen to 700 DEG C, maintain the water vapour of system simultaneously Dividing potential drop 0.1MPa, is processed 2 hours, cooling, takes out sample；Filter cake is contained NH with 400mL₄ ⁺And H⁺Concentration be respectively 1.0mol/L Processing with the mixed solution (ammonium chloride and hydrochloric acid) of 0.2mol/L, the non-framework aluminum in removing sample, dealuminzation condition is at 75 DEG C Lower process 3 hours is filtered, and washs filter cake with hot deionized water, stops washing, filter cake in baking with the pH value of cleaning solution after 7 120 DEG C of dryings 6 hours in case, obtain modified small-grain Y-3.The physico-chemical property of Y-3 is shown in Table 1.

Embodiment 7

By 25 grams of Y-1 molecular sieves (butt 90wt%), 106.5 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar was 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-1.

Use the method for conventional incipient impregnation, by PdC1₂(analyzing pure) and Pt (NH₄)₄C1₂The solution of (analyzing pure) By final catalyst metals amount (Pt 0.15wt %;Pd0.5wt %) step impregnation in type carrier, stand 12h , 110 DEG C of dryings 6 hours, 480 DEG C of roastings 4 hours, prepare catalyst CAT-1,

Character is shown in Table 2.

Embodiment 8

By 30 grams of Y-2 molecular sieves (butt 90wt%), 100 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar was 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-2, use the method for conventional incipient impregnation, by PdC1₂(analyzing pure) and Pt ( NH₄)₄C1₂The solution of (analyzing pure) is by final catalyst metals amount (Pt 0.20wt %;Pd0.4wt %) step impregnation exists On in type carrier, stand 12h, 110 DEG C of dryings 6 hours, 480 DEG C of roastings 4 hours, prepare catalyst CAT-2, character is shown in Table 2.

Embodiment 9

By 40 grams of Y-3 molecular sieves (butt 90wt%), 90 grams of amorphous silica-aluminas (pore volume 0.9ml/g, than

Surface area 350m²/ g, butt 70wt%), (butt 20wt%, nitric acid rubs 120 grams of adhesives with little porous aluminum oxide Your ratio is 0.25) put into mixed grind in roller, add water, be rolled into paste, extrusion, extrusion bar was 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier TCAT-3.

Use the method for conventional incipient impregnation, by PdC1₂(analyzing pure) and Pt (NH₄)₄C1₂The solution of (analyzing pure) By final catalyst metals amount (Pt 0.25wt %;Pd0.6wt %) step impregnation in type carrier, stand 12h , 110 DEG C of dryings 6 hours, 480 DEG C of roastings 4 hours, prepare catalyst CAT-3,

Character is shown in Table 2.

Comparative example 1

1st, fine grain NaY is prepared with reference to CN101722023A.

Feedstock property used in this comparative example is as follows: low alkali sodium metaaluminate: Na₂O content 120g/L, Al₂O₃Content 40g/L；Waterglass: SiO₂Content 250g/L；Aluminum sulfate: Al₂O₃Content 90g/L.

(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.

(2) preparation of gel: temperature is 8 DEG C, under stirring condition, be sequentially added into 59.4mL sulphur in the waterglass of 208mL Acid aluminium, the low sodium metaaluminate of 62.7mL and 42.2mL directed agents, then constant temperature constant speed stirs 1.5 hours, the conjunction that then will obtain Become liquid static aging 8 hours at the temperature disclosed above, obtain gel.

(3) gel in synthesis reactor was raised to 50 DEG C in 20 minutes by crystallization: under agitation, and constant temperature stirs crystallization 7 Hour；After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor being brought up to 120 DEG C, then constant temperature stirs 6 hours. Through filtering, washing and being dried, obtain product little crystal grain CNY-l.

2nd, carrying out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-1.

3rd, carrying out subsequent treatment to CNNY-1, processing mode and condition, with embodiment 4, obtain Reference Product CY-1.CY-1 Physico-chemical property be shown in Table 1.

4th, method for preparing catalyst uses CY-1 molecular sieve with embodiment 8, molecular sieve component.

Comparative example 2

1st, fine grain NaY is prepared with reference to CN1785807A.

The preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.

Being positioned over 14.21g water in beaker, in control beaker, fluid temperature is 60 DEG C, is simultaneously introduced under quick stirring The A1 of 12.79g50wt%₂(SO₄)₃) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, gel PH value be 12.5, after stirring, be loaded in stainless steel cauldron, 60 DEG C of stirring crystallization 6 hours, then heat to 100 DEG C of static crystallizations 60 hours, then filter, washing, dry CNY-2 molecular sieve.

2nd, carrying out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-2.

3rd, carrying out subsequent treatment to CNNY-2, processing mode and condition, with embodiment 4, obtain Reference Product CY-2.CY-2 Physico-chemical property be shown in Table 1.

4th, method for preparing catalyst uses CY-2 molecular sieve with embodiment 8, molecular sieve component.

Comparative example 3

1st, prepared by fine grain NaY

(1) preparation of directed agents: the preparation of directed agents is with NY-1 in embodiment 1.

(2) preparation of amorphous silica-alumina predecessor.

It is 100g A1 that solid sodium aluminate is configured to 0.3L concentration₂O₃ / L sodium aluminate working solution (a).Concentrated ammonia liquor is added Enter appropriate distilled water diluting and become about 10wt% weak aqua ammonia (b).Take containing SiO₂The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5L Degree is 140g SiO₂/ L sodium metasilicate working solution (c).Take the steel retort of one 5 liters, tank adds 0.5 liter of distilled water and stirs Mixing after being heated to 70 DEG C, opening the valve having (a) and (b) and (c) container respectively simultaneously, the flow of control (a) is so that neutralizing anti- At 40 minutes between Ying Shi, and the flow adjusting rapidly (b) makes the pH value of system be maintained at 7～8, and controls the temperature of system 60 About DEG C.After reacting aluminum sulfate completes, stopping adding (b), the silicon-aluminum sol of generation stablizes 40 minutes.

(3) preparation of gel is with embodiment 1.

(4) crystallization is with embodiment 1, obtains products C NY-3, and product property is shown in Table 1.

2nd, carrying out ammonium exchange to raw material small crystal grain NaY molecular sieve, treatment conditions, with embodiment 2, obtain dried sample Numbered CNNY-3.

3rd, carrying out subsequent treatment to CNNY-3, processing mode and condition, with embodiment 4, obtain Reference Product CY-3.CY-3 Physico-chemical property be shown in Table 1.

4th, method for preparing catalyst uses CY-3 molecular sieve with embodiment 8, molecular sieve component.

Comparative example 4

1st, the preparation of CNNY-4 is with comparative example 1.Then the method using CN200910165116.X is modified, specific as follows: Take 100 grams of CNNY-4 100mL deionized water making beating, and under conditions of stirring, be brought rapidly up 95 DEG C, then with uniformly Speed drips the aqueous solution being configured by 25 grams of ammonium hexafluorosilicate and 150m1 deionized water in 2 hours, adds rear slurry 95 2 hours of constant temperature under DEG C stirring condition, stand 10 minutes, through 3 washings, filter, be dried；Sample after above-mentioned drying is placed in In heat-treatment furnace, the heating rate of 500 DEG C/h of control, temperature is risen to 600 DEG C, the water vapor pressure of maintenance system is simultaneously 0.15MPa, is processed 2 hours, cooling, takes out sample；Final sample contains Al with 400mL³⁺And H⁺Concentration be respectively 1.0mol/L With the non-framework aluminum in mixed solution (aluminum nitrate and nitric acid) the removing sample of 0.5mol/L, dealuminzation condition is for processing 2 at 80 DEG C Hour, and wash filter cake with hot deionized water, with the pH value of cleaning solution close to stop after 7 washing, filter cake in an oven 120 DEG C do Dry 5 hours, obtain CY-4.The physico-chemical property of CY-4 is shown in Table 1.

4th, method for preparing catalyst uses CY-4 molecular sieve with embodiment 8, molecular sieve component.

The character of table 1 Y type molecular sieve

Production code member	NY-1	NY-2	Y-1	Y-2	Y-3	CY-1	CY-2	CY-3	CY-4
										Feed intake SiO2/Al2O3Mol ratio	9.1	10.1
SiO2/Al2O3Mol ratio	7.5	8.4	66	84	105	54	25	28	63
										Specific surface area, m2/g	916	898	970	990	1020	926	788	865	921
Pore volume, mL/g	0.39	0.38	219	0.58	0.62	0.49	0.32	0.34	0.48
										Secondary pore (1.7-10nm), %			0.56	66.4	71.1	45.1	27.5	35.2	42.1
External surface area, m2/g	191	182	60.1	249	240	196	164	195	189
										Lattice constant, nm	2.461	2.462	2.436	2.432	2.430	2.437	2.450	2.443	2.436
Relative crystallinity, %	101	110	115	118	116	114	80	85	116
										Average crystallite size, nm	380	430	380	380	430	400	450	400	400

The physico-chemical property of table 2 catalyst

Catalyst is numbered	CAT-1	CAT-2	CAT-3	CCAT-1	CCAT-2	CCAT-3	CCAT-4
								Catalyst forms
Pt, wt%	0.15	0.20	0.25	0.16	0. 19	0.21	0.23
								Pd, wt%	0.50	0.40	0.60	0.49	0.54	0.58	0.60
Small-grain Y molecular sieve, wt%	18	22	29	29	29	22	27
								Amorphous silica-alumina, wt%	62	58	51	51	51	58	53
Aluminum oxide, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
								Specific surface area, m2/g	502	511	535	450	430	427	440
Pore volume, ml/g	0.57	0.59	0.61	0.50	0.46	0.42	0.56
								Secondary pore volume	67	69	71	48	44	42	49

By the invention described above catalyst CAT-1, CAT-2 and CAT-3 and comparative example catalyst CCAT-1, CCAT-2, CCAT- 3 and CCAT-4 carry out reactivity worth evaluation test.Test is carried out on 200ml small hydrogenation device, different with low-voltage hydrogenation Structure product > lube stock of 320 DEG C is raw material, its character is shown in Table 3.Use high-pressure hydrogenation post-refining process process, divide at hydrogen Pressure is 15.0MPa, hydrogen to oil volume ratio the 1000th, reaction temperature 220 DEG C, volume space velocity 0.6h^-1Process conditions under, be hydrogenated with Producing the engineer testing of white oil, reactivity worth evaluation test the results are shown in Table 4.

Table 3 low-voltage hydrogenation isomery > 320 DEG C of lube stock character

Analysis project
		Density (20 DEG C), kg/m3	857.1
Sulphur, g/g	3.0
		Nitrogen, g/g	1.0
Pour point, DEG C	-30
		Viscosity (100 DEG C), mm2/s	5.097
Viscosity (40 DEG C), mm2/s	27.41
		Carbon residue, wt%	0.01
Aromatic hydrocarbons, wt%	10.7

Table 4 catalyst activity evaluation result

Catalyst is numbered	CAT-1	CAT-2	CAT-3	CCAT-1	CCAT-2	CCAT-3	CCAT-4
								Reaction temperature, DEG C	220	221	223	234	236	238	228
Liquid is received, wt%	99.8	99.6	99.5	98.7	98.5	97.4	98.8
								Viscosity (40 DEG C), mm2/s	33.38	33.04	32.78	31.09	29.58	28.37	31.01
Viscosity (100 DEG C), mm2/s	6.678	6.621	6.616	6.109	5.935	5.327	5.948
								Pour point, DEG C	-15	-13	-14	-10	-8	-6	-10
Saybolt color/number	+32	+31	+32	+30	+29	+26	30
								Readily carbonizable substance (100 DEG C)	Pass through	Pass through	Pass through	Pass through	Do not pass through	Do not pass through	Pass through
Condensed-nuclei aromatics (260～420nm)/cm	<0.1	<0.1	<0.1	<0.1	0.2	0.3	<0.1

Claims (24)

1. the preparation method of a catalytic hydro-dearomatization catalyst, comprising: by small crystal grain Y-shaped molecular sieve, amorphous silica-alumina with use oxygen Change adhesive mechanical mixture, the shaping that aluminium is made, be then dried and roasting, make catalyst carrier；Use infusion process at carrier Upper supporting Pt and Pd, drying and roasting, obtain catalytic hydro-dearomatization catalyst；

Wherein small crystal grain Y-shaped molecular sieve is adopted and is prepared with the following method:

(1) preparation of fine grain NaY type molecular sieve；

(2) by fine grain NaY with containing alkaline solution treatment；

(3) the fine grain NaY type molecular sieve that step (2) obtains is prepared as Na₂The little crystal grain NH of O content≤2.5wt%₄NaY；

(4) the molecular sieve hexafluorosilicic acid aqueous ammonium of step (3) gained carries out dealumination complement silicon, the molecular sieve obtaining and accessory substance Separate；

(5) little crystal grain NH is obtained to step (4)₄NaY molecular sieve carries out hydro-thermal process；

(6) molecular sieve obtaining step (5) is with containing NH₄ ⁺And H⁺Mixed solution process, scrubbed and be dried, obtain little crystal grain Y type molecular sieve；

The wherein small crystal grain NaY molecular sieve used by step (1), its character is as follows: SiO₂/Al₂O₃Mol ratio is more than 6.0 and not high In 9.0, average grain diameter is 200～700nm, specific surface 800～1000 m²/ g, pore volume 0.30/～0.45mL/g, relatively Degree of crystallinity is 90%～130%, and cell parameter is 2.460～2.470nm, relatively crystallizes after 3 hours through roasting in 650 DEG C of air Degree is more than 90%, and after processing 2 hours through 700 DEG C of water vapour hydro-thermals, relative crystallinity is more than 90%.

2. in accordance with the method for claim 1, it is characterised in that: the SiO of small crystal grain NaY molecular sieve used₂/Al₂O₃Mole Ratio is 6.5～9.0.

3. in accordance with the method for claim 1, it is characterised in that: the SiO of small crystal grain NaY molecular sieve used₂/Al₂O₃Mole Ratio is 7.0～8.0.

4. in accordance with the method for claim 1, it is characterised in that: small crystal grain NaY molecular sieve used is through roasting in 650 DEG C of air After burning 3 hours, relative crystallinity is 90%～110%, and after processing 2 hours through 700 DEG C of water vapour hydro-thermals, relative crystallinity is 90% ～110%.

5. in accordance with the method for claim 1, it is characterised in that: the preparation method of small crystal grain NaY molecular sieve used, bag Include:

I, preparation directed agents: silicon source, aluminium source, alkali source and water are fed intake according to following proportioning: (6～30) Na₂O:Al₂O₃: (6～ 30)SiO₂: (100～460) H₂Mixture, after stirring, is stirred ageing 0.5～24 hour at 0～20 DEG C and prepares and lead by O To agent；

II, employing preparing amorphous silicon alumnium using carbonization predecessor, on the basis of the weight of the butt of amorphous silica-alumina predecessor, The content that silicon is counted with silica as 40wt%～75wt%；Its preparation process includes:

A, respectively preparation sodium aluminate solution and sodium silicate solution；

B, the part sodium silicate solution adding the preparation of step a in the sodium aluminate solution of step a preparation, then pass to CO₂Gas, Control reaction temperature is 10 ~ 40 DEG C, and the pH value of control cemented into bundles is 8 ~ 11；Wherein as the CO being passed through₂Gas flow accounts for and is always passed through Amount 60% ~ 100% when, add remainder sodium silicate solution, wherein in step b remainder sodium silicate solution with silica Meter accounts for step b and adds 5wt% ~ 85wt% in terms of silica for the sodium silicate solution total amount；

C, at the control temperature and pH value of step b, said mixture ventilate stablize 10 ~ 30 minutes；

III, prepare silica-alumina gel: press (0.5～6) Na₂O:Al₂O₃: (8～15) SiO₂: (100～460) H₂O always feeds intake mole Ratio, adds water, silicon source, guiding under conditions of 0～40 DEG C of quick stirring in the amorphous silica-alumina predecessor of step II gained Agent and alkali source, and control ph is 9.5 ~ 12.0, uniform stirring, obtains silica-alumina gel；Wherein directed agents addition account for sial coagulate The 1%～20% of glue weight,

IV, the reactant mixture of step III gained are through two step dynamic crystallizations, then through filtering, wash, and are dried, obtain little crystal grain NaY molecular sieve.

6. in accordance with the method for claim 5, it is characterised in that in step II, amorphous silica-alumina predecessor, with amorphous silicon On the basis of the weight of the butt of aluminium predecessor, content in terms of silica for the silicon is 55 wt%～70wt%.

7. in accordance with the method for claim 5, it is characterised in that: step b control reaction temperature is 15～35 DEG C.

8. in accordance with the method for claim 5, it is characterised in that: in step b, as the CO being passed through₂Gas flow accounts for total intake When 80% ~ 100%, add remainder sodium silicate solution.

9. in accordance with the method for claim 5, it is characterised in that: in step b, remainder sodium silicate solution is with silica Meter accounts for step b and adds 30wt% ~ 70wt% in terms of silica for the sodium silicate solution total amount.

10. in accordance with the method for claim 5, it is characterised in that in step I and III, silicon source, alkali source are respectively selected from sodium metasilicate And NaOH, in step I, aluminium source is selected from sodium metaaluminate.

11. in accordance with the method for claim 5, it is characterised in that in step III, controls reaction temperature 10 ~ 30 DEG C, pH value 10 ～11.

12. in accordance with the method for claim 5, it is characterised in that step IV uses two step dynamic crystallization, wherein the first steppings The condition of Mobile state crystallization is as follows: temperature controls at 50～90 DEG C, and crystallization time is 0.5～18 hour；Second step enters Mobile state The condition of crystallization is as follows: temperature controls at 80～140 DEG C, and crystallization time is 3～10 hours.

13. in accordance with the method for claim 5, it is characterised in that step IV uses two step dynamic crystallization, wherein the first steppings The condition of Mobile state crystallization is as follows: temperature controls at 60～80 DEG C, and crystallization time is 1～10 hour；It is brilliant that second step enters Mobile state The condition changed is as follows: temperature controls at 80～120 DEG C, and crystallization time is 5～10 hours.

14. in accordance with the method for claim 1, it is characterised in that in step (2), by the water of small crystal grain NaY molecular sieve and alkali Solution making beating mixes, and maintains stir process 1～4h under the temperature conditions of 60～120 DEG C；Alkali wherein used be NaOH, The mixture of KOH or NaOH and KOH；The concentration of the aqueous solution of alkali is 0.1～3 mol/L, and the concentration of slurries Middle molecule sieve is 0.05～1.0g/mL.

15. in accordance with the method for claim 1, it is characterised in that in step (4), compares 1:4 by solid-liquid weight in aqueous medium ~ 1:8 adds little crystal grain NH₄NaY molecular sieve, stirs and is warmed up to 90～120 DEG C, being then added dropwise to hexafluorosilicic acid aqueous ammonium, After dropping finishes, constant temperature stirs 1～2 hour, separates molecular sieve and accessory substance, and filters, is dried；Hexafluorosilicic acid aqueous ammonium Concentration 10 wt% ~ 40wt%, ammonium hexafluorosilicate addition is little crystal grain NH₄10 wt% of NaY molecular sieve ~ 50wt%.

16. in accordance with the method for claim 1, it is characterised in that in step (5), and the condition that described hydro-thermal is processed is as follows: Treatment temperature controls at 500～750 DEG C, and pressure is 0.01～0.50MPa, and the process time is 1.0～4.0 hours.

17. in accordance with the method for claim 1, it is characterised in that in step (5), and the condition that described hydro-thermal is processed is as follows: Treatment temperature controls at 600～700 DEG C, and pressure is 0.05～0.30MPa, and the process time is 1.0～4.0 hours.

18. in accordance with the method for claim 1, it is characterised in that in step (6), by hydro-thermal process after molecular sieve with acid and Containing NH₄ ⁺The mixed solution contact of salt composition, acid therein is hydrochloric acid, carbonic acid, nitric acid, one or more in sulfuric acid, contains NH₄ ⁺Salt be one or more in the ammonium salt containing above acid group；H in mixed solution⁺Concentration be 0.05～0.6mol/L, NH₄ ⁺ Concentration be 0.5～3.0mol/L, exchange temperature is 70～120 DEG C, exchange slurries Middle molecule sieve concentration be 0.1～0.5g/ ML, swap time is 0.5～3.0 hour, and exchange step repeats 1～4 time.

19. in accordance with the method for claim 1, it is characterised in that: step (3) uses the method for ammonium salt exchange, and process is as follows: With NaY molecular sieve as raw material, exchanging 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of solubility ammonium salt, molecular sieve exists Concentration in exchange slurries is 0.05～0.50g/mL, repeated exchanged l～5 time, filters off mother liquor, washing, is dried；Ammonium salt is chlorination One or more in ammonium, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, the concentration of ammonium salt solution is 0.5～5.0mol/L.

20. in accordance with the method for claim 1, it is characterised in that: in described catalytic hydro-dearomatization catalyst, the content of Pt is 0.1wt%～0.5wt%, Pd content is 0.3wt%～0.8wt%.

21. in accordance with the method for claim 1, it is characterised in that in described catalytic hydro-dearomatization catalyst carrier, with carrier Weight on the basis of, its composition includes: the content of small crystal grain Y-shaped molecular sieve is 5wt%～40wt%, the content of amorphous silica-alumina For 20wt%～65wt%, the content of aluminum oxide is 10wt%～40wt%.

22. in accordance with the method for claim 1, it is characterised in that in described catalytic hydro-dearomatization catalyst, with the weight of carrier On the basis of amount, its composition includes: the content of small crystal grain Y-shaped molecular sieve is 10wt%～25wt%, and the content of amorphous silica-alumina is 30wt%～60wt%, the content of aluminum oxide is 15wt%～30wt%.

23. in accordance with the method for claim 1, it is characterised in that: nothing used is mixed with small-grain Y molecular sieve and adhesive SiO in amorphous silicon-alumina₂Weight content be 20%～60%, the pore volume of amorphous silica-alumina is 0.6～1.1 mL/g, specific surface area It is 300～500 m²/g。

24. in accordance with the method for claim 1, it is characterised in that: drying and the roasting condition of carrier are as follows: through 80 ~ 150 DEG C It is dried 3 ~ 10 hours, 500 ~ 600 DEG C of roastings 3 ~ 6 hours；The condition of the drying of catalyst and roasting is as follows: at 100 ~ 150 DEG C It is dried 1 ~ 12 hour, roasting 3 ~ 6 hours at 450 ~ 550 DEG C.