CN101890376A - Titanium-silicon composite oxide carrier and preparation method thereof - Google Patents
Titanium-silicon composite oxide carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium-silicon composite oxide carrier and a preparation method thereof. The carrier is prepared from titanium hydroxide-silicon hydroxide gel prepared by a super-solubilizing micelle method; and because the gel contains surfactant and hydrocarbon components, nano titanium oxide and silicon oxide particles formed by dehydrating the polymerized titanium hydroxide and the polymerized silicon hydroxide still have a rod-like basic structure after molding and roasting, and the nano particles are randomly piled to form a framework structure. The carrier has large pore volume, large aperture, high porosity, large outer surface orifice and good pore penetrability, does not inactivate a catalyst due to orifice blockage for macromolecules in particular compared with an orifice of an ink bottle type, and is favorable for increasing the deposition of impurities and prolonging the running period of the catalyst. The carrier can be used for catalytic reaction containing macromolecular reactants or products.
Description
Technical field
The present invention relates to a kind of titanium-silicon composite oxide carrier and preparation method thereof, relate in particular to a kind of macropore titanium-silicon composite oxide 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, is subject to people's attention always.But the quality of oil becomes heavy, variation day by day in recent years, and strict more to product quality, subsequent technique is also more and more harsher to the requirement of charging.In addition, since the mankind entered 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 2000ppm, and the mid-90 is reduced to 500ppm, by 2005, requires sulfur content to be lower than 50ppm.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 to equipment requirement height, the 2nd, and cost is higher, so be not desirable way; Doubly just can reach sulfur content is lower than 50ppm then must to bring up to present 3-4 to activity with regard to catalyst.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.
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 duct concentrates on 8～15nm and reaches more than 80%, and catalyst has very high initial activity.The macroporous aluminium oxide duct is run through continuously to the residual oil molecule, but too concentrating on about 10nm-20nm of duct is to be unfavorable for the catalyst long-term operation.Beds stops up and to cause device to stop work, catalyst changeout more, and its chief reason is exactly: the concentrated duct of the used macroporous aluminium oxide of catalyst carrier is stopped up by metal and carbon residue and is become 10nm when following at present, and big molecule can't be penetrated into inside, duct in the residual oil.
Containing a large amount of nitrogen in the residual oil is 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.At the residual oil combination catalyst,, make big molecule asphalitine partial crushing form little asphalitine micelle even before residual hydrogenation denitrogenation, removal of ccr by hydrotreating catalyst, Hydrodemetalation catalyst is arranged.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 enter 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.
At present, adopt the compound carrier of two or more oxides to improve the performance of catalyst carrier as catalyst.CN1316486A discloses a kind of preparation method of nanometer titanium-silicon composite oxide carrier of hydrogenation, this method is used technology such as sol-gel process and supercritical drying, prepare high-ratio surface, the titanium silicon complex of 2-40nm, it is raw material that its shortcoming has been to use the more expensive alkoxide of price, and the aperture is less.CN 1210759A discloses a kind of preparation method who is used for the benzene hydrogenating catalyst carrier, utilizes the particle diameter 1-2.5nm of the Ti-Si composite oxide that sol-gel process prepares to account for 72%, is not mesoporous material, and the scope of application is narrower, and the aperture is too little.
Summary of the invention
At weak point of the prior art, the invention provides a kind of good to big molecular diffusion performance, hold strong titanium-silicon composite oxide carrier of impurity ability and preparation method thereof.
Titanium-silicon composite oxide carrier of the present invention, contain rod-like nano titania-silica composite oxides in the described carrier, the diameter of described rod-like nano titania-silica composite oxides is 50nm～350nm, preferred 80nm～300nm, and length is 2～10 times of diameter.Described rod-like nano titania-silica composite oxides are piled into tower structure in disorder in titanium-silicon composite oxide carrier, make carrier form large pore volume, the large aperture, and macropore duct connectivity is good, and the aperture is bigger, helps macromolecular diffusion.
The weight content of described rod-like nano titania-silica composite oxides in titanium-silicon composite oxide carrier is 30%～98%, is preferably 60%～90%.
The physicochemical property of described titanium-silicon composite oxide carrier is as follows: pore volume is 1.0～3.2ml/g, is preferably 1.1～2.3ml/g, and specific surface is 180～450m
2/ g is preferably 200～429m
2/ g, average pore size is 12～80nm, is preferably 15～60nm, porosity is 60%～93%, is preferably 80%～93%.
The said porosity of the present invention is the porosity of the particle inner duct that records with mercury injection method.
In the described titanium-silicon composite oxide carrier, the weight content of titanium oxide is 7%～70%, and the weight content of silica is 30%～93%.
The pore size distribution of described titanium-silicon composite oxide carrier is as follows: shared pore volume is more than 75% of total pore volume to bore dia in the hole more than the 10nm, is preferably 80%～94%.The pore size distribution of titanium-silicon composite oxide carrier of the present invention is adjustable controlled in 10～300nm scope, the concrete pore size distribution of described titanium-silicon composite oxide carrier can determine according to concrete application, generally selects according to the molecular size and the existence of institute's raw material to be processed and generation product.
The crushing strength of described titanium-silicon composite oxide carrier is 6～80N/mm, is preferably 12～40N/mm.
In the described titanium-silicon composite oxide carrier, can contain the component of being introduced by adhesive, its content accounts for below 65% of carrying alumina body weight, is preferably below 40%, such as little porous aluminum oxide and/or macroporous aluminium oxide.
Can also contain conventional auxiliary agent in the titanium-silicon composite oxide carrier of the present invention, as in boron, zirconium, phosphorus and the fluorine one or more.
In the titanium-silicon composite oxide carrier of the present invention, weight with titanium-silicon composite oxide carrier is benchmark, auxiliary agent is 0.5%～30.0% in the content of oxide, being preferably boron oxide content is 0.5%～10.0%, phosphorous oxide content is 0.5%～10.0%, zirconia content is 0.5%～15.0%, and fluorine is 0.5%～5.0% in element content.
The preparation method of titanium-silicon composite oxide carrier of the present invention comprises the steps:
(1) preparation nanometer titanium silicon complex hydroxide gel,
(2) material that obtains of step (1) after drying, through moulding, drying and roasting obtain titanium-silicon composite oxide carrier of the present invention.
The described nanometer titanium of step of the present invention (1) silicon complex hydroxide gel is to adopt the super solubilising micelle of fused salt method to prepare, and such as disclosed method in 200510046480.6, also can adopt following method of the present invention, specifically comprises the steps:
A, hydrocarbon component, VB value are mixed less than 1 surfactant;
B, in the presence of the mixture of steps A gained, the reaction of titanium source and silicon source and precipitating reagent obtains containing the gel of nanometer titanium silicon complex hydroxide, is specifically made by following a kind of method at least:
Method one:
Titanium source and/or silicon source slowly join in the mixture of steps A gained, are mixed to form evenly super solubilising micelle; Again remainder titanium source and/or silicon source are added drop-wise in the above-mentioned system; Add precipitating reagent then in above-mentioned system, 80 ℃～120 ℃ were carried out precipitation reaction 4～30 hours, obtained the nanometer titanium silicon complex hydroxide micelle that contains of the present invention;
Method two:
With titanium source and/or silicon source and precipitant mix evenly after, be heated to fusion, slowly join in the mixture of steps A gained then, be mixed to and form evenly super solubilising micelle, again with remainder titanium source/or the silicon source be added drop-wise in the above-mentioned system; Under airtight condition, under 70 ℃～200 ℃, carry out the homogeneous precipitation reaction, the reaction time is 2～8 hours, aging 0～30 hour then, obtains containing nanometer titanium silicon complex hydroxide micelle;
Titanium source described in the step B is one or more in titanium trichloride, titanium tetrachloride, titanium tetrabromide, titanyl sulfate, titanyl nitrate, titanium sulfate, Titanium Nitrate, titanium tetrafluoride and the titanium tetra iodide.Silicon source described in the step B is one or both in Ludox, ethyl orthosilicate (TEOS) and the positive silicic acid propyl ester.
Wherein titanium source and organosilicon source (ethyl orthosilicate (TEOS) and/or positive silicic acid propyl ester) adopts the form of alcoholic solution to add in titanium source and the silicon source, being about to titanium source and organosilicon source is dissolved in the low mass molecule alcohol earlier, join then in the system, the silicon source directly is added drop-wise in the system when adopting Ludox.Among the present invention, water can add in the arbitrary steps before forming super solubilising micelle, can together add with titanium source and/or silicon source, also can add separately.
Weight with step B gained mixture is benchmark, the consumption of silicon source (butt), titanium source (butt), precipitating reagent, water and low mass molecule alcohol is 60.0%～90.0%, the consumption of surfactant is 0.1%～6.0%, better is 0.5%～4.0%, preferably 0.8%～2.0%; The consumption of hydrocarbon component is 3.0%～30.0%, better is 3.0%～15.0%, preferably 4.0%～8.0%.
Described precipitating reagent is selected from one or more in NaOH, potassium hydroxide, ammonia, ammonium carbonate, potash, sodium carbonate, sodium acid carbonate, carbonic hydroammonium, urea, hexamethylenetetramine and the ammonium citrate.Wherein method one described precipitating reagent can be in NaOH, ammonia, potassium hydroxide, ammonium carbonate, potash, sodium carbonate, sodium acid carbonate, carbonic hydroammonium and the ammonia one or more, and the described precipitating reagent of method two can be in ammonium carbonate, potash, sodium carbonate, sodium acid carbonate, carbonic hydroammonium, urea, hexamethylenetetramine and the ammonium citrate one or more.
The described low mass molecule alcohol of the inventive method is a kind of or mixture of methyl alcohol, ethanol, propyl alcohol and butanols;
The used VB value of the present invention is the water-in-oil type surfactant less than 1 surfactant.Relevant VB value notion please refer to " A Study of Identifying Emulsion Type of Surfactant--Volume Balance Value " paper that this patent people is published in the Journal of colloid and interface science fourth phase in 2002.The VB value is a kind of constant of hydrophilic and oleophilic performance of more effective judgement surfactant than the HLB value, both have following difference: 1) the VB value of HLB value 3-6 water-in-oil type surfactant is less than 1, but the HLB to many surfactants is difficult for measuring, many surfactants do not have the HLB value, and any surfactant all can directly calculate the VB value according to the chemical constitution of surfactant; 2) some HLB value can form water-in-oil emulsion about 10, and the VB value is 1 to be boundary, determines its oleophylic or hydrophily.The VB value is an oil soluble surfactant less than 1; The VB value is the water soluble surfactant active greater than 1.The used surfactant of the present invention is selected from SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride, two sweet esters, ethylene glycol monostearate, the diglycol monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl maleic acid diethylene glycol (DEG) ester, polyisobutenyl maleic acid triethyleneglycol ester, polyisobutenyl maleic acid MEA ester, polyisobutenyl maleic acid diethanol amine ester, polyisobutenyl maleic acid triethanolamine ester, the two succimides of hanging of T-152, the two succimides of hanging of T-154, the single succimide of hanging of T-151, T-153 are hung succimide and T-155 more and are hung in the succimide one or more more.
The employed hydrocarbon component of steps A is one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetable oil, animal oil.Wherein vacuum distillate is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more mixture of the dewaxing of four line distillates or wax-containing distillate, can come from paraffinic base, intermediate base or naphthene base crude; The decompression slack wax is vacuum 1st side cut distillate, second line of distillation distillate, subtracts three-way distillate, subtracts one or more slack waxs that obtain in the four line distillates, as being the second line of distillation slack wax, subtracting three-way slack wax, subtracting four line slack waxs and composition thereof; The residual oil slack wax is frivolous coal tar and/or heavy deasphalting slack wax; Deasphalted oil is frivolous coal tar and/or heavy deasphalted oil.Vegetable oil is one or more in soya-bean oil, peanut oil, rape seed oil, castor oil, sunflower oil, coconut oil and the palm oil; Animal oil is one or more in butter, sheep oil and the lard.
Also can be in surfactant with cosurfactant, the effect of cosurfactant can reduce the consumption of surfactant, can form more stable complexed surfactant film, helps the stability of surfactant film.Cosurfactant comes from one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, odium stearate, enuatrol, potassium stearate, potassium oleate, lecithin, phosphoric acid fat, AEO (10), aliphatic acid polyethenoxy ether (15), APES (7), aliphatic amine polyoxyethylene ether (15), polyethylene glycol (400), tall oil acid amides, dodecyl sodium sulfate and the dodecyl alcohol acyl phosphate.
Before step of the present invention (2) the titaniferous silicon complex hydroxide gel drying, preferably, remove impurity earlier through washing.Washing process is as follows: at first use organic solvent such as ethanol or acetone, washed product 1～3 time.
Titaniferous silicon complex hydroxide gel drying described in the step (2) can adopt the supercritical fluid extraction dry technology, is preferably ethanol, CO
2The supercritical fluid extraction dry technology.
The described forming method of step (2) can adopt the extruded moulding method, process is as follows: nanometer titanium silicon complex hydroxide gel, binding agent, peptizing agent, water and cosolvent are mixed, this process can adopt conventional charging sequence, preferably nanometer titanium silicon complex hydroxide gel, binding agent is mixed; Peptizing agent, water and cosolvent are mixed, be added to then in the mixture of nano-aluminum hydroxide gel and binding agent, 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 0.1%～20% (mass fraction) of nanometer titanium silicon complex hydroxide gel drying powder and binder mixtures weight, described water preferably adopts deionized water, consumption is 5%～100% (mass fraction) of nanometer titanium silicon complex hydroxide xeraphium and binder mixtures weight, preferred 20%～70%.Peptization course also needs to add cosolvent, and cosolvent is one or more in methyl alcohol, ethanol and the propyl alcohol, and consumption is 1%～20% (mass fraction) of nanometer titanium silicon complex hydroxide gel drying powder and binder mixtures weight.
Described binding agent preferably adopts intends thin water-aluminum hydroxide, intending thin water-aluminum hydroxide can be that macropore is intended thin water-aluminum hydroxide, also can be that aperture is intended thin water-aluminum hydroxide, the component that its consumption is introduced binding agent finally accounts for below 65% of carrying alumina body weight, is preferably 5%～40%.
Drying condition after the described moulding is as follows: carried out drying 1～30 hour under 100～130 ℃ of temperature.Described roasting can be adopted a conventional one-step baking method, condition was as follows: 180～1200 ℃ of roastings 4～80 hours, programming rate is 0.1～5 ℃/min, preferably divide one-step baking, condition was as follows: 180～300 ℃ of roasting temperatures 1～10 hour, 500～1200 ℃ of roastings 2～60 hours, programming rate was 1～5 ℃/min.
Can also contain conventional auxiliary agent in the titanium-silicon composite oxide carrier of the present invention, as in boron, zirconium, phosphorus and the fluorine one or more.Described auxiliary agent is introduced carrier fashion can adopt conventional method, such as introducing with nanometer titanium silicon complex hydroxide gel mixing method; The preparation titanium-silicon composite oxide carrier adopts infusion process to introduce then earlier; Also can adopt above-mentioned two kinds of methods respectively to introduce part of auxiliary.
Titanium-silicon composite oxide carrier of the present invention is that the hydroxide gel that adopts super solubilising micelle method to obtain is a raw material, and roasting obtains after moulding.Because super solubilising method is to adopt VB value less than the reversed phase micelle that 1 surfactant forms, and obtains unique super solubilising nanometer " reactor ", the nano particle process self assembly of reaction generation obtains the titanium silicon complex hydroxide gel of club shaped structure.Owing to contain surfactant and hydrocarbon component in the titanium silicon complex hydroxide gel, in forming process, still can keep club shaped structure, and in high-temperature calcination process, surfactant is progressively deviate from, surfactant still has the carrying out that reaction is being controlled in self assembly during this, makes the hydroxide of polymerization deviate from the nano-titanium oxide and the monox composite oxides particle that form behind the moisture and still has bar-shaped basic structure.Bar-shaped nano-titanium oxide and monox composite oxides be unordered being deposited in together mutually, the frame structure that forms does not have fixing outer surface, 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 the template agent in carrier, make titanium-silicon composite oxide 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-silicon composite oxide carrier by the size of this organic moiety amount.
Conventional method is not owing to there is the template agent, 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 agent during moulding, the factor of pressure will not have the effect that destroys duct and pore volume, peptization acid can be deviate from Ti-Si composite oxide and binding agent very secure bond the frame structure that forms after the template agent and just can keep very high intensity together like this.
The hydrocarbon component that contains in the titanium silicon complex 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 super 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, hydrocarbon component in the huge mixing lipophilic group under pressure, depend merely on and be not enough to be kept in the hydroxide particle of nanometer self assembly with the interaction of surfactant lipophilic group, 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-silicon composite oxide carrier is formed from nanometer to micron-sized different frames structure pore.
The titanium-silicon composite oxide carrier of the inventive method gained can be used for handling to contain containing macromolecular course of reaction in big molecular raw material or the product,, alkene oligomerization saturated, catalytic reforming, hydrogenation dearomatization, Aromatizatian catalytic agent carrier such as hydrofinishing, hydrocracking, isomerization, alkylation, catalytic cracking, alkene, be especially suitable for use as hydrofining catalyst carrier, especially the carrier of Hydrobon catalyst.
Description of drawings
Fig. 1 is ESEM (SEM) figure of embodiment 1 gained titanium-silicon composite oxide carrier of the present invention.
The specific embodiment
The present invention is further described below in conjunction with 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.
Embodiment 1
The heating of 40g Ludox, 240g urea is mixed, slowly add in 90 ℃ the mixture of 105g second line of distillation distillate, 20g polyisobutenyl maleic acid triethanolamine ester, and under this temperature, mixed 10 minutes.The 149g titanium tetrachloride is dissolved in the 200ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-1 of the present invention.
Embodiment 2
The 66g ethyl orthosilicate is dissolved in the 85g ethanol, adds the heating of 74g urea mix for 75 ℃, slowly add in 75 ℃ the mixture of 70g second line of distillation distillate, 12g polyisobutenyl maleic acid triethanolamine ester, and under this temperature, mixed 10 minutes.The 126g titanium tetrachloride is dissolved in the 120ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-2 of the present invention.
Embodiment 3
The heating of 100g Ludox, 160g urea is mixed in the mixture of 49g second line of distillation distillate, 15g polyisobutenyl maleic acid triethanolamine ester of 90 ℃ of slow addings, and under this temperature, mixed 10 minutes.The 94.4g titanium tetrachloride is dissolved in the 100ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-3 of the present invention.
Embodiment 4
The heating of 134g Ludox, 120g urea is mixed in the mixture of 35g second line of distillation distillate, 12g polyisobutenyl maleic acid triethanolamine ester of 90 ℃ of slow addings, and under this temperature, mixed 10 minutes.The 61.5g titanium tetrachloride is dissolved in the 80ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-4 of the present invention.
Embodiment 5
The heating of 150g Ludox, 80g urea is mixed in the mixture of 30g second line of distillation distillate, 10g polyisobutenyl maleic acid triethanolamine ester of 90 ℃ of slow addings, and under this temperature, mixed 10 minutes.The 47.2g titanium tetrachloride is dissolved in the 60ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-5 of the present invention.
Embodiment 6
The heating of 174g Ludox, 40g urea is mixed in the mixture of 25g second line of distillation distillate, 8g polyisobutenyl maleic acid triethanolamine ester of 90 ℃ of slow addings, and under this temperature, mixed 10 minutes.The 24.5g titanium tetrachloride is dissolved in the 40ml ethanol, adds then in the above-mentioned micelle, mix.Under 120 ℃ of temperature, keep temperature, pressure, reacted 6 hours.Reaction is washed with distilled water to no anion, centrifugation after finishing.Following dry 10 hours at 100 ℃ at last.Nanometer titanium hydroxide-silicon hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.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 alumina support TS-6 of the present invention.
The performance of table 1 embodiment 1-6 titania-silica complex carrier
| Sample | TS-1 | TS-2 | TS-3 | TS-4 | TS-5 | TS-6 |
| Pore volume/cm 3.g -1 | 1.9 | 1.68 | 1.54 | 1.37 | 1.19 | 1.1 |
| Specific surface/m 2.g -1 | 223 | 210 | 220 | 228 | 226 | 231 |
| Average pore diameter/nm | 34 | 32 | 28 | 24 | 21 | 19 |
| Pore size distribution, % | ||||||
| ＜10nm | 6 | 8 | 9 | 11 | 12 | 15 |
| 10-100nm | 68 | 70 | 70 | 71 | 73 | 73 |
| ＞100nm | 32 | 24 | 21 | 18 | 15 | 12 |
| Bulk density/g.cm -3 | 0.29 | 0.31 | 0.33 | 0.35 | 0.39 | 0.41 |
| Porosity/% | 93 | 91 | 90 | 88 | 86 | 80 |
| Intensity, N/mm | 12 | 15 | 18 | 22 | 19 | 32 |
Claims (17)
1. titanium-silicon composite oxide carrier, wherein contain rod-like nano titania-silica composite oxides, in titanium-silicon composite oxide carrier, be piled into tower structure in disorder, the diameter of described rod-like nano titania-silica composite oxides is 50nm～350nm, and length is 2～10 times of diameter.
2. according to the described carrier of claim 1, it is characterized in that the weight content of described rod-like nano titania-silica composite oxides in titanium-silicon composite oxide carrier is 30%～98%.
3. according to the described carrier of claim 1, it is characterized in that the physicochemical property of described titanium-silicon composite oxide carrier is as follows: pore volume is 1.0～3.2ml/g, and specific surface is 180～450m
2/ g, average pore size is 12～80nm, porosity is 60%～93%.
4. according to the described carrier of claim 1, it is characterized in that the physicochemical property of described titanium-silicon composite oxide carrier is as follows: pore volume is 1.1～2.3ml/g, and specific surface is 200～429m
2/ g, average pore size is 15～60nm, porosity is 80%～93%.
5. according to the described carrier of claim 1, it is characterized in that in the described titanium-silicon composite oxide carrier that the weight content of titanium oxide is 7%～70%, the weight content of silica is 30%～93%.
6. according to the described carrier of claim 1, it is characterized in that the pore size distribution of described titanium-silicon composite oxide carrier is as follows: shared pore volume is more than 75% of total pore volume to bore dia in the hole more than the 10nm.
7. according to the described carrier of claim 1, the crushing strength that it is characterized in that described titanium-silicon composite oxide carrier is 6～80N/mm.
8. according to the described carrier of claim 1, it is characterized in that in the described titanium-silicon composite oxide carrier, containing in auxiliary agent boron, zirconium, phosphorus and the fluorine one or more, is benchmark with the weight of titanium-silicon composite oxide carrier, and auxiliary agent is 0.5%～30.0% in the content of oxide.
9. the preparation method of the arbitrary described carrier of claim 1～7 comprises the steps:
(1) preparation nanometer titanium silicon complex hydroxide gel,
(2) material that obtains of step (1) after drying, through moulding, drying and roasting obtain titanium-silicon composite oxide carrier of the present invention;
The described nanometer titanium of step (1) silicon complex hydroxide gel is to adopt the preparation of the super solubilising micelle of fused salt method.
10. in accordance with the method for claim 9, it is characterized in that the preparation process of the described nanometer titanium of step (1) silicon complex hydroxide gel is as follows:
A, hydrocarbon component, VB value are mixed less than 1 surfactant;
B, the gel that contains nanometer titanium silicon complex hydroxide are made by following a kind of method at least:
Method one:
Titanium source and/or silicon source slowly join in the mixture of steps A gained, are mixed to form evenly super solubilising micelle; Again remainder titanium source and/or silicon source are added drop-wise in the above-mentioned system; Add precipitating reagent then in above-mentioned system, 80 ℃～120 ℃ were carried out precipitation reaction 4～30 hours, obtained the nanometer titanium silicon complex hydroxide micelle that contains of the present invention;
Method two:
With titanium source and/or silicon source and precipitant mix evenly after, be heated to fusion, slowly join in the mixture of steps A gained then, be mixed to and form evenly super solubilising micelle, again with remainder titanium source/or the silicon source be added drop-wise in the above-mentioned system; Under airtight condition, under 70 ℃～200 ℃, carry out the homogeneous precipitation reaction, the reaction time is 2～8 hours, aging 0～30 hour then, obtains containing nanometer titanium silicon complex hydroxide micelle;
Titanium source described in the step B is one or more in titanium trichloride, titanium tetrachloride, titanium tetrabromide, titanyl sulfate, titanyl nitrate, titanium sulfate, Titanium Nitrate, titanium tetrafluoride and the titanium tetra iodide; Silicon source described in the step B is one or both in Ludox, ethyl orthosilicate and the positive silicic acid propyl ester;
Wherein titanium source and organosilicon source adopt the form of alcoholic solution to join in the system, and the silicon source directly is added drop-wise in the system when adopting Ludox; Wherein add in the arbitrary steps of water before forming super solubilising micelle;
Weight with step B gained mixture is benchmark, the consumption of silicon source (butt), titanium source (butt), precipitating reagent, water and low mass molecule alcohol is 60.0%～90.0%, the consumption of surfactant is 0.1%～6.0%, and the consumption of hydrocarbon component is 3.0%～30.0%.
11. in accordance with the method for claim 10, it is characterized in that the weight with step B gained mixture is benchmark, the consumption of surfactant is 0.5%～4.0%, and the consumption of hydrocarbon component is 3.0%～15.0%.
12. in accordance with the method for claim 10, it is characterized in that described low mass molecule alcohol is a kind of or mixture of methyl alcohol, ethanol, propyl alcohol and butanols.
13. in accordance with the method for claim 10, it is characterized in that the titanium source described in the step B is one or more in titanium trichloride, titanium tetrachloride, the titanium tetrabromide; Silicon source described in the step B is a Ludox.
14. in accordance with the method for claim 10, it is characterized in that before step of the present invention (2) the titaniferous silicon complex hydroxide gel drying that through washing, process is as follows earlier: with organic solvent ethanol or acetone, washed product 1～3 time.
15. in accordance with the method for claim 10, it is characterized in that the described forming method of step (2) adopts the extruded moulding method, process is as follows: nanometer titanium silicon complex hydroxide gel, binding agent, peptizing agent, water and cosolvent are mixed moulding in banded extruder then; In the described extrusion process, controlled pressure is at 10～50MPa.
16. in accordance with the method for claim 15, it is characterized in that described peptizing agent is an acetic acid, formic acid, nitric acid, hydrochloric acid, in phosphoric acid and the sulfuric acid one or more, consumption is 0.1%～20% (mass fraction) of nanometer titanium silicon complex hydroxide gel drying powder and binder mixtures weight, the consumption of described water is 5%～100% (mass fraction) of nanometer titanium silicon complex hydroxide xeraphium and binder mixtures weight, cosolvent is a methyl alcohol, in ethanol and the propyl alcohol one or more, consumption are 1%～20% (mass fraction) of nanometer titanium silicon complex hydroxide gel drying powder and binder mixtures weight; Described binding agent adopts intends thin water-aluminum hydroxide, and the component that its consumption is introduced binding agent finally accounts for 5%～65% of carrying alumina body weight.
17. in accordance with the method for claim 9, it is characterized in that the drying condition after the described moulding is as follows: under 100～130 ℃ of temperature, carried out drying 1～30 hour.An one-step baking method is adopted in described roasting, condition was as follows: 180～1200 ℃ of roastings 4～80 hours, programming rate is 0.1～5 ℃/min, perhaps adopt and divide one-step baking, condition was as follows: 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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| CN103861574A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing titanium-silicon composite oxide |
| CN115448316A (en) * | 2022-09-21 | 2022-12-09 | 江西联锴科技有限公司 | Preparation method of large-aperture spherical silicon dioxide |
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| CN1112240C (en) * | 2000-10-26 | 2003-06-25 | 中国石油化工股份有限公司 | Macroreticular alumina carrier containing Si and Ti and its preparing process |
| CN1782032A (en) * | 2004-12-01 | 2006-06-07 | 中国石油天然气股份有限公司 | Process for preparing diesel oil hydrog-refining catalyst using TiO2-SiO2 compound oxide as carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103861574A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing titanium-silicon composite oxide |
| CN103861574B (en) * | 2014-02-28 | 2015-11-04 | 中国海洋石油总公司 | A kind of preparation method of Ti-Si composite oxide |
| CN115448316A (en) * | 2022-09-21 | 2022-12-09 | 江西联锴科技有限公司 | Preparation method of large-aperture spherical silicon dioxide |
| CN115448316B (en) * | 2022-09-21 | 2024-02-27 | 江西联锴化学有限公司 | Preparation method of large-aperture spherical silicon dioxide |
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