CN104588073B - Hydrogenation dearomatization catalyst and preparation method thereof - Google Patents
Hydrogenation dearomatization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrogenation dearomatization catalyst and a preparation method thereof. The catalyst comprises a main active component Pt, an auxiliary component Pd and a carrier prepared from a small-grain Y type molecular sieve, alumina and amorphous silicon aluminum. According to the preparation method, the small-grain Y type molecular sieve with the characteristics of great dealumination depth, good crystallinity retentivity and well-developed secondary pores is used as an acid component and cooperates with the amorphous silicon aluminum, the main active component and the auxiliary component, so the hydrogenation dearomatization catalyst has higher hydrogenation dearomatization activity and is especially applicable to hydrogenation dearomatization and decoloring of heavy aromatic-containing naphthenic high-viscosity white oil and solvent naphtha.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and preparation method thereof, more particularly, to catalytic hydro-dearomatization catalyst and its
Preparation method.This catalyst is suitable for the hydrogenation process of aromatic hydrocarbons, is particularly suitable for the hydrogenation dearomatization of the naphthene base crude oil containing heavy aromatics
Hydrocarbon process.
Background technology
Under aerobic conditions, hydrotreating generates oily (as top-grade lubricating oil, food-level white oil etc.) to daylight, ultraviolet spoke
Penetrate very sensitive, be exposed to daylight and in the air causes oil product appearance property unstable, oil product color can be deepened, it is heavy to produce when serious
Form sediment.Such oil requires viscosity low, and flash-point and boiling point are high, and volatility is little.Colorless and odorless, arene content is low, non-corrosiveness, good
Thermostability and oxidation stability, are difficult to cause gel, and biological property is good, meets environmental requirement.
Solve the above problems, most efficient method is exactly that it is carried out with deep hydrogenation aromatic hydrocarbons saturation.Added using conventional
Hydrogen catalyst for refining, because the fault of construction of catalyst and cycloalkyl viscous crude fraction have, viscosity is big, molecular weight is high, condensed ring knot
Feature more than structure, leads to the polycyclic aromatic hydrocarbon in macromole fraction to be difficult to sufficiently be hydrogenated with saturation, 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, (100 DEG C) of readily carbonizable substance passes through to be less than the requirement of the indexs such as 0.1cm with ultraviolet absorptivity (260nm-420nm).
Catalyst also should have preferable selectivity simultaneously, so that the indexs such as viscosity, pour point and the flash-point of hydrofinishing product is changed not
Greatly.And in such catalyst adopt y type molecular sieve, the such as lube oil hydrogenation such as cn1317368c, cn201010197869.1 essence 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 generally 1000nm about, its crystal grain is larger, and duct is relatively long, and diffusional resistance is big,
Macromole is difficult to enter and is reacted inside duct, and after reaction, product is also more difficult diffuses out, so its catalytic performance receives
Restriction.Compared with conventional y type molecular sieve, little crystal grain y type molecular sieve has bigger external surface area and more outer surface active center,
Be conducive to improving macromole hydrocarbon cracking capability, thus there is more superior catalytic perfomance.Meanwhile, reduce y type molecular sieve
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 is made all to be used for catalyzed conversion it is necessary to make micropore diffusion speed big
In endoporus catalyzed conversion speed.Shortening the evolving path is the best way.Overcome micropore diffusion limit an effective way be
Reduce zeolite crystal size.This not only can increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously.
Ep0204236 compares to little crystal grain nay molecular sieve and big crystal grain nay molecular sieve, and result shows, the former is to heavy-oil catalytic
Cracking has higher activity and preferable selectivity.
Little crystal grain nay molecular sieve is that do 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 little crystal grain y type zeolite, and the method is gas to be dried with Silicon chloride.
Body and little crystal grain nay zeolitic contact, obtain after washing, because the heat of its raw material itself and hydrothermal stability are just poor, simultaneously
This inventive method is to process molecular sieve by the way of gas phase dealumination complement silicon, and this makes the heat of product and hydrothermal stability worse,
Activity is low.Especially poor to heat stability and hydrothermal stability little crystal grain nay zeolite, the sial framing structure in molecular sieve
Less stable, easily causes the removing of framework aluminum in modifying process, simultaneously also some framework silicon also with removing,
Part skeleton is caused the phenomenon caved in occur so that the crystallization reservation degree of product is relatively low, the activity of molecular sieve is not high.
Cn200910165116.x discloses a kind of little crystal grain y type molecular sieve and preparation method thereof.Handled by the method
Raw material little crystal grain nay molecular sieve is the method preparation disclosed in cn101722023a, i.e. sio2/al2o3Mol ratio be 4.0～
6.0, mean diameter, in 100～700nm, passes sequentially through successive modified i.e. ammonium exchange, at ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal
The mixed aqueous solution of reason, aluminium salt and acid is processed, and obtains little crystal grain y molecular sieve.In the method, need first to raw material ammonium hexafluorosilicate
After dealumination complement silicon is processed, then carry out hydrothermal treatment consists etc. and process, so could reduce the caving in of framing structure of molecular sieve, raising divides
The crystallization reservation degree of son sieve, but after the method is due to first using ammonium hexafluorosilicate dealumination complement silicon to process, due to occurring the sial isomorphous to take
In generation, molecular sieve silica constructed of aluminium ratio is more complete, then carries out hydrothermal treatment consists, and the secondary pore of formation is few, and secondary pore proportion is low, no
Beneficial to the diffusion of product, aromatic hydrocarbons saturation is low.
At present, because the hydrothermal stability of little crystal grain nay molecular sieve is poor, structural instability, through successive modified it is impossible to
Obtain structural integrity, degree of crystallinity is high and little crystal grain y type molecular sieve that have more secondary pore.
In preparation process, silicon and aluminum are easy to run off existing method little crystal grain nay type molecular sieve, and silicon utilization rate is low, and silicon,
Reuniting, easily occurs in aluminum distributing inhomogeneity, and therefore still cannot to prepare silica alumina ratio high for existing method, and heat stability and hydro-thermal steady
Qualitative and good little crystal grain nay type molecular sieve.Through successive modified it is impossible to obtain structural integrity, degree of crystallinity is high and has more
The little crystal grain y type molecular sieve of secondary pore, for catalytic hydro-dearomatization catalyst, aromatic hydrocarbons saturation is low.
Content of the invention
For overcoming weak point of the prior art, the invention provides a kind of catalytic hydro-dearomatization catalyst and its preparation side
Method.This catalyst adopts the little crystal grain y type 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 cycloalkyl high viscosity white oil and the solvent containing heavy aromatics
The hydrogenation aromatics-removing of oil and decolorization.
Catalytic hydro-dearomatization catalyst of the present invention, composition includes: main active component is pt, and adjuvant component is pd, and by little crystalline substance
The carrier of grain y type molecular sieve, aluminium oxide and amorphous silica-alumina composition, wherein said little crystal grain y type molecular sieve, its property is such as
Under: sio2/ a12o3Mol ratio is 40～120, and average grain diameter is 200～700nm, preferably 300～500nm, relatively crystallizes
Degree >=95%, preferably 95% ~ 120%, lattice constant 2.425～2.435nm, specific surface area is 900～1200m2/ g, pore volume
For 0.5～0.80ml/g, the pore volume shared by the secondary pore of 1.7～10nm is more than the 50%, preferably 50% ~ 80% of total pore volume,
More preferably 60% ~ 80%.
The property of catalytic hydro-dearomatization catalyst of the present invention is as follows: specific surface area is 350～550m2/ g, preferably 380～
500m2/ g, pore volume is 0.5～1.0ml/g, preferably 0.6～0.9ml/g.
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: little crystal 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 aluminium oxide is 10wt%～40wt%, preferably 15wt%～
30wt%.
The preparation method of catalytic hydro-dearomatization catalyst of the present invention, comprises the steps:
By little crystal grain y type molecular sieve, amorphous silica-alumina and the binding agent mechanical mixture made with aluminium oxide, molding, then
It is dried and roasting, make catalyst carrier；Using infusion process in supported on carriers pt and pd, drying and roasting, it is hydrogenated with
Dearomatization catalyst.
The preparation method of described little crystal grain y type molecular sieve, comprises the steps:
(1) preparation of little crystal grain nay type molecular sieve；
(2) little crystal grain nay type molecular sieve is prepared into na2Little crystal grain nh of o content≤2.5wt%4nay；
(3) little crystal grain nh is obtained to step (2)4Nay molecular sieve carries out hydrothermal treatment consists；
(4) molecular sieve of step (3) gained carries out dealumination complement silicon with hexafluorosilicic acid aqueous ammonium, the molecular sieve obtaining and pair
Product separates；
(5) molecular sieve obtaining step (4) is with containing nh4 +And h+Mixed solution process, be washed out and be dried, obtain
To little crystal grain y type molecular sieve.
Little crystal grain nay molecular sieve described in step (1), its property 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
Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, through relative crystallinity after 650 DEG C of in the air roastings 3 hours
For more than 90%, generally 90%～110%, preferably 90% ~ 105%, through after 700 DEG C of water vapour hydrothermal treatment consists 2 hours relatively
Degree of crystallinity is more than 90%, generally 90%～110%, preferably 90% ~ 105%.
In step (1) in the inventive method, the preparation method of little crystal grain nay type molecular sieve is as follows:
I, preparation directed agents: silicon source, silicon source, alkali source and water are fed intake according to following proportioning: (6～30) na2O:al2o3: (6
～30) sio2: (100～460) h2O, after stirring, mixture is stirred at 0～20 DEG C ageing and is obtained for 0.5～24 hour
Directed agents；
Ii, adopt 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 silicon dioxide as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes:
A, respectively preparation sodium aluminate solution and sodium silicate solution；
The part sodium silicate solution adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to co2
Gas, controlling reaction temperature is 10 ~ 40 DEG C, preferably 15～35 DEG C, and the ph value controlling 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 silicon dioxide in terms of silicon dioxide
5wt% ~ 85wt%, preferably 30wt% ~ 70wt%；
C, at the control temperature and ph value of step b, said mixture ventilation 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 ii gained under conditions of quick stirring, and control
Ph value processed is 9.5 ~ 12.0, and uniform stirring obtains silica-alumina gel；Wherein directed agents addition account for silica-alumina gel weight 1%～
20%,
Iv, the reactant mixture of step iii 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 silicate and sodium hydroxide.In step i, silicon 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, 0～40 DEG C of controlling reaction temperature, preferably 10 ~ 30 DEG C, ph value 9.5～12.0, preferably ph value 10～
11.
In step iv, the reactant mixture of gained carries out crystallization and adopts two step dynamic crystallizations, and the wherein first step enters Mobile state
The condition of crystallization is as follows: at 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step carries out dynamic crystallization
Condition is as follows: at 80～140 DEG C, crystallization time is 3～10 hours to temperature control, after the completion of crystallization, then through filtering, washing, do
Dry, prepared product.Two step dynamic crystallization conditions are preferably as follows: the first step: temperature control at 60～80 DEG C, crystallization time be 1～
10 hours；Second step: at 80～120 DEG C, crystallization time is 5～10 hours to temperature control.
In step (3), the condition of described hydrothermal treatment consists 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 process time is 1.0～4.0 hours.
In step (4), aqueous medium adds little crystal grain nh4Nay molecular sieve (solid-liquid weight is than 1:4 ~ 1:8), stirring is simultaneously
It is warmed up to 90～120 DEG C, is then added dropwise to hexafluorosilicic acid aqueous ammonium, constant temperature stirs 1～2 hour after completion of dropping, separate
Molecular sieve and by-product, and filter, be dried.The concentration 10 wt ~ 40wt% of hexafluorosilicic acid aqueous ammonium, ammonium hexafluorosilicate adds
Measure as nh410 wt% of nay molecular sieve ~ 50wt%.
In step (5), by the y molecular sieve after hydrothermal treatment consists 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, sulphuric acid,
Containing nh4 +Salt be one or more of 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 be 70～120 DEG C, exchange serosity in molecular 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 solution, wash with water
Wash, be dried.
Other operating procedures in the Modified Y Zeolites preparation method of the present invention, such as ammonium salt exchange can be normal using this area
The operational approach of rule and condition, specific as follows: with nay molecular sieve as raw material, with solubility ammonium salt such as ammonium chloride, ammonium carbonate, nitre
The aqueous solution of sour ammonium, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate etc., the concentration of ammonium salt solution is 0.5～5.0mol/l.?
70～120 DEG C, at preferably 80～100 DEG C exchange 0.5～3.0 hour, y molecular sieve exchange serosity in concentration be 0.05～
0.50g/ml, repeated exchanged l～5 time, filter off mother solution, washing, be dried.
Adhesive therefor of the present invention is made up of little porous aluminum oxide and mineral acid and/or organic acid.Aperture oxidation used
Aluminum 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 little crystal grain y molecular sieve and binding agent can be by altogether
The sedimentation method or grafting copolymerization process preparation, are prepared by conventional method in document.Sio in prepared amorphous silica-alumina2Weight
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, the method introducing metal pt and pd adopts infusion process.The present invention will be amorphous
The complex of sial and y type molecular sieve and binding agent kneading, molding, drying and roasting obtain carrier, then adopt infusion process to bear
After carrying pt and pd, drying and roasting, obtain catalytic hydro-dearomatization catalyst.Wherein, catalyst can be become according to actual needs
Type, shape can be cylindrical bars, Herba Trifolii Pratentis 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 be using the method for saturation dipping or excessive dipping, and after impregnating metal pt and pd, catalyst is carried out
It is dried and the condition of roasting is as follows: in 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.
, when processing naphthene base crude oil, typically under hydrogen existence condition, reaction pressure is for reaction condition for catalyst of the present invention
10 ~ 20mpa, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 7.0h during liquid-1, 180 ~ 250 DEG C of reaction temperature.
Catalytic hydro-dearomatization catalyst of the present invention due to using little crystal grain y type molecular sieve as acidic components, this molecular sieve
Have the characteristics that high silica alumina ratio, high-crystallinity, secondary pore be many, 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 cycloalkanes based raw material, the hydrogenation dearomatization of the cycloalkanes based 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, and good stability, so in follow-up modification process, especially just entered before dealumination complement silicon
Row hydrothermal treatment consists, are so conducive to improving the ratio shared by secondary pore of molecular sieve, and because the particularity of raw material makes molecule
Sieve remains in that good stability through hydrothermal treatment consists, is also beneficial to follow-up dealumination complement silicon, the carrying out of acid treatment, and not
Affect the stability of final molecular sieve.The little crystal grain y type molecular sieve of the method preparation being provided with the present invention is higher in acquisition
sio2/a12o3While mol ratio, the ratio shared by secondary pore is higher, and maintains the stability of y type molecular sieve, molecular sieve
There is higher specific surface area and higher degree of crystallinity.Using this little crystal grain y type molecular sieve and amorphous silica-alumina kneading and compacting, so
Dip loading active metal pt and pd more afterwards, is more beneficial for cooperating of catalyst hydrogenation activity component and carrier component, carries
The activity of high catalyst, stability, purpose product selectivity.
Specific embodiment
In order to the present invention is better described, to further illustrate the present invention with reference to embodiment and comparative example.But this
Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention: specific surface area, pore volume adopt low temperature liquid nitrogen physics
Absorption method, relative crystallinity and cell parameter adopt x optical diffraction method, and silica alumina ratio adopts chemical method, and the crystal grain of molecular sieve is big
Measure by the way of little (scanning electron microscope) using sem.Wt% is mass fraction.
Embodiment 1
The present embodiment is preparing raw material little crystal grain nay type molecular sieve
The preparation of ny-1
(1) preparation of directed agents: take 8g sodium hydrate solid to be dissolved in 80g water, add sodium metaaluminate 2.5 g (al2o3
Content is 45wt%, na2O content is 41wt%), then add 40g waterglass (sio2Content is 28wt%, na2O content is 8
Wt%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(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).By strong aqua ammonia plus
Enter appropriate distilled water diluting and become about 10wt% weak ammonia (b).Take containing sio2The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5l
Spend for 140g sio2/ l sodium silicate working solution (c).Take one 5 liters of steel retort, add 0.5 liter of distilled water in tank and stir
Mix after being heated to 70 DEG C, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) with
Make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the ph value of system be maintained at 7～8, and control system
Temperature is at 60 DEG C about.After the completion of reacting aluminum sulfate, stop adding (b), the addition of (c) is 0.17l, the silicon-aluminum sol of generation
After stablizing 20 minutes, continuously add (c) 0.33l, add in 10 minutes, start the ageing process of system, keep ph value 8.0,
Temperature 60 C, aging 30 minutes.
(3) preparation of gel
1l h is added in the serosity obtained by step (2)2o、140g sio2/ l sodium silicate working solution 0.6l and step
(1) directed agents 100g prepared, the ph value of gel is 11.5,15 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 2.5
Hour.
(4) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heat up
To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry nay zeolite product ny-1, property is listed in table l.
The preparation of ny-2
(1) preparation of directed agents: take 10 g sodium hydrate solids to be dissolved in 90g water, add sodium metaaluminate 3 g (al2o3
Content is 45wt%, na2O content is 41wt%), then add 50g waterglass (sio2Content is 28wt%, na2O content is
8wt%), in 20 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(2) preparation of amorphous silica-alumina predecessor
It is 80g a1 that Solid aluminum sulfate is configured to 0.5l concentration2o3/ l aluminum sulfate working solution (a).Strong aqua ammonia is added
Appropriate distilled water diluting becomes about 10wt% weak ammonia (b).Take containing sio2The sodium silicate solution of 28wt%, then it is diluted to 0.4l concentration
For 150g sio2/ l sodium silicate working solution (c).Take one 5 liters of steel retort, add 0.5 liter of distilled water in tank and stir
After being heated to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) so that in
With the response time at 40 minutes, and the flow of adjustment (b) rapidly makes the ph value of system be maintained at 7～8, and the temperature of control system
At 60 DEG C about.After the completion of reacting aluminum sulfate, stop adding (b), the addition of (c) is 0.2l, and the silicon-aluminum sol of generation is stable
After 20 minutes, continuously add (c) 0.2l, add in 10 minutes, start the ageing process of system, keep ph value 8.0, temperature 60
DEG C, aging 30 minutes.
(3) preparation of gel
1.2l h is added in the serosity obtained by step (2)2o、150g sio2/ l sodium silicate working solution 0.8l and step
Suddenly directed agents 120g that prepared by (1), the ph value of gel is 12,30 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 3 little
When.
(4) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, then heat up
To 120 DEG C, stirring crystallization 5 hours, then filter, washing, dry nay zeolite product ny-2, property is listed in table l.
Embodiment 2
First ammonium exchange is carried out to raw material little crystal grain nay molecular sieve ny-1.Compound concentration is that 0.5mol/l ammonium nitrate is water-soluble
10 liters of liquid.Weigh 1000 grams of little crystal grain nay molecular sieve, be added in 10 liters of aqueous ammonium nitrate solutions preparing, speed of agitator is
300rpm, constant temperature stirring l hour at 90 DEG C, then filtering molecular sieve, and stay sample, analyze na2O content；Repeat above-mentioned behaviour
Make, na in molecular sieve2O content reach 2.5wt%, obtain dried sample number into spectrum be nny-1.
Embodiment 3
First ammonium exchange is carried out to raw material little crystal grain nay molecular sieve ny-2.Compound concentration is that 0.8mol/l ammonium nitrate is water-soluble
10 liters of liquid.Weigh 1000 grams of little crystal grain nay molecular sieve, be added in 10 liters of aqueous ammonium nitrate solutions preparing, speed of agitator is
300rpm, constant temperature stirring l hour at 95 DEG C, then filtering molecular sieve, and stay sample, analyze na2O content；Repeat above-mentioned behaviour
Make, na in molecular sieve2The content of o reaches 2.5wt%, and obtaining dried sample number into spectrum is nny-2.
Embodiment 4
Take 100 grams of nny-1 to be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, with
When maintain system water vapor pressure be 0.15mpa, process 2 hours, cooling, take out sample；Sample deionized water is pulled an oar, and
Stirring under conditions of be brought rapidly up 95 DEG C, then with uniform speed in 2 hours Deca by 25 grams of ammonium hexafluorosilicate
With the aqueous solution of 150m1 deionized water configuration, add rear slurry 2 hours of constant temperature under 95 DEG C of stirring conditions, stand 10 minutes,
Through 3 washings, filter；Filter cake is contained nh with 500ml4 +And h+Concentration be respectively 0.6mol/l and 0.1mol/l mixing molten
Liquid (ammonium chloride and hydrochloric acid) is processed, the non-framework aluminum in removing sample, and dealuminzation condition is to process 2 hours at 80 DEG C, and is gone with heat
Ion water washing filter cake, stops washing, filter cake 120 DEG C of dryings 5 hours in an oven after 7 with the ph value of cleaning mixture, obtains
Modified little crystal grain y-1, the physico-chemical property of y-1 is shown in Table 1.
Embodiment 5
Take 100 grams of nny-1 molecular sieves to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, temperature is risen to
650 DEG C, maintain the steam partial pressure 0.08mpa of system simultaneously, process 2 hours, cooling, take out sample；By sample deionized water
Making beating, and stirring under conditions of be brought rapidly up 90 DEG C, then with uniform speed in 2 hours Deca by 30 grams of hexafluoros
Ammonium silicate and the aqueous solution of 150m1 deionized water configuration, add rear slurry 2 hours of constant temperature under 90 DEG C of stirring conditions, standing
10 minutes, through 3 washings, filter；Filter cake is contained nh with 400ml4 +And h+Concentration be respectively 0.8mol/l and 0.2mol/l
Mixed solution (ammonium nitrate and nitric acid) process, the non-framework aluminum in removing sample, dealuminzation condition be process at 70 DEG C 3 little
When, filter, and wash filter cake with hot deionized water, stop washing after 7 with the ph value of cleaning mixture, filter cake in an oven 120
DEG C drying 5 hours, obtains modified little crystal grain y-2, the physico-chemical property of y-2 is shown in Table 1.
Embodiment 6
Take 100 grams of nny-2 molecular sieves to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, temperature is risen to
700 DEG C, maintain the steam partial pressure 0.1mpa of system simultaneously, process 2 hours, cooling, take out sample；Sample deionized water is beaten
Slurry, and stirring under conditions of be brought rapidly up 100 DEG C, then with uniform speed in 2 hours Deca by 20 grams of hexafluoros
Ammonium silicate and the aqueous solution of 150m1 deionized water configuration, add rear slurry 2 hours of constant temperature under 100 DEG C of stirring conditions, standing
10 minutes, through 3 washings, filter；Filter cake is contained nh with 400ml4 +And h+Concentration be respectively 1.0mol/l and 0.2mol/l
Mixed solution (ammonium chloride and hydrochloric acid) process, the non-framework aluminum in removing sample, dealuminzation condition be process at 75 DEG C 3 little
When filter, and wash filter cake with hot deionized water, stop washing after 7 with the ph value of cleaning mixture, 120 DEG C in an oven of filter cake
It is dried 6 hours, obtain modified little crystal 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 is rubbed 120 grams of binding agents with little porous aluminum oxide
You are than being 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, obtain carrier tcat-1.
Using the method for conventional incipient impregnation, by pdc12(analysis is pure) and pt (nh4)4c12The solution of (analysis is 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, prepared catalyst cat-1,
Property 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 is rubbed 120 grams of binding agents with little porous aluminum oxide
You are than being 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, obtain carrier tcat-2, using the method for conventional incipient impregnation, by pdc12(analysis is pure) and pt (
nh4)4c12The solution of (analysis is pure) presses 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, prepared catalyst cat-2, property 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 is rubbed 120 grams of binding agents with little porous aluminum oxide
You are than being 0.25) put into mixed grind in chaser, add water, be rolled into paste, extrusion, extrusion bar in 110 DEG C of dryings 4 hours, then
In 550 DEG C of roastings 4 hours, obtain carrier tcat-3.
Using the method for conventional incipient impregnation, by pdc12(analysis is pure) and pt (nh4)4c12The solution of (analysis is 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, prepared catalyst cat-3,
Property is shown in Table 2.
Comparative example 1
1st, little crystal grain nay is prepared with reference to cn101722023a.
In this comparative example, feedstock property used 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, sequentially adds 59.4ml sulfur in the waterglass of 208ml
Sour aluminum, the low sodium metaaluminate of 62.7ml and 42.2ml directed agents, then constant temperature constant speed stirring 1.5 hours, then by the conjunction obtaining
Become liquid static aging 8 hours at the temperature disclosed above, obtain gel.
(3) crystallization: under agitation, in 20 minutes, the gel in synthesis reactor is raised to 50 DEG C, constant temperature stirs crystallization 7
Hour；After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor is brought up to 120 DEG C, then constant temperature stirs 6 hours.
Through filtering, washing and be dried, obtain product little crystal grain cny-l.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve, treatment conditions, with embodiment 2, obtain dried sample
Numbering is cnny-1.
3rd, cnny-1 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cy-1.cy-1
Physico-chemical property be shown in Table 1.
4th, with embodiment 8, molecular sieve component adopts cy-1 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
Comparative example 2
1st, little crystal 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.
14.21g water is positioned in beaker, controls temperature of liquid in beaker to be 60 DEG C, be 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, in 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, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve, treatment conditions, with embodiment 2, obtain dried sample
Numbering is cnny-2.
3rd, cnny-2 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cy-2.cy-2
Physico-chemical property be shown in Table 2.
4th, with embodiment 8, molecular sieve component adopts cy-1 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
Comparative example 3
1st, little crystal grain nay preparation.
(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 40gal that solid sodium aluminate is configured to concentration2o3/ l sodium aluminate working solution, takes containing sio2The silicic acid of 28wt%
Sodium solution, then it is diluted to concentration for 100g sio2/ l sodium silicate working solution.1l sodium aluminate working solution is taken to be placed in plastic cans
In, it is subsequently adding 0.6l sodium silicate working solution, 20 DEG C of controlling reaction temperature, be passed through the co that concentration is 50v%2Gas, when ph value
Reach and when 10.0, stop logical co2, then divulge information and stablize 20 minutes.
(3) preparation of gel is with embodiment 1.
(4) crystallization, with embodiment 1, obtains product cny-3, and product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve, treatment conditions, with embodiment 2, obtain dried sample
Numbering is cnny-3.
3rd, cnny-3 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cy-3.cy-3
Physico-chemical property be shown in Table 2.
4th, with embodiment 8, molecular sieve component adopts cy-3 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
Comparative example 4
1st, with the cnny-1 of comparative example 1 preparation as raw material, the method then adopting cn200910165116.x is modified, specifically
As follows: to take 100 grams of cnny-1 100ml deionized water making beating, and be brought rapidly up 95 DEG C under conditions of stirring, then with equal
Even speed Deca in 2 hours, by the aqueous solution of 25 grams of ammonium hexafluorosilicate and the configuration of 150m1 deionized water, adds rear slurry
2 hours of constant temperature under 95 DEG C of stirring conditions, stand 10 minutes, through 3 washings, filter, be dried；By sample after above-mentioned drying
It is placed in heat-treatment furnace, controls the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, maintain the water vapor pressure of system simultaneously
For 0.15mpa, process 2 hours, cooling, take out sample；Final sample contains al with 400ml3+And h+Concentration be respectively 1.0mol/
The mixed solution (aluminum nitrate and nitric acid) of l and 0.5mol/l removes the non-framework aluminum in sample, and dealuminzation condition is to process at 80 DEG C
2 hours, and wash filter cake with hot deionized water, washing, 120 DEG C in an oven of filter cake are stopped after 7 with the ph value of cleaning mixture
It is dried 5 hours, obtain cy-4.The physico-chemical property of cy-4 is shown in Table 1.
2nd, with embodiment 8, molecular sieve component adopts cy-4 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
Comparative example 5
1st, little crystal grain nay is prepared with reference to cn92105661.3
Feedstock property used by nay 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: sequentially add the low sodium metaaluminate of 60ml aluminum sulfate, 60ml in the waterglass of 220ml,
Then constant temperature constant speed stirs 0.5 hour, prepared silica-alumina gel.
(3) crystallization: under agitation, in 30 minutes, the gel in synthesis reactor is raised to 140 DEG C, constant temperature stirs crystallization
2 hours；Add 35ml directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, through filtering, washing and do
Dry, obtain product cny-5, product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve cny-5, treatment conditions, with embodiment 2, obtain dried
Sample number into spectrum is cnny-5.
3rd, cnny-5 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cy-5.cy-5
Physico-chemical property be shown in Table 1.
4th, with embodiment 8, molecular sieve component adopts cy-5 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
Comparative example 6
1st, take 100gnny-1, adopt the method for cn200910165116.x modified the nny-1 of the present invention, specifically modified
Method, with comparative example 4, obtains Reference Product cy-6.The physico-chemical property of cy-6 is shown in Table 1.
2nd, with embodiment 8, molecular sieve component adopts cy-1 molecular sieve to method for preparing catalyst, and catalyst property is shown in Table 2.
The property 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 | cy-5 | cy-6 |
| Feed intake sio2/al2o3Mol ratio | 9.1 | 10.1 | |||||||||
| sio2/al2o3Mol ratio | 7.5 | 8.4 | 66 | 84 | 105 | 50 | 25 | 28 | 63 | 24 | 65 |
| Specific surface area, m2/g | 916 | 898 | 950 | 990 | 1020 | 892 | 780 | 805 | 921 | 711 | 935 |
| Pore volume, ml/g | 0.39 | 0.38 | 0.53 | 0.58 | 0.62 | 0.33 | 0.32 | 0.34 | 0.48 | 0.30 | 0.51 |
| Secondary pore (1.7-10nm), % | 62.1 | 66.4 | 71.1 | 37.1 | 27.5 | 35.2 | 42.1 | 25.2 | 46.0 | ||
| External surface area, m2/g | 191 | 182 | 2161 | 249 | 240 | 170 | 159 | 190 | 189 | 145 | 209 |
| Lattice constant, nm | 2.461 | 2.462 | 2.436 | 2.432 | 2.430 | 2.441 | 2.450 | 2.443 | 2.436 | 2.449 | 2.436 |
| Relative crystallinity, % | 101 | 110 | 115 | 118 | 116 | 95 | 80 | 85 | 116 | 78 | 117 |
| Average crystallite size, nm | 380 | 430 | 380 | 380 | 430 | 400 | 450 | 400 | 400 | 450 | 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 | ccat-5 | ccat-6 |
| Catalyst forms | |||||||||
| Pt, wt% | 0.15 | 0.20 | 0.25 | 0.16 | 0. 19 | 0.21 | 0.23 | 0.25 | 0.20 |
| Pd, wt% | 0.50 | 0.40 | 0.60 | 0.49 | 0.54 | 0.58 | 0.60 | 0.60 | 0.40 |
| Y molecular sieve, wt% | 18 | 22 | 29 | 29 | 29 | 22 | 27 | 29 | 22 |
| Amorphous silica-alumina, wt% | 62 | 58 | 51 | 51 | 51 | 58 | 53 | 51 | 58 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 497 | 509 | 534 | 450 | 430 | 427 | 440 | 389 | 452 |
| Pore volume, ml/g | 0.58 | 0.59 | 0.62 | 0.50 | 0.46 | 0.42 | 0.56 | 0.42 | 0.51 |
| Pore size distribution (4-10nm), % | 62 | 64 | 63 | 48 | 44 | 42 | 49 | 39 | 49 |
The invention described above catalyst and comparative example catalyst are carried out reactivity worth evaluation test.Test is little in 200ml
Carry out on type hydrogenation plant, with low-voltage hydrogenation isomate, as raw material, its property is shown in Table 3 for 320 DEG C of lube stock.Using
High-pressure hydrogenation post-refining process process, hydrogen dividing potential drop be 15.0mpa, hydrogen to oil volume ratio 1000,220 DEG C of reaction temperature, volume
Air speed 0.6h-1Process conditions under, carried out being hydrogenated with the engineer testing producing 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 properties
| Analysis project | |
| Density (20 DEG C), kg/m3 | 857.1 |
| Sulfur, 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 | ccat-5 | ccat-6 |
| Reaction temperature, DEG C | 221 | 222 | 224 | 234 | 236 | 238 | 228 | 238 | 229 |
| Liquid is received, wt% | 99.8 | 99.6 | 99.5 | 98.7 | 98.5 | 97.4 | 98.8 | 97.9 | 98.8 |
| Viscosity (40 DEG C), mm2/s | 33.38 | 33.04 | 32.78 | 31.09 | 29.58 | 28.37 | 31.01 | 26.91 | 31.00 |
| Viscosity (100 DEG C), mm2/s | 6.678 | 6.621 | 6.616 | 6.109 | 5.935 | 5.327 | 5.948 | 5.812 | 5.943 |
| Pour point, DEG C | -15 | -13 | -13 | -10 | -8 | -6 | -10 | -8 | -10 |
| Saybolt color/number | +32 | +31 | +32 | +30 | +29 | +26 | +30 | +25 | +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 | 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 | 0.5 | <0.1 |
Claims (30)
1. a kind of catalytic hydro-dearomatization catalyst, composition includes: main active component is pt, and adjuvant component is pd, and by little crystal grain y type
The carrier of molecular sieve, aluminium oxide and amorphous silica-alumina composition, wherein said little crystal grain y type molecular sieve, its property is as follows:
sio2/a12o3Mol ratio is 40～120, and average grain diameter is 200～700nm, relative crystallinity >=95%, 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.
2. according to the catalyst described in claim 1 it is characterised in that the average grain diameter of described little crystal grain y type molecular sieve
For 300～500nm.
3. according to the catalyst described in claim 1 it is characterised in that the relative crystallinity of described little crystal grain y type molecular sieve is
95%~120%.
4. according to the catalyst described in claim 1 it is characterised in that 1.7～10nm in described little crystal grain y type molecular sieve
The pore volume shared by secondary pore account for the 50% ~ 80% of total pore volume.
5. according to the catalyst described in claim 1 it is characterised in that 1.7～10nm in described little crystal grain y type molecular sieve
The pore volume shared by secondary pore account for the 60% ~ 80% of total pore volume.
6. according to the catalyst described in 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%.
7. according to the catalyst described in 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 little crystal grain y type molecular sieve is 5wt%～40wt%, and the content of amorphous silica-alumina is
20wt%～65wt%, the content of aluminium oxide is 10wt%～40 wt%.
8. according to the catalyst described in claim 1 it is characterised in that in described catalytic hydro-dearomatization catalyst carrier, with carrier
Weight on the basis of, its composition include: the content of little crystal grain y type molecular sieve be 10wt%～25wt%, the content of amorphous silica-alumina
For 30wt%～60wt%, the content of aluminium oxide is 15wt%～30wt%.
9. according to the catalyst described in claim 1 it is characterised in that the property of described catalytic hydro-dearomatization catalyst is as follows: ratio
Surface area is 350～550m2/ g, pore volume is 0.5～1.0ml/g.
10. the preparation method of the arbitrary described catalyst of claim 1 ~ 9, comprising:
By little crystal grain y type molecular sieve, amorphous silica-alumina and the binding agent mechanical mixture made with aluminium oxide, molding, then it is dried
And roasting, make catalyst carrier；Using infusion process in supported on carriers pt and pd, drying and roasting, obtain hydrogenation dearomatization
Hydrocarbon catalyst.
11. in accordance with the method for claim 10 it is characterised in that described little crystal grain y type molecular sieve is adopted and is made with the following method
Standby:
(1) preparation of little crystal grain nay type molecular sieve；
(2) little crystal grain nay type molecular sieve is prepared into na2Little crystal grain nh of o content≤2.5wt%4nay；
(3) little crystal grain nh is obtained to step (2)4Nay molecular sieve carries out hydrothermal treatment consists；
(4) molecular sieve of step (3) gained carries out dealumination complement silicon with hexafluorosilicic acid aqueous ammonium, the molecular sieve obtaining and by-product
Separate；
(5) molecular sieve obtaining step (4) is with containing nh4 +And h+Mixed solution process, be washed out and be dried, obtain little
Crystal Particle Size Y Zeolites,
Little crystal grain nay molecular sieve wherein used by step (1), its property is as follows: sio2/al2o3Mol ratio is not more than 6.0 and high
In 9.0, average grain diameter is 200～700nm, specific surface 800～1000 m2/ g, pore volume 0.30～0.45ml/g, tie relatively
Brilliant degree is 90%～130%, and cell parameter is 2.460～2.470nm, through relative crystallinity after 650 DEG C of in the air roastings 3 hours
For more than 90%, it is more than 90% through relative crystallinity after 700 DEG C of water vapour hydrothermal treatment consists 2 hours.
12. in accordance with the method for claim 11 it is characterised in that: the sio of little crystal grain nay molecular sieve used2/al2o3Rub
That ratio is 6.5～9.0.
13. in accordance with the method for claim 11 it is characterised in that: the sio of little crystal grain nay molecular sieve used2/al2o3Rub
That ratio is 7.0～8.0.
14. in accordance with the method for claim 11 it is characterised in that: little crystal grain nay molecular sieve used is through 650 DEG C of in the airs
After roasting 3 hours, relative crystallinity is 90%～110%, through relative crystallinity after 700 DEG C of water vapour hydrothermal treatment consists 2 hours is
90%～110%.
15. in accordance with the method for claim 11 it is characterised in that: the preparation method of little crystal grain nay molecular sieve used, bag
Include:
I, preparation directed agents: silicon source, silicon source, alkali source and water are fed intake according to following proportioning: (6～30) na2O:al2o3: (6～
30)sio2: (100～460) h2O, after stirring, mixture is stirred at 0～20 DEG C ageing 0.5～24 hour and is obtained and lead
To agent；
Ii, adopt 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 silicon dioxide as 40wt%～75wt%；Its preparation process includes:
A, respectively preparation sodium aluminate solution and sodium silicate solution；
The part sodium silicate solution adding step a to prepare in b, the sodium aluminate solution prepared to step a, then passes to co2Gas,
Controlling reaction temperature is 10 ~ 40 DEG C, and the ph value controlling 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 is with silicon dioxide
Meter accounts for step b and adds 5wt% ~ 85wt% in terms of silicon dioxide for the sodium silicate solution total amount；
C, at the control temperature and ph value of step b, said mixture ventilation stablize 10 ~ 30 minutes；
Iii, prepare silica-alumina gel: by (0.5～6) na2O:al2o3: (8～15) sio2: (100～460) h2O always feeds intake mole
Than, 0～40 DEG C quick stir under conditions of to the amorphous silica-alumina predecessor of step ii gained in add water, silicon source, guiding
Agent and alkali source, and control ph value for 9.5 ~ 12.0, uniform stirring, obtain silica-alumina gel；Wherein directed agents addition accounts for sial and coagulates
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.
16. in accordance with the method for claim 15 it is characterised in that in step ii, amorphous silica-alumina predecessor, with amorphous
On the basis of the weight of the butt of sial predecessor, the content that silicon is counted with silicon dioxide is for 55 wt%～70wt%.
17. in accordance with the method for claim 15 it is characterised in that: step b controlling reaction temperature be 15～35 DEG C.
18. in accordance with the method for claim 15 it is characterised in that: in step b, as the co being passed through2Gas flow accounts for total intake
80% ~ 100% when, add remainder sodium silicate solution.
19. in accordance with the method for claim 15 it is characterised in that: in step b, remainder sodium silicate solution is with titanium dioxide
Silicon meter accounts for step b and adds 30wt% ~ 70wt% in terms of silicon dioxide for the sodium silicate solution total amount.
20. in accordance with the method for claim 15 it is characterised in that in step i and iii, silicon source, alkali source are respectively selected from silicic acid
Sodium and sodium hydroxide, in step i, silicon source is selected from sodium metaaluminate.
21. in accordance with the method for claim 15 it is characterised in that in step iii, 10 ~ 30 DEG C of controlling reaction temperature, ph value
10～11.
22. in accordance with the method for claim 15 it is characterised in that step iv adopts two step dynamic crystallizations, the wherein first stepping
The condition of Mobile state crystallization is as follows: at 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；Second step enters Mobile state
The condition of crystallization is as follows: at 80～140 DEG C, crystallization time is 3～10 hours to temperature control.
23. in accordance with the method for claim 15 it is characterised in that step iv adopts two step dynamic crystallizations, the wherein first stepping
The condition of Mobile state crystallization is as follows: at 60～80 DEG C, crystallization time is 1～10 hour to temperature control；It is brilliant that second step enters Mobile state
The condition changed is as follows: at 80～120 DEG C, crystallization time is 5～10 hours to temperature control.
24. in accordance with the method for claim 11 it is characterised in that in step (3), the condition of described hydrothermal treatment consists is as follows:
Treatment temperature controls at 500～750 DEG C, and pressure is 0.01～0.50mpa, and process time is 1.0～4.0 hours.
25. in accordance with the method for claim 11 it is characterised in that in step (3), the condition of described hydrothermal treatment consists is as follows:
Treatment temperature controls at 600～700 DEG C, and pressure is 0.05～0.30mpa, and process time is 1.0～4.0 hours.
26. in accordance with the method for claim 11 it is characterised in that in step (4), compares 1 by solid-liquid weight in aqueous medium:
4 ~ 1:8 adds little crystal grain nh4Nay molecular sieve, stirs and is warmed up to 90～120 DEG C, is then added dropwise to hexafluorosilicic acid aqueous ammonium,
Constant temperature stirring after completion of dropping, separates molecular sieve and by-product, and filters, is dried, and wherein hexafluorosilicic acid aqueous ammonium is dense
Degree 10wt% ~ 40wt%, ammonium hexafluorosilicate addition is little crystal grain nh410wt% ~ the 50wt% of nay molecular sieve.
27. in accordance with the method for claim 11 it is characterised in that in step (5), by the molecular sieve after hydrothermal treatment consists and acid
With containing nh4 +Salt composition mixed solution contact, exchange molecular sieve in na+With removing molecular sieve in part non-framework aluminum,
Acid therein is one or more of hydrochloric acid, carbonic acid, nitric acid, sulphuric acid, containing nh4 +Salt be in the ammonium salt containing above acid group one
Plant or multiple；H in mixed solution+Concentration be 0.05～0.6mol/l, nh4 +Concentration be 0.5～3.0mol/l, exchange temperature
For 70～120 DEG C, the concentration exchanging molecular sieve in serosity is 0.1～0.5g/ml, and swap time is 0.5～3.0 hour, exchanges
Step repeats 1～4 time.
28. in accordance with the method for claim 11 it is characterised in that: step (2) adopt ammonium salt exchange method, process is such as
Under: with nay molecular sieve as raw material, exchanged 0.5～3.0 hour at 70～120 DEG C with the aqueous solution of solubility ammonium salt, molecular sieve
Concentration in exchanging serosity is 0.05～0.50g/ml, repeated exchanged l～5 time, filters off mother solution, washing, is dried；Ammonium salt is chlorine
Change one or more of ammonium, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, the concentration of ammonium salt solution
For 0.5～5.0mol/l.
29. in accordance with the method for claim 11 it is characterised in that: mix used with little crystal grain y molecular sieve and binding agent
Sio in amorphous silica-alumina2Weight content be 20%～60%, the pore volume of amorphous silica-alumina is 0.6～1.1 ml/g, specific surface
Amass as 300～500 m2/g.
30. in accordance with the method for claim 11 it is characterised in that: the drying of carrier and roasting condition are as follows: through 80 ~ 150
DEG C drying 3 ~ 10 hours, in 500 ~ 600 DEG C of roastings 3 ~ 6 hours；The condition of the drying of catalyst and roasting is as follows: 100 ~ 150
DEG C drying 1 ~ 12 hour, roasting 3 ~ 6 hours at 450 ~ 550 DEG C.
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| CN110540874B (en) * | 2018-05-29 | 2021-05-04 | 中国石油化工股份有限公司 | Processing technology of naphthenic oil |
| CN110540873B (en) * | 2018-05-29 | 2021-05-04 | 中国石油化工股份有限公司 | Method for processing naphthenic oil |
| CN110540871B (en) * | 2018-05-29 | 2021-05-04 | 中国石油化工股份有限公司 | Processing method of naphthenic oil |
| CN110540872B (en) * | 2018-05-29 | 2021-05-04 | 中国石油化工股份有限公司 | Naphthenic oil treatment process |
| CN108940354B (en) * | 2018-06-26 | 2021-02-23 | 中海油天津化工研究设计院有限公司 | C10+Heavy aromatics selective hydrogenation ring-opening catalyst and preparation method thereof |
| BR112021022558A2 (en) * | 2019-07-03 | 2022-01-11 | Mitsui Mining & Smelting Co Ltd | Method to produce a zeolite |
| CN114453014B (en) * | 2020-10-21 | 2023-07-28 | 中国石油化工股份有限公司 | Hydrodearene catalyst and preparation method and application thereof |
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