CN101327453B - Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst - Google Patents
Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst Download PDFInfo
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Abstract
The present invention relates to an Al2O3-SiO2-TiO2 composite oxide and a supported hydrogenation-dearomatization catalyst which is obtained with the composite oxide as a support. The composite oxide support is the Al2O3-SiO2-TiO2 composite oxide which is obtained by assembling and synthesizing an aluminium source, a silicon source and a titanium source by a sol-gel method, the specific surface area of the Al2O3-SiO2-TiO2 composite oxide is 250 to 400m<2>/g, the pore volume is 0.4 to 0.6cm<3>/g, and the aperture is 4 to 10nm. The composite oxide is used as the support to support noble metal and becomes deep hydrogenation-dearomatization catalyst to be used for the hydrogenation-dearomatization treatment of oil, and particularly, the composite oxide shows the stability and the dearomatization activity better than the normal catalyst in the deep hydrogenation-dearomatization reaction of diesel oil.
Description
Technical field
The present invention relates to a kind of Al
2O
3-SiO
2-TiO
2Composite oxides and be the load type catalytic hydro-dearomatization catalyst that carrier obtains with these composite oxides.The invention belongs to catalyst technical field.
Background technology
Along with the aggregate demand of vehicle fuel grows with each passing day, the discharge capacity of pollutant is also increasing in the vehicle exhaust, and the atmosphere polluting problem that causes is more and more serious; Meanwhile, people are also more and more stronger to the consciousness of environmental protection.Therefore, market is to the quality requirement increasingly stringent of oil product, and countries in the world have been revised strict standard of fuel in succession.Aspect indexs such as sulfur content, arene content, density and Cetane number to diesel product in new specification have proposed harsher requirement, and are particularly strict more to the requirement of sulfur content and arene content.For example in the Europe IV standard diesel oil index request sulfur content less than 10 μ g/g, arene content less than 11m%.Though the sulfur content index reduces significantly than before in China's diesel oil, arene content does not still change, and compares with advanced country that still there is a big difference.Diesel oil is carried out the further investigation that deep hydrofinishing particularly takes off aromatic hydrocarbons, and free of contamination to produce " clean diesel " becomes one of important topic of oil refining worker.
Improve the desulfurization of diesel oil and take off the aromatic hydrocarbons effect, can study breakthrough from improving catalyst property and hydrogenation technique (comprising equipment) two aspects, but prior art up to the present shows, adopt existing hydrogenation plant and operating condition, can't satisfy the requirement of deep desulfuration and deeply de-aromatizing.For reaching the purpose that reduces arene content in the diesel oil, except changing the industrial operation condition, catalyst and the new catalytic material of developing high hydrogenation performance are the keys that addresses this problem.
Domestic and international research institution takes off aromatic hydrocarbons to diesel oil deep and has all carried out active research, dicyclo in the discovery diesel oil is some heterocycles and polycyclic aromatic hydrocarbon particularly, for example dibenzothiophenes class, naphthalene class, acenaphthene class and the most difficult the removing of acenaphthylene class material are the refining difficult points of present diesel oil deep.Efficient deeply hydrodearomatized catalyst and relevant new material that exploitation has high hydrogenation performance have crucial meaning to effective lifting hydrogenation dearomatization performance.
For load hydrogenation catalyst, its catalysis effect of the interaction partners of the specific surface of carrier and pore structure feature and carrier and active metal component has obvious influence, and the carrier material of Hydrobon catalyst exploitation is at present mainly paid close attention to exploitation and had the carrier material of bigger serface more and increase dispersion degree of active components to improve the number in activated centre; How to make full use of simultaneously the increase of active component surface energy and the increase of blemish structure and improve the interaction of carrier and metal active constituent, thereby increase the metal active position to improve the catalytic activity of catalyst; In addition, improvement can also be passed through modulation structural promoter or preparation condition to catalyst performance, makes that the surface acidity of carrier and catalyst and acid distribution are more reasonable.Design and develop novel functional carrier material based on this condition, and the hydrogenation dearomatization catalyst of synthesizing high specific surface area and stability will be brought into play higher catalytic performance.
In order to obtain to have carrier than bigger serface and macroporous structure, a lot of researchs all propose to use the template agent, though can reach the specific area of increase carrier material and the effect of pore structure,, adopt the organic granular template also to increase preparation technology's complexity and catalyst cost.In the present application, conventional diesel oil hydrogenation aromatics-removing catalyst is to have the Al than bigger serface
2O
3Perhaps molecular sieve is that the catalyst of carrier loaded PtPd is main, takes off the aromatic hydrocarbons effect preferably though have, and it is very poor that stability still shows, and can not satisfy in the industrial production requirement to the long cycle life of catalyst; And Al
2O
3Though perhaps the catalyst of molecular sieve carrier load NiW also has certain fragrant effect of taking off, effect is unsatisfactory, particularly is difficult to remove dicyclo or polycyclic aromatic hydrocarbon, and this also is the one of the main reasons that is difficult to reach deeply de-aromatizing at present.
Summary of the invention
The technical problem underlying that institute of the present invention desire solves provides a kind of aluminum-silicon-titanium composite oxide carrier, for having the high dispersing microporous/mesoporous material than Large ratio surface, can be used for preparing highly active catalytic hydro-dearomatization catalyst.
The present invention provides a kind of load hydrogenation catalyst of realizing the diesel oil deepness hydrogenation dearomatization hydrocarbon on the other hand, characteristics by used aluminum-silicon-titanium composite oxide carrier, catalytic activity and stable aspect all show excellent effect, not only have the good aromatic hydrocarbons effect of taking off, product also has long cycle lie.
The present invention also provides the method for preparing above-mentioned aluminum-silicon-titanium composite oxide carrier and corresponding load hydrogenation catalyst, being self-assembled into by sol-gal process is the composite of three kinds of oxides, synthesis condition is relatively simple, be easy to control, and prepare described oxide carrier and need not to use expensive template agent.
Aluminum-silicon-titanium composite oxide carrier provided by the invention is for synthesizing the Al that obtains by sol-gal process with aluminium source, silicon source and the assembling of titanium source
2O
3-SiO
2-TiO
2Composite oxides, its specific area are 250～400m
2/ g, pore volume are 0.4～0.6cm
3/ g, aperture 4～10nm.
In the aluminum-silicon-titanium composite oxide carrier of the present invention, Al
2O
3-SiO
2-TiO
2The proportionate relationship of three kinds of oxides is adjustable, but its mass ratio is preferably 30-60:5-40:5-40.
Preparing described aluminum-silicon-titanium composite oxide carrier is that employing boehmite, ethyl orthosilicate and titanium alkoxide are primary raw material, adopt inorganic acid or organic acid hydrolysis, form by Prepared by Sol Gel Method, described inorganic acid comprises hydrochloric acid or nitric acid, and described organic acid comprises formic acid, acetate or adipic acid.
Among the present invention the characteristics of the synthetic method of aluminum-silicon-titanium composite oxide carrier be in building-up process by the hydrolyzation catalysis of acid, adopt the sol-gal process self assembly to synthesize three component Al
2O
3-SiO
2-TiO
2Composite oxide material is aggregate by abundant hydroxyl and static, hydrogen bond action with the plurality of raw materials self assembly, and suitable means such as employing speed control method, delay method and method of double crossing guarantee the control of assembling process and the quality of assembly element.According to the three component composite oxide carriers that this method not only can obtain having ideal surfaced character, the advantage of another aspect is that synthesis condition is relatively simple, is easy to control, need not to use expensive template agent.
Particularly, described sol-gal process is realized according to following process:
Boehmite is mixed with uniform aluminium colloidal sol slurries with alcohols solvent and acid solution;
Titanium alkoxide and ethyl orthosilicate are made silicon titanium colloidal sol under alcohols solvent and acid effect;
The speed of this silicon titanium colloidal sol with 3-5mL/ minute is added dropwise in the aluminium colloidal sol slurries, makes gel;
With roasting behind the made gel drying, obtain described aluminum-silicon-titanium composite oxide carrier;
Described acid is inorganic acid or organic acid soln.
Boehmite is broken into slurries with 1.0-1.3 times of alcohols solvent of its mass fraction, keep the agitation and dropping acid solution afterwards until forming aluminium colloidal sol.The method according to this invention during preparation aluminium colloidal sol, breaks into slurries with alcoholic solvent earlier with boehmite, slowly drips acid solution, especially nitric acid (preferably red fuming nitric acid (RFNA)) to sediment then and disappear under vigorous stirring, forms uniform aluminium colloidal sol slurries.For the benefit of form colloidal sol, preferably anhydrous alcoholic solvent of alcoholic solvent that uses in this process and acid solution and high concentrated acid.
The method of prepare silicon titanium colloidal sol comprises: the titanium alkoxide is made titanium colloidal sol with the alcohols solvent dissolving, and the dropping ethyl orthosilicate is made mixed serum, to be added to by the drips of solution that alcohols solvent, acid and water are mixed with then in this mixed serum, and stir and made silicon titanium colloidal sol in 10-30 minute;
In the silicon titanium colloidal sol of being prepared, the mol ratio of titanium alkoxide, alcohols solvent, acid and water is 1: (9～30): (0.2-1): (0.8-1.2).
More than drip the feed liquid operation and all should preferably control 3-5mL/ minute rate of addition keeping slowly dropping under the stirring condition.
The present invention is used to provide the titanium alkoxide in titanium source for having general formula Ti (OR)
4Salt, the R in the formula is the alkyl of C1-C4, for example, methyl, ethyl, propyl group, isopropyl and butyl etc., available titanium alkoxide can comprise tetrabutyl titanate, isopropyl titanate, butanols titanium, tetra isopropyl titanium etc.The lower alcohol solvent that the alcoholic solvent that preparation process is used generally can be used always, for example alcoholic solvent commonly used such as ethanol, isopropyl alcohol.
Above-mentioned preparation colloidal sol and gel process can at room temperature be finished, and generally are no more than 32 ℃.The gel that makes can be in vacuum drying chamber or the micro-wave oven inner drying, for example (for example 100-120 ℃ of vacuum drying 5-24 hour or microwave drying, can reach same effect in dry 15-20 minute in the 800W microwave device), dried product needs roasting at a certain temperature, thereby obtain titanium sial composite oxides, roasting condition can adopt 400-900 ℃ of roasting 3-6 hour.
The composite oxides of said process preparation adopt infusion process carrying metal component PtPd can make the bimetallic hydrogenation catalyst.
So, the present invention also provides a kind of load type catalytic hydro-dearomatization catalyst, two noble metal catalysts of it has utilized aluminum-silicon-titanium composite oxide carrier load of the present invention Pt and Pd, the load capacity of Pt is the 0.3-1.2% of total catalyst quality, and the load capacity of Pd is the 0.1-0.8% of total catalyst quality.
This catalyst can be used for the deep hydrogenation of oil product, realizes high-efficiency desulfurization and takes off aromatic hydrocarbons.At the character of handling oil product, can adjust the load capacity of reactive metal, for example, can be low supported catalyst, the load capacity of Pt is the 0.3-0.6% of total catalyst quality, the load capacity of Pd is the 0.1-0.2% of total catalyst quality; Can also be the high capacity catalyst, the load capacity of Pt be the 0.8-1.2% of total catalyst quality, and the load capacity of Pd is the 0.5-0.8% of total catalyst quality.The former can be used for the catalytic treatment of the lower oil product of sulfur-bearing, for example, and second section deeply de-aromatizing of diesel oil; The latter then can be used for sulfur-bearing and contains the higher desulfurizing oil of aromatic hydrocarbons and take off aromatic hydrocarbons.
Load processing as for reactive metal Pt and Pd can be finished according to common process fully, can be common dipping or step impregnation.
In a word, the present invention adopt the sol-gal process self assembly to synthesize to have bigger serface, mesoporous Al
2O
3-SiO
2-TiO
2Composite oxide carrier has overcome pure TiO
2Specific area is little, the weak point of poor stability, its specific area, pore volume and aperture and conventional hydrofining catalyst carrier γ-Al
2O
3Similar, and surface acidity and acid strength distribute and all are better than conventional Al
2O
3Carrier helps the carrying out of deeply hydrodearomatized reaction.Further become active good hydrofinishing deeply de-aromatizing catalyst after the carried metal component, satisfied the requirement of diesel oil deepness hydrogenation dearomatization hydrocarbon.
FCC diesel oil with the different places of production is raw material, to Al
2O
3-SiO
2-TiO
2Composite oxides are that the loaded noble metal catalyst of carrier carries out active appraisal experiment, find that the aromatic hydrocarbons effect of taking off of catalyst is better than Al with routine
2O
3And to Al
2O
3Carry out the TiO that obtains after the Ti modification
2-Al
2O
3Catalyst for carrier.
Under the reaction condition that relaxes: 300～350 ℃ of reaction temperatures, reaction pressure 4～6MPa, hydrogen-oil ratio 500～800, volume space velocity is 0.8～1.5h during liquid
-1, the taking off fragrant rate and can reach more than 95% of catalyst of the present invention.For example, can be sulfur content that total aromatic hydrocarbons in the diesel oil of 432ppm is removed to 1.0m% from 19.9m%, dicyclo and polycyclic aromatic hydrocarbon can be removed to 0 fully from 6.0m%; Simultaneously, two sections diesel hydrogenation for removal sulphur in simulation take off in the aromatic hydrocarbons reaction, in second section reaction, the total aromatic hydrocarbons in the ultra-low-sulphur diesel can be removed to 0.5m% from 30.1m%, dicyclo and polycyclic aromatic hydrocarbon are removed to 0 from 5.2m%, take off fragrant rate and also reach more than 97%, satisfy Europe-IV diesel quality standard.And, the stability result of catalyst shows: take off the aromatic hydrocarbons reaction for two sections diesel hydrogenation for removal sulphur, catalyst of the present invention is after testing through 500 hours, still the total aromatic hydrocarbons in the diesel oil can be removed to 0.8m% from 30.1m%, dicyclo and polycyclic aromatic hydrocarbon are removed to 0 from 5.2m%, demonstrate this catalyst and have the advantages of excellent stability energy and take off the aromatic hydrocarbons activity.
The specific embodiment
Below further specify embodiment of the present invention and the beneficial effect that produced by specific embodiment, understand essence of the present invention place better to help the reader, but but can not be interpreted as any qualification the present invention's practical range.
Embodiment 1
Take by weighing the boehmite of certain mass, break into slurries with absolute ethyl alcohol, the quality of used absolute ethyl alcohol is 1.0～1.3 times of boehmite quality, under intense stirring condition, slowly drip red fuming nitric acid (RFNA) then, disappear until sediment, form uniform slurries, obtain aluminium colloidal sol.
Deionized water, nitric acid are dissolved in the absolute ethyl alcohol successively, and the mol ratio of water, nitric acid, ethanol is 1:0.3:10, obtains solution A; Take by weighing the Ti (OC of certain mass
4H
9)
4Be dissolved in and make titanium colloidal sol in the ethanol, Ti (OC
4H
9)
4With the mol ratio of ethanol be 1:5; The ethyl orthosilicate of certain mass slowly is added drop-wise in the above-mentioned titanium colloidal sol, continues stirring it is fully dissolved each other, note is B; After A and B stirred 20 minutes respectively, at room temperature, solution A is poured in the speed control injector, controlling sample introduction speed then is 4mL/min, and under intense agitation, be added drop-wise among the B, continue stirring and obtained silicon titanium colloidal sol C in 10～30 minutes, controlling the total ratio of tetrabutyl titanate, ethanol, nitric acid and deionized water in this process is 1:15:0.3:1.
C pours in the speed control injector with silicon titanium colloidal sol, splash into gradually in the aluminium colloidal sol of vigorous stirring, in the process that drips, regulate the speed 4mL/min that drips, after dripping off, vigorous stirring is until forming gel, then with this gel in 110 ℃ of following vacuum drying 10 hours (vacuum is less than 80mmHg), distinguish roasting 3 hours down at 400 ℃ and 500 ℃ afterwards; The product of gained is Al
2O
3-SiO
2-TiO
2Composite oxide carrier, the quality of raw materials used boehmite, ethyl orthosilicate and tetrabutyl titanate is respectively by the Al in the complex carrier that obtains after the roasting
2O
3: SiO
2: TiO
2Ratio is calculated, and mass ratio is 10: 8: 2; 10: 6: 4; 10: 5: 5; 10: 4: 6 and 10: 2: 8, be designated as carrier 1-5, part carrier hole structural property is referring to table 1.
Synthesized Al
2O
3-SiO
2-TiO
2Behind the complex carrier, equal-volume step impregnation PdPt metal component on this complex carrier.Used slaine is respectively chloroplatinic acid (H
2PtCl
66H
2O) and palladium bichloride (PdCl
2), at first with a certain amount of chloroplatinic acid (H
2PtCl
66H
2O) and palladium bichloride (PdCl
2) be dissolved in respectively in the watery hydrochloric acid of 0.2mol/L, being made into dipping solution respectively, the mass fraction that makes Pt in the final catalyst is 0.8～1.2%, the mass fraction of Pd is 0.5～0.8%.The complex carrier order is inserted described platinum salt and palladium salt maceration extract obtains PtPd/Al
2O
3-SiO
2-TiO
2Two noble metal catalyst presomas, the catalyst precursor of each dipping back gained was put into ultrasonic oscillator ultrasonic 20 minutes, then 110 ℃ dry 12 hours down, under 500 ℃, roasting is 4 hours in the air atmosphere afterwards.The catalyst that obtains is corresponding with above-mentioned carrier, is labeled as PdPt/ carrier 1-5, or catalyst 1-5.
The pore structure feature of part catalyst is referring to table 2.
Table 1.Al
2O
3-SiO
2-TiO
2The BET characterization result of series composite oxides
Annotate: S
BET: specific area; V
BJH: pore volume; Diameter Average pore: average pore size
Table 2.PtPd/Al
2O
3-SiO
2-TiO
2The surface nature of catalyst series
Embodiment 2
Method according to embodiment 1 prepares complex carrier, and different is, wherein be that adipic acid is used in acid, prepare Al
2O
3-SiO
2-TiO
2The BET of series composite oxides characterizes similar to embodiment 1 result.
This carrier further floods precious metals pt and Pd, makes PtPd/Al
2O
3-SiO
2-TiO
2Catalyst series.
Embodiment 3
With embodiment 1 method, synthesized Al
2O
3-SiO
2-TiO
2Behind the complex carrier, equal-volume floods the PdPt metal component altogether on complex carrier, prepares PtPd/Al
2O
3-SiO
2-TiO
2Catalyst, wherein the mass fraction of Pd is 0.3～0.6%, and the mass fraction of Pd is 0.1～0.2%, and the order of dipping is Pd behind the first Pt.The preparation method is: used slaine is respectively chloroplatinic acid (H
2PtCl
66H
2O) and palladium bichloride (PdCl
2), at first with a certain amount of chloroplatinic acid (H
2PtCl
66H
2O) and PdCl
2Be dissolved in the watery hydrochloric acid of 0.2mol/L and be made into common dipping solution, adopt co-impregnation to obtain PtPd/Al
2O
3-SiO
2-TiO
2Two noble metal catalyst presomas after the impregnating metal active component, are put into the ultrasonic dispersion of ultrasonic oscillator 20 minutes with this catalyst precursor, following dry 12 hours at 110 ℃ then, under 500 ℃, roasting is 4 hours in the air atmosphere afterwards, prepares low carrying capacity PtPd/Al at last
2O
3-SiO
2-TiO
2Catalyst.
Embodiment 4
Prepare complex carrier with embodiment 1 method, but adopt isopropyl titanate as the titanium source in the preparation complex carrier process, and adopt isopropyl alcohol dissolving isopropyl titanate to prepare titanium colloidal sol, described solution A is the mixed solution of isopropyl alcohol, nitric acid and deionized water.The mol ratio of controlling isopropyl titanate, isopropyl alcohol, nitric acid and deionized water in the silicon titanium colloidal sol preparation process is 1:20:0.5:1.The quality of raw materials used boehmite, ethyl orthosilicate and isopropyl titanate is respectively by the Al in the complex carrier that obtains after the roasting
2O
3: SiO
2: TiO
2Ratio is calculated, and the BET feature of carrier is similar to embodiment 1 preparation carrier.
This carrier is made high capacity and low load capacity PtPd/Al according to the method dipping of embodiment 1 and 3
2O
3-SiO
2-TiO
2Catalyst is labeled as PdPt/ carrier 1A-5A, or catalyst 1A-5A.
Embodiment 5
Adopting hydrogenated diesel oil and catalysis to split the formulated according to a certain percentage ready-mixed oil of diesel oil, is that 5MPa, temperature are that 350 ℃, air speed are 1.0h at pressure
-1With hydrogen-oil ratio be under 600 the condition, adopt the high carrying capacity noble metal catalyst among the embodiment 1, carry out deeply hydrodearomatized experiment, the main character of raw materials used oil such as following table 3, the hydrogenation aromatics-removing result is as shown in table 4 below:
The main character of table 3. feedstock oil
The high content of metal PtPd/Al of table 4.
2O
3-SiO
2-TiO
2Catalyst series
Be used for diesel oil hydrogenation deeply de-aromatizing reaction result
Result from table 4 as can be seen, above-mentioned aluminium silicon titanium composite carried catalyst all shows good desulfurization degree and higher to take off virtue active, particularly the removal efficiency of polycyclic aromatic hydrocarbon all reaches 100%, shows that this series has good hydrogenation performance.And diesel oil has satisfied the sulfur content of Europe-IV standard and the index of total aromatic hydrocarbons and polycyclic aromatic hydrocarbon behind the hydrogenation of catalyst 1～4 sample gained.
Embodiment 6: catalytic activity and stability experiment
Adopting first section oil product that hydrodesulfurization obtains later on, is that 5MPa, temperature are that 350 ℃, air speed are 1.0h at pressure
-1With hydrogen-oil ratio be under 600 the condition, adopt the low carrying capacity loaded noble metal catalyst among the embodiment 3, carry out deeply hydrodearomatized experiment, the main character of raw materials used oil such as following table 5, it is as shown in table 6 below to take off the aromatic hydrocarbons effect.
The main character of second section raw materials used oil of hydrogenation reaction of table 5.
From table 6 reaction result as can be seen, when being used for second section hydrogenation dearomatization hydrocarbon reaction, should show more superior hydrogenation dearomatization activity by low carrying capacity noble metal catalyst series, the removal efficiency of total aromatic hydrocarbons all reaches more than 96.7%, the removal efficiency of polycyclic aromatic hydrocarbon all reaches 100%, shows that this series has good hydrogenation aromatics-removing performance.The hydrogenated diesel oil of all catalyst sample gained all satisfies the total aromatic hydrocarbons of Europe-IV standard and the index of polycyclic aromatic hydrocarbon, shows that this series composite oxide carrier catalyst under the low carrying capacity of noble metal, shows good hydrogenation performance.
Table 6. hangs down content of metal PtPd/Al
2O
3-SiO
2-TiO
2Catalyst series
Diesel oil hydrogenation deeply de-aromatizing reaction result
With embodiment 6 methods, the catalyst 3A that chooses in the table 6 carries out 500 hours experiment long cycle life, and it is as shown in table 7 below that it takes off the aromatic hydrocarbons result.
Table 7. catalyst takes off aromatic hydrocarbons experimental result long cycle life
Show by reaction result in the table 7, in second section very low diesel oil deepness hydrogenation dearomatization hydrocarbon experiment of sulfur content, even through 500 hours, the removal efficiency of total aromatic hydrocarbons can reach more than 97.7%, the removal efficiency of dicyclo and polycyclic aromatic hydrocarbon still keeps 100%, and it is respond well to take off aromatic hydrocarbons, and activity stability keeps good, prove that this catalyst has advantages of excellent stability energy and good deeply de-aromatizing activity, is expected to realize industrial applications in hydrogenation deeply de-aromatizing process.
Claims (10)
1. an aluminum-silicon-titanium composite oxide carrier synthesizes the Al that obtains for by sol-gal process aluminium source, silicon source and titanium source being assembled
2O
3-SiO
2-TiO
2Composite oxides, its specific area are 250～400m
2/ g, pore volume are 0.4～0.6cm3/g, aperture 4～10nm.
2. aluminum-silicon-titanium composite oxide carrier according to claim 1, wherein, Al
2O
3-SiO
2-TiO
2The mass ratio of three kinds of oxides is 30-60: 5-40: 5-40.
3. the preparation method of claim 1 or 2 described aluminum-silicon-titanium composite oxide carriers, it is characterized in that adopting boehmite, ethyl orthosilicate and titanium alkoxide is primary raw material, adopt inorganic acid or organic acid hydrolysis, form by following Prepared by Sol Gel Method, described inorganic acid is selected from hydrochloric acid or nitric acid, and described organic acid is selected from formic acid, acetate or adipic acid:
Boehmite is mixed with uniform aluminium colloidal sol slurries with alcohols solvent and described organic acid soln or inorganic acid solution;
Titanium alkoxide and ethyl orthosilicate are made silicon titanium colloidal sol under alcohols solvent and described organic acid or inorganic acid effect;
The speed of this silicon titanium colloidal sol with 3-5mL/ minute is added dropwise in the aluminium colloidal sol slurries, makes gel;
With roasting behind the made gel drying, obtain described aluminum-silicon-titanium composite oxide carrier.
4. preparation method according to claim 3 wherein, breaks into slurries with boehmite with 1.0-1.3 times of alcohols solvent of its mass fraction, keeps afterwards to drip acid solution under the stirring condition until forming aluminium colloidal sol.
5. preparation method according to claim 3, wherein, the method of prepare silicon titanium colloidal sol comprises: the titanium alkoxide is made titanium colloidal sol with the alcohols solvent dissolving, and the dropping ethyl orthosilicate is made mixed serum, to be added to by the drips of solution that alcohols solvent, acid and water are mixed with then in this mixed serum, and stir and made silicon titanium colloidal sol in 10-30 minute;
In the silicon titanium colloidal sol of being prepared, the mol ratio of titanium alkoxide, alcohols solvent, acid and water is 1: (9～30): (0.2-1): (0.8-1.2).
6. according to each described preparation method of claim 3-5, wherein, described titanium alkoxide is for having general formula Ti (OR)
4Salt, the R in the formula is the alkyl of C1-C4; Described alcohols solvent is selected from ethanol or isopropyl alcohol.
7. preparation method according to claim 3, wherein, described Drying of gels condition is 100-120 ℃ of dry 5-24 hour or microwave drying.
8. according to claim 3 or 7 described preparation methods, behind the gel drying in 400-900 ℃ of roasting 3-6 hour.
9. load type catalytic hydro-dearomatization catalyst, two noble metal catalysts of its Pt that has been claim 1 or 2 described aluminum-silicon-titanium composite oxide carrier loads and Pd, the load capacity of Pt is the 0.3-1.2% of total catalyst quality, and the load capacity of Pd is the 0.1-0.8% of total catalyst quality.
10. load type catalytic hydro-dearomatization catalyst according to claim 9, wherein, this catalyst is that the load capacity of Pt is 0.3-0.6%, the load capacity of Pd is the low supported catalyst of 0.1-0.2%, perhaps for the load capacity of Pt is 0.8-1.2%, the load capacity of Pd is the high capacity catalyst of 0.5-0.8%.
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