CN101890371B - Titanium dioxide-aluminum oxide composite carrier and preparation method thereof - Google Patents
Titanium dioxide-aluminum oxide composite carrier and preparation method thereof Download PDFInfo
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- CN101890371B CN101890371B CN200910011625A CN200910011625A CN101890371B CN 101890371 B CN101890371 B CN 101890371B CN 200910011625 A CN200910011625 A CN 200910011625A CN 200910011625 A CN200910011625 A CN 200910011625A CN 101890371 B CN101890371 B CN 101890371B
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Abstract
The invention discloses a titanium dioxide-aluminum oxide composite carrier and a preparation method thereof. Titanium hydroxide-aluminum hydroxide gel prepared by supersolubility micelles is used as a raw material, and the gel contains a surfactant and a hydrocarbon substance, so after the gel is molded and roasted, nanometer titanium dioxide and aluminum oxide particles formed by removing water from polymerized titanium hydroxide and aluminum hydroxide still have a rodlike basic structure and accumulate unorderly to form a frame structure. The composite carrier has the advantages of large pore volume, large pore diameter, high porosity, large orifices on the external surface, and high penetrability of pore channel; and particularly for macromolecules, a catalyst does not have ink bottle-shaped orifices, so the orifices cannot be blocked so as not to inactivate the catalyst. The composite carrier is favorable for increasing the sediment accumulation of impurities and prolonging the running period of the catalyst. The composite carrier can be used for catalytic reaction of macromolecular reactants or products.
Description
Technical field
The present invention relates to a kind of titanium dioxide-aluminum oxide composite carrier and preparation method thereof, particularly relate to a kind of large pore volume titanium dioxide-aluminum oxide composite carrier as residuum hydrodesulfurization, hydrodenitrogeneration and removal of ccr by hydrotreating catalyst carrier and preparation method thereof.
Background technology
Hydrodesulfurization is the important process process in the Ammonia Production of raw material as petroleum refining with the oil, receives people's attention always.But the quality of oil becomes heavy, variation day by day in recent years, and strict more to the requirement of product quality, subsequent technique is also more and more harsher to the requirement of charging.In addition, since the mankind got into 21 century, people's environmental consciousness constantly strengthened, and the environmental protection legislation is more and more stricter, to NO in the motor vehicles discharging waste gas
x, SO
xAnd the restriction of arene content is harsh more.The sulfur content of initial stage nineties european diesel standard is 2000 μ g/g, and the mid-90 is reduced to 500 μ g/g, 2005, requires sulfur content to be lower than 50 μ g/g.Based on above reason, the hydrodesulfurization technology of gasoline and diesel oil just develops towards the cleaning petroleum fuel direction of processing high-sulfur oils and production super-low sulfur.With present appointed condition, conventional hydrofinishing is difficult to reach the requirement of ultra-deep desulfurization, and in order to reduce sulfur content, the response parameter that only changes is as improving H
2Pressure, reduce air speed, improve reaction temperature etc.But this method one is high to equipment requirements, the 2nd, and cost is higher, so be not desirable way; With regard to catalyst, then must bring up to present 3～4 times to activity just can reach sulfur content and be lower than 50 μ g/g.Therefore, press for the requirement that catalyst that development has a high hydrodesulfurization activity satisfies the oil product deep desulfuration.This just requires and must carry out more extensive research to Hydrobon catalyst, with continuous developing new catalyst, satisfies actual needs.But the development of new catalyst is difficulty relatively, just can improve activity of such catalysts greatly and catalyst carrier is carried out modification, and therefore, many researchers focus on carrier is furtherd investigate.
Because environmental requirement is harsh day by day, the hydrofinishing technology has obtained unprecedented attention.In a period of time that can estimate, traditional M o (W)-Ni (Co)/γ-Al
2O
3The type Hydrobon catalyst will be given more sustained attention.Make such catalyst performance that at present has been in the stage of taping the latent power that a bigger leap arranged, excellent carrier has conclusive beyond doubt.
N type semiconductor TiO
2Have many properties as catalyst carrier, receive people's attention just day by day.But it is less relatively that its shortcoming is a specific area, generally is not more than 100m
2/ g; Active Detitanium-ore-type is at high temperature stable inadequately, is easy to become the rutile structure of inertia; Bad mechanical strength and acidity a little less than, it is difficult in the industry is widely used.The approach that its defective is solved has two: the one, study better preparation method; The 2nd, it is carried out modification, in the hope of obtaining good novel hydrogenation catalyst carrier material.To TiO
2The inorganic material of carrying out modification mainly contains Al
2O
3, SiO
2And ZrO
2Deng.Some researchers have been carried out TiO in recent years
2-Al
2O
3, TiO
2-SiO
2Etc. the research of binary composite oxide carrier, TiO
2Load on and have, improve its catalytic performance than increasing its decentralization on bigger serface and the constitutionally stable oxide carrier.A large amount of researchs show that transition metal is supported on TiO
2-Al
2O
3Or TiO
2-SiO
2The complex carrier surface has than directly being supported on Al
2O
3, SiO
2The surface has higher catalytic activity.TiO in these composite oxides
2-Al
2O
3System obtains paying attention to the most widely.
Up to the present, residue fixed-bed used catalyst carrier still is to use classical alumina support.High-temperature roasting method, pH value swing method and steam treatment can obtain being applicable to the macroporous aluminium oxide of residual oil, and the pore volume that the duct concentrates on 8～15nm accounts for more than 80%, and catalyst has very high initial activity.The macroporous aluminium oxide duct is run through the residual oil molecule continuously, but the duct too concentrates on about 10nm～20nm, is unfavorable for the catalyst long-term operation.Beds stops up and causes device to stop work; Catalyst changeout more; Its chief reason is exactly: the concentrated duct of catalyst carrier big pore aluminium oxide is stopped up by metal and carbon residue and is become less than 10nm when following at present, in the residual oil greatly molecule can't be penetrated into inside, duct.
Sulphur, nitrogen a large amount of in the residual oil are present in the asphalitine micelle.The asphaltene molecules diameter is at 4～5nm, the asphalitine micelle of formation be in colloid as being present under the stabilizer function in the residual oil, its diameter from 10nm to hundreds of nm.In the residual hydrogenation catalyst series, even in residuum hydrodesulfurization, denitrogenation, take off and have Hydrodemetalation catalyst to make big molecule asphalitine partial crushing form little asphalitine micelle before the carbon residue catalyst.Because hydrodenitrogeneration and to take off the duct of carbon residue catalyst improper; When the duct concentrated on the 10nm left and right sides, little asphalitine micelle still can not get into catalyst inside, can be in denitrogenation, take off carbon residue catalyst outer surface and react; Make metal impurities stop up the duct of outer surface, cause catalysqt deactivation.
In order to realize desulfurization, denitrogenation, to take off carbon residue catalyst long-term operation, when catalyst assurance desulfurization, denitrogenation, taking off carbon residue, must improve the appearance metal ability of catalyst, must improve extremely micron-sized duct ratio of 30nm.The method that adopts at present mainly is the physics port-creating method, can obtain 30nm to micron-sized macropore duct, but this duct is discontinuous running through, and the duct is dispersity, and the aperture is the ink bottle type.Because this duct is discontinuous running through, and is limited to the reactant diffusion.Carbon black and polystyrene are that template generates orderly large pore material, and the duct belongs to the ink bottle orifice type, and the residual oil bulky molecular catalysis can't be carried out in most of duct.
CN 1316486A discloses a kind of titanium oxide and aluminium oxide complex, and the particle diameter of its basic granules is 2～40nm, and specific area is at 400m
2More than/the g, pore volume is greater than 0.6ml/g.This complex is to adopt sol-gel-Supercritical Drying Technology preparation.Though do not provide its average pore size in this patent, can know that by formula d=4V/S (wherein d is an average diameter, and S is a specific surface, and V is a pore volume) under the suitable situation of pore volume, its specific surface is big more, its average pore size is just more little.Like the titanium dioxide-aluminum oxide carrier of gained among the embodiment 7, its specific surface is 420.31m
2/ g, pore volume are 0.7501ml/g, and can get its average pore size thus is 7.1nm, and the average pore size of this carrier is less, is unfavorable for macromolecular diffusion in the raw material, thereby has influenced reaction rate, even can influence the removal efficiency of impurity in the raw material.
Summary of the invention
The objective of the invention is to weak point of the prior art, the invention provides a kind of large pore volume, Large ratio surface, macroporosity, good titanium dioxide-aluminum oxide composite carrier of big molecular diffusion performance and preparation method thereof.
Titanium dioxide-aluminum oxide composite carrier of the present invention contains the rod-like nano titanium dioxide-aluminum oxide, and the physicochemical property of said titanium dioxide-aluminum oxide composite carrier is following: pore volume is 1.0～2.1ml/g, is preferably 1.3～1.8ml/g, and specific surface is 180～420m
2/ g is preferably 200～350m
2/ g, average pore size is 10～70nm, is preferably 15～50nm, porosity is 55%～88%, is preferably 75%～85%.
The said porosity of the present invention is the porosity of the particle inner duct that records with mercury injection method.
In the titanium dioxide-aluminum oxide composite carrier of the present invention, titania weight content is 2.0%～60.0%.
The diameter of the rod-like nano titanium dioxide-aluminum oxide compound that contains in the described titanium dioxide-aluminum oxide composite carrier is 50nm～500nm, preferred 80nm～300nm, and length is 2～10 times of diameter.Described rod-like nano titanium dioxide-aluminum oxide is piled into tower structure in disorder in carrier, make carrier form large pore volume, large aperture, and macropore duct connectivity is good, and the aperture is bigger, helps macromolecular diffusion.The weight content of described rod-like nano titanium dioxide-aluminum oxide compound in the titanium dioxide-aluminum oxide carrier is 30%～100%, is preferably 60%～90%.
The pore size distribution of described titanium dioxide-aluminum oxide composite carrier is following: bore dia accounts for more than 75% of total pore volume in the hole more than the 10nm, is preferably 80%～94%.The pore size distribution of titanium dioxide-aluminum oxide carrier of the present invention is adjustable in 10～1000nm scope; The concrete pore size distribution of said titanium dioxide-aluminum oxide carrier can confirm according to concrete application, and the raw material that generally will handle according to institute is selected with the molecular size and the existence of generation product.
The crushing strength of described titanium dioxide-aluminum oxide composite carrier is 6～80N/mm, is preferably 12～40N/mm.
In the described titanium dioxide-aluminum oxide carrier, can also contain the component of being introduced by adhesive, its content accounts for below 70% of titanium dioxide-aluminum oxide vehicle weight, is preferably 10%～40%, such as little porous aluminum oxide and/or macroporous aluminium oxide.
The preparation method of titanium dioxide-aluminum oxide composite carrier of the present invention comprises the steps:
(1) preparation of nanometer titanium hydroxide-gel aluminum hydroxide,
(2) the nanometer titanium hydroxide-gel aluminum hydroxide of step (1) gained is after drying, and moulding again through drying and roasting, obtains titanium dioxide-aluminum oxide carrier of the present invention.
The described nanometer titanium hydroxide-gel aluminum hydroxide of step (1) is to adopt the preparation of the ultra solubilising micelle of fused salt method, and is such as the disclosed ultra solubilising micelle method of CN200610134167.2, specific as follows:
A, hydrocarbon component, VB value are mixed less than 1 surfactant;
B, contain titanium hydroxide-gel aluminum hydroxide and make by following at least a method:
Method one:
Under the normal pressure, aluminium salt and titanium salt splash in the mixture of steps A gained, are mixed to form evenly ultra solubilising micelle; In above-mentioned system, add precipitating reagent and/or aqueous catalyst solution, under 50～120 ℃ of temperature, reacted 1～10 hour, aging 0～30 hour then, be preferably 3～24 hours, obtain containing titanium hydroxide-gel aluminum hydroxide;
Method two:
Aluminium salt and titanium salt are splashed in the mixture of steps A gained, be mixed to and form evenly ultra solubilising micelle; In confined conditions, below the ammonia critical-temperature, add precipitating reagent and/or catalyst liquefied ammonia; Or in confined conditions,, feed precipitating reagent and/or catalyst ammonia gas react at 30～300 ℃; Aging 0～30 hour then, be preferably 1～8 hour, obtain containing titanium hydroxide-gel aluminum hydroxide;
Method three:
Aluminium salt, titanium salt and precipitating reagent and/or catalyst are splashed in the mixture of steps A gained, be mixed to and form evenly ultra solubilising micelle; Under airtight condition, with resulting mixture in 70～200 ℃ of thermotonuses 1～10 hour, aging 0～30 hour then, be preferably 1～8 hour, obtain containing titanium hydroxide-gel aluminum hydroxide;
Described aluminium salt and titanium salt are inorganic salts and/or organic alkoxide, and wherein inorganic salts can adopt the inorganic salts that contain the crystallization water, also can adopt the inorganic salts that do not contain the crystallization water.Different according to the mode that adds steps A, said aluminium salt and titanium salt comprise water-soluble inorganic salt, pure dissolubility salt and eutectic, and wherein pure dissolubility salt is divided into pure dissolubility inorganic salts and organic alkoxide.Alleged water soluble salt is a water soluble inorganic salt; Alcohol dissolubility inorganic salts are to be soluble in low mass molecule alcohol or to react the inorganic salts that generate the alkoxide that is dissolved in low mass molecule alcohol with low son alcohol; Organic alkoxide is the alkoxide that is dissolved in low mass molecule alcohol; Low mass molecule alcohol is to be selected from ethanol, propyl alcohol, isopropyl alcohol, n-butanol and the isobutanol one or more; Eutectic be meant can be in-50 ℃～50 ℃ a certain temperature be the inorganic matter of liquid phase, such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetrafluoride and titanium tetra iodide etc.
In method one, method two and the method three; Titanium salt and aluminium salt can select one of following manner to add: I, can adopt water soluble salt separately, II, also can adopt pure dissolubility inorganic salts separately, III, can partly adopt water soluble salt; Part adopts pure dissolubility inorganic salts; IV, part adopt water soluble salt and/or pure dissolubility inorganic salts, and part adopts organic alkoxide, and wherein inorganic salts account for more than the 20wt%; V, on the basis of above-mentioned I, II, III or IV, increase eutectic.
It is following that water-soluble inorganic salt, pure dissolubility inorganic salts, organic alkoxide and eutectic splash into mode:
Water-soluble inorganic salt adds in the described mixture of steps A, can molten state splash into, and melting range is preferably 50～120 ℃ at 50～200 ℃.The inorganic salts of different melting points can splash into behind the mixed melting, also splash into respectively after the fusion respectively.Water-soluble inorganic salt can also aqueous solution form splash into, but wants the Total Water of guarantee system to be no more than the scope of requirement.Alcohol dissolubility salt adding mode is and splashes in the described mixture of steps A after low mass molecule alcohol mixes, and when adopting multiple pure dissolubility salt, can splash into together with after low mass molecule alcohol mixes, and also can splash into respectively more respectively with after low mass molecule alcohol mixes.Eutectic can above-mentioned water soluble salt and/or pure dissolubility salt splash into form uniformly ultra solubilising micelle in the described mixture of steps A before, splash into afterwards or simultaneously.
Weight with the mixture of step B gained is benchmark; The consumption of aluminium salt (butt), titanium salt (butt), precipitating reagent, catalyst, low mass molecule alcohol and water is 60.0wt%～93.0wt%; Be preferably 75.0wt%～92.0wt%, the water yield is as the 100wt%～350wt% of the theoretical water requirement of reaction water, is preferably 100wt%～300wt%; The consumption of precipitating reagent is the 100wt%～300wt% of theoretical requirement; The consumption of low mass molecule alcohol is 0～30wt%, and amount of surfactant is 0.1wt%～15.0wt%, better is 0.5wt%～12.0wt%; The consumption of hydrocarbon component is 6.9wt%～32.0wt%, better is 7.5wt%～24.5wt%.
Wherein water can add with the crystallization water and/or free water form in steps A and/or step B; Low mass molecule alcohol adds with pure dissolubility titanium salt and/or aluminium salt.
The condition of the described nanometer titanium hydroxide of step (2)-gel aluminum hydroxide drying is following: 100～130 ℃ of baking temperatures, 1～30 hour drying time.
Among the present invention, in order to obtain purer titanium dioxide-aluminum oxide, also can be with the nanometer titanium hydroxide-gel aluminum hydroxide of step (1) gained through washing Zhiyin ion weight concentration less than 0.5%, and then carry out step (2).Described washing generally adopts water washing just can reach requirement, with water washing to the weight concentration of Na ion and Fe ion all below 0.5%, water wherein preferably adopts distilled water or deionized water.
The said forming method of step (2) can adopt the conventional method for preparing carrier, preferred pressed disc method or extruded moulding method.Described pressed disc method process is following: with the dry powder of nanometer titanium hydroxide-gel aluminum hydroxide, putting into tablet press machine, is under 0.08～20.00MPa condition at pressure, compression molding.In the pressed disc method, can in the dry powder of nanometer titanium hydroxide-gel aluminum hydroxide, add releasing agent, releasing agent is a carbon black, and consumption is 0～5.0% of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium body weight, is preferably 0.1%～5.0%.
Described extrusion method process is following: nanometer titanium hydroxide-gel aluminum hydroxide xeraphium, binding agent, peptizing agent, water and cosolvent are mixed; This process can be conventional charging sequence, preferably earlier nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binding agent are mixed; Again peptizing agent, water and cosolvent are mixed in the mixture that is added to nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binding agent then, stir, on batch mixer, mix, moulding in banded extruder then.Described batch mixer can be kneader or roller.In the described extrusion process, controlled pressure is at 10～50MPa.Described peptizing agent can be in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and the sulfuric acid one or more; Consumption is 1%～15% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight; Described water preferably adopts deionized water; Consumption is 5%～100% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight, preferred 20%～70%.Peptization course also need add cosolvent, and cosolvent is one or more in methyl alcohol, ethanol and the propyl alcohol, and consumption is 1%～15% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight.
Described binding agent preferably adopts titaniferous to intend thin water-aluminum hydroxide; Intending thin water-aluminum hydroxide can be that the macropore titaniferous is intended thin water-aluminum hydroxide; Also can be that the aperture titaniferous is intended thin water-aluminum hydroxide; The component that its consumption is introduced binding agent finally accounts for below 70% of titanium dioxide-aluminum oxide vehicle weight, is preferably 5%～50%.
Drying condition after the said moulding is following: under 100～130 ℃ of temperature, carried out drying 1～30 hour.Described roasting can be adopted a conventional one-step baking method; Condition was following: 180～1200 ℃ of roastings 4～80 hours; Programming rate was 0.1～5 ℃/min, preferably divides one-step baking, and condition is following: 180～300 ℃ of roasting temperatures 1～10 hour; 500～1200 ℃ of roastings 2～60 hours, programming rate was 1～5 ℃/min.
Titanium dioxide-aluminum oxide composite carrier of the present invention is that the hydroxide gel that adopts ultra solubilising micelle method to obtain is that raw material roasting after moulding obtains.Because ultra solubilising method is to adopt VB value less than the reversed phase micelle that 1 surfactant forms, and obtains unique ultra solubilising nanometer " reactor ", the nano particle process self assembly of reaction generation obtains the hydroxide gel of club shaped structure.Owing to contain surfactant and hydrocarbon component in the hydroxide gel; In forming process, still can keep club shaped structure; And in high-temperature calcination process; Surfactant is progressively deviate from, and surfactant still has the carrying out that self assembly property is being controlled reaction during this, makes the hydroxide of polymerization deviate from the nanometer oxide particle that forms behind the moisture and still has bar-shaped basic structure.Bar-shaped nano-oxide is unordered being deposited in together each other, and the frame structure of formation does not have fixing outer surface, and the aperture is bigger; The duct penetrability is good; Especially concerning big molecule, can not resemble the aperture of ink bottle type, stop up because of the aperture and make catalysqt deactivation; Help increasing the deposition of impurity, prolong the service cycle of catalyst.
The cumulative volume of hydroxide nano particle self-assembly organic moiety of the present invention is exactly the solvent hydrocarbon component sum of surfactant VB value lipophilic group part and reversed phase micelle.This part behind shaping and roasting, will form the duct part as template in carrier, make titanium dioxide-aluminum oxide composite carrier have bigger pore volume, aperture and porosity.The present invention can be adjusted pore volume, aperture, porosity and the pore size distribution of titanium dioxide-aluminum oxide composite carrier by the size of this organic moiety amount.
Conventional method is not owing to there is template, and the intensity of the catalyst carrier of being synthesized and pore volume are conflicting, and along with the adding of peptizing agent and the increase of pressure, the pore volume of porous powder and aperture will reduce.And in the inventive method because the existence of template during moulding; The factor of pressure will not have the effect that destroys duct and pore volume; Peptization acid can be deviate from the frame structure that forms after the template and just can keep very high intensity with titanium dioxide-aluminum oxide composite carrier very secure bond together like this.
The hydrocarbon component that contains in the hydroxide gel of the present invention mainly contains two effects in the nanometer self assembling process: the one, and as the reversed micelle solvent of ultra solubilising micelle system, the 2nd, together play the effect of expanding the duct with surfactant.Interaction between the lipophilic group of hydrocarbon component and surfactant is the effect between the hydrophobic bond, and adhesion is less.When moulding, under the effect of pressure and/or adhesive, bonding has taken place between the hydroxide, owing to contain the hydrophilic radical of strong interaction, surfactant and hydroxide have also formed strong absorption and have interacted.When hydrocarbon component content is very high; The VB value is less in the hydroxide gel, the hydrocarbon component in the huge mixing lipophilic group under pressure, depending merely on interacts with the surfactant lipophilic group is not enough to be kept in the hydroxide particle of nanometer self assembly; This has just caused the part hydrocarbon component to leave nanometer self assembly particle; Form hydrocarbon accumulation, caused the distribution of duct wide region, the large pore volume titanium dioxide-aluminum oxide composite carrier is formed from nanometer to micron-sized different frames structure pore.
Titanium dioxide-aluminum oxide composite carrier of the present invention can be used for containing in the catalytic reaction of macromolecular reaction thing or product; Refining such as residual hydrogenation; Macromolecular polymerization reaction, reactions such as big molecule and high molecular hydrogenation reaction, dehydrogenation reaction, oxidation reaction, aromatisation, isomerization, alkylation, reformation catalysis, etherificate.The high diffusion of the penetrability of carrier of the present invention can make big molecule and macromolecule in the duct, be diffused into the reaction position easily, and the macromolecule that forms is diffused out outside the caltalyst.
Description of drawings
Fig. 1 is ESEM (SEM) figure of Comparative Examples 1 conventional titanium dioxide-aluminum oxide carrier.
Fig. 2 is the SEM figure (40000 times of multiplication factors) of embodiment 1 gained titanium dioxide-aluminum oxide carrier.
The specific embodiment
Pore volume among the present invention, specific surface, average pore size, pore size distribution, porosity adopt mercury injection method to record.Crushing strength adopts intensity meter to measure.
Comparative Examples 1
With concentration is that the sodium metaaluminate of 30g/L places in the glue jar, keeps 25 ℃ of temperature, feeds the neutralization of 40v% carbon dioxide, adds 20gTiO constantly stirring
2/ L metatitanic acid slurries (pH is 8, and granularity is less than 40u) make carrier contain 10% TiO
2, it is 10 that feeding 40v% carbon dioxide is neutralized to pH, filtration drying, and pulverizing is 120 orders.Claim that the 100g powder adds 5g acetic acid, the 100g deionized water, moulding in banded extruder, controlled pressure is at 35MPa.Article shaped was carried out drying 8 hours under 100 ℃～120 ℃ temperature, in 4 hours, be warming up to 800 ℃, and constant temperature 4 hours obtains titanium dioxide-aluminum oxide carrier DTA1.
Embodiment 1
Under stirring condition, 375g nine water aluminum nitrates and 90g urea are mixed and heated to 100 ℃, are added in the mixture of the 150HVI neutral oil of 32g polyisobutene maleic acid triethanolamine ester and 88g under the equal temperature condition, form ultra solubilising micelle.In 200g ethanol, add the 96g titanium tetrachloride, be added dropwise in the above-mentioned micelle, 100 ℃ of confined reactions 3 hours, obtain nanometer titanium hydroxide-gel aluminum hydroxide then.With 200ml distilled water washing three times, 120 ℃ of dryings of warp 10 hours.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA1 of the present invention.
Embodiment 2
The titanium dioxide-aluminum oxide carrier TA1 of embodiment 1 gained is soaked reactive metal, contain 14% (mass fraction) MoO among the gained residuum hydrodesulfurization catalyst HDS-1
3, 4% (mass fraction) NiO.
Residuum hydrodesulfurization catalyst HDS-1 is used for residual oil raw material (character is seen table 2) hydrodesulfurization experiment, and experimental condition is seen table 3, and result of the test is seen table 4.
Comparative Examples 2
The alumina support DTA1 of Comparative Examples 1 gained is soaked reactive metal, contain 14% (mass fraction) MoO among the gained residuum hydrodesulfurization catalyst HDS-2
3, 4% (mass fraction) NiO.
Test method according to embodiment 2 adopts residuum hydrodesulfurization catalyst HDS-2 to test, and experimental condition is seen table 3, and result of the test is seen table 4.
The hydrogenation catalyst that nano-titanium oxide-alumina composite oxide of the present invention makes has Large ratio surface, large pore volume, large aperture, when being used to handle heavy oil residue, shows good desulphurizing activated.
Embodiment 3
Embodiment 1 forming method is changed to pressed disc method, and process is following: dry powder of nanometer titanium hydroxide-gel aluminum hydroxide and 12g carbon black are put into tablet press machine, are under the 0.08MPa condition at pressure, compression molding.Article shaped was carried out drying 8 hours under 120 ℃ of temperature, 260 ℃ of roasting temperatures 3 hours, 750 ℃ of roastings 4 hours, wherein programming rate was 4 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA2 of the present invention.
Embodiment 4
The roasting condition of article shaped among the embodiment 1 is changed to: be raised to 1500 ℃ with the programming rate of 3 ℃/min from 180 ℃ and carry out roasting, obtain titanium dioxide-aluminum oxide carrier TA3 of the present invention.
Embodiment 5
With 480g nine water aluminum nitrates, 18g titanium tetrafluoride, 192g urea and 34g ethanol heating and melting, splash into 50 ℃ 207g and subtract in the two mixtures of hanging succimide of four line distillates and 55g T-154 and mix, add the 14g TEPA then and mix.In confined conditions, under 150 ℃ of temperature, keep this temperature and pressure, reacted 3 hours.After reaction finishes, with washing with alcohol 1 time, be washed with distilled water to no anion then, centrifugation is at last 100 ℃ of dryings 20 hours down.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA4 of the present invention.
Embodiment 6
The preparation method of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium is with embodiment 1.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 50g and binding agent boehmite 50g are mixed; 3.5g phosphoric acid (mass concentration 85%), 15g water and 3g cosolvent propyl alcohol are mixed; Be added to then in the mixture of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binding agent, stir, on batch mixer, mix; Moulding in banded extruder then, controlled pressure is at 30MPa.Article shaped was carried out drying 12 hours under 120 ℃ of temperature, 280 ℃ of roasting temperatures 2 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA5 of the present invention.
Embodiment 7
Embodiment 5 forming processes are changed into: dry powder of nanometer titanium hydroxide-gel aluminum hydroxide and 20g carbon black are put into tablet press machine, are under the 1.0MPa condition at pressure, compression molding.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 210 ℃ of roasting temperatures 3 hours, 750 ℃ of roastings 4 hours, wherein programming rate was 4 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA6 of the present invention.
Embodiment 8
248g aluminium isopropoxide, 247g titanium tetra iodide and 98g ethanol are heated to 90 ℃ of fusions; Splash in 90 ℃ the mixture of 178g vacuum 1st side cut distillate, 48g polyethylene propylene maleic acid glycol ester; Splash into 200g ammoniacal liquor (weight concentration 50wt%) then; Add 40g 1 at last, the 6-hexamethylene diamine mixes.Be washed with distilled water to no anion, centrifugation.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA7 of the present invention.
Embodiment 9
With 37g titanium tetrabromide, 675g nine water aluminum nitrates and 450g isobutanol heating and melting, splash in 75 ℃ the mixture of 65g second line of distillation distillate, 15g fatty acid monoglyceride.The mixed liquor that splashes into 40g hexamethylenetetramine and 10g water then mixes.In confined conditions, feed 120g liquefied ammonia, be warming up to then under 120 ℃ of temperature, keep temperature, pressure, reacted 3 hours.After reaction finishes,, be washed with distilled water to no anion then, centrifugalize with washing with alcohol 1 time.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide alumina gel xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA8 of the present invention.
Embodiment 10
With 634g 18 water aluminum sulfate, 60g titanium trichloride, 500g ammonium oxalate and 120g n-butanol heating and melting, the 65g soya-bean oil, the 15g T-151 list that splash into 85 ℃ are hung in the mixture of succimide.The mixed liquor that splashes into 40g TBAH and 5g water then mixes.In confined conditions, under 150 ℃ of temperature, keep temperature, pressure, reacted 3 hours.After reaction finishes,, be washed with distilled water to no anion then, centrifugalize with washing with alcohol 1 time.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA9 of the present invention.
Embodiment 11
With 94g titanium tetrachloride, 384g ammonium carbonate and 150g propyl alcohol heating and melting; Splash in 85 ℃ the 65g second line of distillation slack wax, 15g SP-80,5g calcium mahogany sulfonate and mix; The 500g nine water aluminum nitrates of fusion are splashed in the said mixture; And under 85 ℃ of temperature, mixed 20 minutes, add the 40g TPAOH then and mix.In confined conditions, 150 ℃ of thermotonuses 3 hours.After reaction finishes,, be washed with distilled water to no anion then, centrifugalize with washing with alcohol 1 time.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA10 of the present invention.
Embodiment 12
With 289g 18 water aluminum sulfate, 50g titanium tetrafluoride, 340g carbonic hydroammonium and 100g ethanol heating and melting; Splash in 85 ℃ the mixture of 65g second line of distillation slack wax, 15g polyisobutenyl maleic acid MEA ester; Mixed 20 minutes under this temperature, add the 40g TMAH then and mix.In confined conditions, 150 ℃ of thermotonuses 3 hours.After reaction finishes,, be washed with distilled water to no anion then, centrifugalize with washing with alcohol 1 time.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA11 of the present invention.
Embodiment 13
With 450g Aluminum Chloride Hexahydrate, 120g titanyl nitrate, 270g urea and 80g methyl alcohol heating and melting, splash in 85 ℃ the mixture of 65g150SN neutral oil, 15g aliphatic acid two sweet esters, 8g enuatrol, and under this temperature, mixed 20 minutes.The mixed liquor that adds 40g tetraethyl ammonium hydroxide and 5g water then mixes.In confined conditions, under 150 ℃ of temperature, reacted 3 hours.After reaction finishes,, be washed with distilled water to no anion then, centrifugalize with washing with alcohol 1 time.Following dry 20 hours at 100 ℃ at last.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA12 of the present invention.
Embodiment 14
With 580g nine water aluminum nitrates and the dissolving of 180g ethanol Hybrid Heating, the 280g that splashes into 80 ℃ subtracts in the mixture of three-way distillate, 48g polyisobutenyl maleic acid diethanol amine ester and 72g water, and under this temperature, mixes 15 minutes.Splash into the 464g titanium trichloride then and be solubilized in the reaction system, mix.In confined conditions, under the critical-temperature of liquefied ammonia, add 306g liquefied ammonia, mix; More than critical-temperature, keep 180 ℃, and supercritical pressure is carried out neutralization reaction.After reaction finished, reactant was washed with distilled water to no anion, centrifugation, at last 100 ℃ dry 20 hours down.Nanometer titanium hydroxide-gel aluminum hydroxide xeraphium 160g and binding agent boehmite 40g are mixed; The rare nitric acid of 2.6g (mass concentration 17%), 60g water and 10g cosolvent ethanol are mixed, stir, on batch mixer, mix, moulding in banded extruder then, controlled pressure is at 10MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained titanium dioxide-aluminum oxide carrier TA13 of the present invention.
The character of table 1 embodiment of the invention gained titanium dioxide-aluminum oxide carrier
| Sample | TA1 | DTA1 | TA2 | TA3 | TA4 | TA5 |
| Pore volume/cm 3.g -1 | 1.82 | 0.42 | 1.80 | 2.00 | 1.18 | 1.20 |
| Specific surface/m 2.g -1 | 316 | 216 | 180 | 180 | 262 | 208 |
| Average pore diameter/nm | 23.0 | 7.7 | 40.0 | 44.0 | 18.0 | 23.0 |
| Pore size distribution, % | ||||||
| ＜10nm | 17 | 88 | 17 | 13 | 8 | 11 |
| 10-100nm | 55 | 5 | 80 | 56 | 89 | 70 |
| ＞100nm | 28 | 7 | 3 | 31 | 3 | 9 |
| Porosity/% | 87 | 42 | 86 | 87 | 88 | 88 |
| Intensity, N/mm | 8 | 41 | 22 | 36 | 11 | 29 |
The character of table 1 (continuous 1) embodiment of the invention gained titanium dioxide-aluminum oxide carrier
| Sample | TA6 | TA7 | TA8 | TA9 | TA10 | TA11 | TA12 | TA13 |
| Pore volume/cm 3.g -1 | 1.82 | 1.51 | 1.68 | 1.80 | 2.00 | 1.21 | 2.10 | 2.05 |
| Specific surface/m 2.g -1 | 220 | 215 | 234 | 198 | 180 | 278 | 240 | 197 |
| Average pore diameter/nm | 33.0 | 28.0 | 29.0 | 36.0 | 44.0 | 17.0 | 35.0 | 42.0 |
| Pore size distribution, % | ||||||||
| ＜10nm | 24 | 19 | 10 | 12 | 13 | 18 | 9 | 11 |
| 10-100nm | 52 | 41 | 58 | 80 | 58 | 56 | 72 | 63 |
| ＞100nm | 22 | 40 | 32 | 3 | 29 | 24 | 9 | 28 |
| Porosity/% | 83 | 82 | 83 | 86 | 87 | 81 | 78 | 83 |
| Intensity, N/mm | 18 | 28 | 13 | 22 | 36 | 28 | 29 | 17 |
Table 2 feedstock oil character
| Density (20 ℃), g/cm 3 | 1.018 |
| ?S，wt％ | 2.56 |
| ?N，wt％ | 0.76 |
| Carbon residue, wt% | 15.6 |
Table 3 appreciation condition
| Appreciation condition | |
| Reaction temperature, ℃ | 380 |
| The hydrogen dividing potential drop, MPa | 14.7 |
| H 2/oil(v/v) | 1000 |
| LHSV，h -1 | (0.54 always) |
Table 4 desulfurization result
| Catalyst | Desulfurization degree, wt% |
| Embodiment 2 | 85 |
| Comparative Examples 2 | 82 |
Claims (23)
1. a titanium dioxide-aluminum oxide composite carrier contains the rod-like nano titanium dioxide-aluminum oxide, and the diameter of described rod-like nano titanium dioxide-aluminum oxide compound is 50nm～500nm, and length is 2～10 times of diameter, in carrier, is piled into tower structure in disorder; The physicochemical property of said titanium dioxide-aluminum oxide composite carrier is following: pore volume is 1.0～2.1ml/g, and specific surface is 180～420m
2/ g, average pore size is 10～70nm, porosity is 55%～88%.
2. according to the described carrier of claim 1, it is characterized in that the physicochemical property of described titanium dioxide-aluminum oxide composite carrier is following: pore volume is 1.3～1.8ml/g, and specific surface is 200～350m
2/ g, average pore size is 15～50nm, porosity is 75%～85%.
3. according to the described carrier of claim 1, it is characterized in that in the described titanium dioxide-aluminum oxide composite carrier that titania weight content is 2.0%～60.0%.
4. according to the described carrier of claim 1, the diameter of the rod-like nano titanium dioxide-aluminum oxide compound that it is characterized in that containing in the described titanium dioxide-aluminum oxide composite carrier is 80nm～300nm, and length is 2～10 times of diameter.
5. according to the described carrier of claim 1, it is characterized in that the weight content of described rod-like nano titanium dioxide-aluminum oxide compound in the titanium dioxide-aluminum oxide carrier is 30%～100%.
6. according to the described carrier of claim 1, it is characterized in that the weight content of described rod-like nano titanium dioxide-aluminum oxide compound in the titanium dioxide-aluminum oxide carrier is 60%～90%.
7. according to the described carrier of claim 1, it is characterized in that the pore size distribution of described titanium dioxide-aluminum oxide composite carrier is following: shared pore volume is more than 75% of total pore volume to bore dia in the hole more than the 10nm.
8. according to the described carrier of claim 1, it is characterized in that the pore size distribution of described titanium dioxide-aluminum oxide composite carrier is following: the shared pore volume in the hole of bore dia more than 10nm is 80%～94% of total pore volume.
9. according to the described carrier of claim 1, it is characterized in that the pore size distribution of described titanium dioxide-aluminum oxide carrier is adjustable in 10～1000nm scope.
10. according to the described carrier of claim 1, the crushing strength that it is characterized in that described titanium dioxide-aluminum oxide composite carrier is 6～80N/mm.
11. according to the described carrier of claim 1, the crushing strength that it is characterized in that described titanium dioxide-aluminum oxide composite carrier is 12～40N/mm.
12., it is characterized in that in the described titanium dioxide-aluminum oxide carrier that contain the component of being introduced by adhesive, its content accounts for below 70% of titanium dioxide-aluminum oxide vehicle weight according to the described carrier of claim 1.
13. the preparation method of the arbitrary said titanium dioxide-aluminum oxide composite carrier of claim 1～12 comprises the steps:
(1) preparation of nanometer titanium hydroxide-gel aluminum hydroxide,
(2) the nanometer titanium hydroxide-gel aluminum hydroxide of step (1) gained is after drying, and moulding again through drying and roasting, obtains the titanium dioxide-aluminum oxide carrier;
The described nanometer titanium hydroxide-gel aluminum hydroxide of step (1) is to adopt the preparation of the ultra solubilising micelle of fused salt method.
14., it is characterized in that the preparation method of the described nanometer titanium hydroxide-gel aluminum hydroxide of step (1) comprises according to the described method of claim 13:
A, hydrocarbon component, VB value are mixed less than 1 surfactant;
B, contain titanium hydroxide-gel aluminum hydroxide and make by following at least a method:
Method one:
Under the normal pressure, aluminium salt and titanium salt splash in the mixture of steps A gained, are mixed to form evenly ultra solubilising micelle; In above-mentioned system, add precipitating reagent and/or aqueous catalyst solution, under 50～120 ℃ of temperature, reacted 1～10 hour, aging 0～30 hour then, obtain containing titanium hydroxide-gel aluminum hydroxide;
Method two:
Aluminium salt and titanium salt are splashed in the mixture of steps A gained, be mixed to and form evenly ultra solubilising micelle; In confined conditions, below the ammonia critical-temperature, add precipitating reagent and/or catalyst liquefied ammonia; Or in confined conditions,, feed precipitating reagent and/or catalyst ammonia gas react at 30～300 ℃; Aging 0～30 hour then, obtain containing titanium hydroxide-gel aluminum hydroxide;
Method three:
Aluminium salt, titanium salt and precipitating reagent and/or catalyst are splashed in the mixture of steps A gained, be mixed to and form evenly ultra solubilising micelle; Under airtight condition, resulting mixture in 70～200 ℃ of thermotonuses 1～10 hour, aging 0～30 hour then, is obtained containing titanium hydroxide-gel aluminum hydroxide;
Wherein water can add with the crystallization water and/or free water form in steps A and/or step B;
Low mass molecule alcohol adds with pure dissolubility titanium salt and/or aluminium salt;
Weight with the mixture of step B gained is benchmark; Aluminium salt is 60.0wt%～93.0wt% in butt, titanium salt in the consumption of butt, precipitating reagent and/or catalyst, low mass molecule alcohol and water; The water yield is the 100wt%～350wt% as the theoretical water requirement of reaction water; The consumption of precipitating reagent is the 100wt%～300wt% of theoretical requirement, and the consumption of low mass molecule alcohol is 0～30wt%, and amount of surfactant is 0.1wt%～15.0wt%; The consumption of hydrocarbon component is 6.9wt%～32.0wt%.
15. according to the described method of claim 13; It is characterized in that the weight with the mixture of step B gained is benchmark; Aluminium salt is 75.0wt%～92.0wt% in butt, titanium salt in the consumption of butt, precipitating reagent and/or catalyst, low mass molecule alcohol and water; The water yield is the 100wt%～300wt% as the theoretical water requirement of reaction water; The consumption of precipitating reagent is the 100wt%～300wt% of theoretical requirement, and the consumption of low mass molecule alcohol is 0～30wt%, and amount of surfactant is 0.5wt%～12.0wt%; The consumption of hydrocarbon component is 7.5wt%～24.5wt%.
16., it is characterized in that the dry condition of the described nanometer titanium hydroxide of step (2)-gel aluminum hydroxide is following: 100～130 ℃ of baking temperatures, 1～30 hour drying time according to the described method of claim 13.
17. according to the described method of claim 13, the nanometer titanium hydroxide-gel aluminum hydroxide that it is characterized in that step (1) gained carries out step (2) then through washing weight concentration to Na ion and Fe ion all below 0.5%.
18., it is characterized in that the said forming method of step (2) adopts pressed disc method or extruded moulding method according to the described method of claim 13.
19. according to the described method of claim 18, it is characterized in that described pressed disc method process is following: with the dry powder of nanometer titanium hydroxide-gel aluminum hydroxide, putting into tablet press machine, is under 0.08～20.00MPa condition at pressure, compression molding.
20. according to the described method of claim 19; It is characterized in that in the described pressed disc method; In the dry powder of nanometer titanium hydroxide-gel aluminum hydroxide, add releasing agent, releasing agent is a carbon black, and consumption is 0.1%～5.0% of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium body weight.
21., it is characterized in that described extrusion method process is following: earlier nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binding agent are mixed according to the described method of claim 18; Again peptizing agent, water and cosolvent are mixed, be added to then in the mixture of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binding agent, stir, on batch mixer, mix moulding in banded extruder then; In the described extrusion process, controlled pressure is at 10～50MPa.
22. according to the described method of claim 21; It is characterized in that described peptizing agent is one or more in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and the sulfuric acid; Consumption is 1%～15% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight; Described hydromining is used deionized water, and consumption is 5%～100% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight; Described cosolvent is one or more in methyl alcohol, ethanol and the propyl alcohol, and consumption is 1%～15% (mass fraction) of nanometer titanium hydroxide-gel aluminum hydroxide xeraphium and binder mixtures weight; Described binding agent adopts titaniferous to intend thin water-aluminum hydroxide, and the component that its consumption is introduced binding agent finally accounts for below 70% of carrying alumina body weight.
23., it is characterized in that the drying condition after the said moulding of step (2) is following: under 100～130 ℃ of temperature, carried out drying 1～30 hour according to the described method of claim 18; An one-step baking method or substep roasting method are adopted in described roasting; A described one-step baking method condition is following: 180～1200 ℃ of roastings 4～80 hours, programming rate was 0.1～5 ℃/min; Described substep roasting method condition is following: 180～300 ℃ of roasting temperatures 1～10 hour, 500～1200 ℃ of roastings 2～60 hours, programming rate was 1～5 ℃/min.
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| CN103861658B (en) * | 2014-02-28 | 2015-12-02 | 中国海洋石油总公司 | A kind of preparation method of spherical titania-alumina mixed oxide |
| CN104353503B (en) * | 2014-11-12 | 2016-05-18 | 中国海洋石油总公司 | A kind of preparation method of spherical sial complex carrier |
| CN104353504B (en) * | 2014-11-12 | 2016-05-18 | 中国海洋石油总公司 | A kind of preparation method of spherical titanium aluminium complex carrier |
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| CN105195118A (en) * | 2015-10-12 | 2015-12-30 | 常州新日催化剂有限公司 | Macroporous structure titanium oxide desulfurization catalyst and preparation method thereof |
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| CN111686749B (en) * | 2019-03-13 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN113666402B (en) * | 2021-08-13 | 2022-07-08 | 吉林大学 | Hydroxy aluminum oxide nano material and preparation method thereof |
| CN114405493A (en) * | 2021-12-20 | 2022-04-29 | 西安凯立新材料股份有限公司 | Preparation method of high-strength large-aperture alumina-titanium oxide composite carrier |
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