CN100345763C - Nano compound oxide preparation method - Google Patents
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- CN100345763C CN100345763C CNB2005100464806A CN200510046480A CN100345763C CN 100345763 C CN100345763 C CN 100345763C CN B2005100464806 A CNB2005100464806 A CN B2005100464806A CN 200510046480 A CN200510046480 A CN 200510046480A CN 100345763 C CN100345763 C CN 100345763C
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Abstract
The present invention discloses a method for preparing nano compound oxide. Fusant can be solubilized in mixture of hydrocarbon components and surface active agents to form ultra-solubilization micelles for coating the fusant by oil. Fusant and precipitation agents in the micelles carry out reaction in situ to generate hydroxide which is limited in the micelles, which avoids increasing the particle diameter. Then, the hydroxide is baked to prepare nano compound oxide. The method of the present invention has the advantages of little dosage of the surface active agents and the hydrocarbon components, low cost, monodisperse states of the micelles, narrow particle size distribution range, high product yield, simple manufacturing technology and industrial production of large batch. The nano compound oxide prepared by the present invention has large specific surface area and large pore volume, and especially serves as catalyst carriers.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite oxide, relate in particular to a kind of preparation method who is used for the nano composite oxide of support of the catalyst.
Background technology
Hydrogenating desulfurization is the important process process in the Ammonia Production of raw material as refining of petroleum 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 quality product, 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 aromaticity content is harsh more.The sulphur content of initial stage nineties European diesel standard is 2000ppm, and the mid-90 is reduced to 500ppm, is 350ppm at present, by 2005, requires sulphur content to be lower than 50ppm.Based on above reason, the hydrogenating desulfurization technology of gasoline and diesel oil just develops towards the cleaning oil fuel direction of processing high-sulfur oils and production super low sulfur.With present appointed condition, conventional hydrofining is difficult to reach the requirement of ultra-deep desulfurization, and in order to reduce sulphur content, the reaction parameter that only changes is as improving H
2Pressure, reduce air speed, improve temperature of reaction etc.But this method one is to the equipment requirements height, the 2nd, and cost is higher, so be not the ideal way; Doubly just can reach sulphur content is lower than 50ppm then must to bring up to present 3-4 to activity with regard to catalyzer.Therefore, press for the requirement that catalyzer 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 support of the catalyst is carried out modification, and therefore, many investigators focus on carrier is furtherd investigate.
At present, adopt the compound carrier of two or more oxide compounds to improve the performance of support of the catalyst as catalyzer.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 method and supercritical drying, prepare high-ratio surface, the titanium silicon complex body of 2-40nm, it is raw material that its shortcoming has been to use the more expensive alkoxide of price.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 method prepares to account for 72%, is not mesoporous material, and the scope of application is narrower.
The existing method for preparing nano-oxide particles mainly is the precipitator method.Because the distinctive shortcoming of the precipitator method itself, promptly the particle diameter of nano-oxide is wayward, and distribution range is wide, easily reunites etc.CN 1192991A discloses a kind of employing Preparation by Uniform Precipitation nano zine oxide method, utilizes urea to do the precipitation from homogeneous solution agent, but hydrolysis temperature height (122～126 ℃), the easy polymerization of urea need be carried out in autoclave, and the production control difficulty is big, yield poorly, still do not solve agglomeration traits.CN 1334243A discloses the method that reverse micro emulsion prepares nano zircite, and the consumption of required tensio-active agent, hydro carbons and water is big in this method, and output is extremely low, and the shortcoming of separation difficulty.
Summary of the invention
For overcoming weak point of the prior art, the preparation method of the nano composite oxide that the invention provides that a kind of nanometer particle size is easy to control, particle size distribution range is narrow, productive rate is high, tensio-active agent and hydrocarbon component consumption is little.
The contriver finds through a large amount of experiments, melts can be solubilized in hydrocarbon component and the water-in-oil-type surfactant mixtures, form super solubilising nanometer micelle, carry out the control reaction of restricted in-situ nano micelle with the nanometer micelle, reaction, the weathering process of melts and precipitation agent are all carried out in the nanometer micelle, limit growing up of micelle, formed the micelle that contains nanometer oxyhydroxide, after roasting, formed nano-oxide again.
Based on above-mentioned design, the preparation method of nano composite oxide of the present invention, wherein composite oxides comprise two kinds of different oxide compounds at least, comprise the steps:
(1) hydrocarbon component, VB value are mixed less than 1 tensio-active agent and cosurfactant;
(2) micelle that contains nanometer oxyhydroxide is made by one of following method:
Method one:
Under normal pressure, the inorganic melts of fused is slowly joined in the mixture of step (1) gained, be mixed to and form evenly super solubilising micelle; In above-mentioned system, add precipitation agent, carry out precipitin reaction; Aging 0～30 hour then, obtain the nanometer oxyhydroxide micelle that contains of the present invention.
Method two:
The inorganic melts of fused is slowly joined in the mixture of step (1) gained, make it form evenly super solubilising micelle; In confined conditions, below the ammonia critical temperature, the critical temperature of preferred 30 ℃～ammonia, precipitation agent liquefied ammonia is joined in the above-mentioned system, or in confined conditions, at 30～300 ℃, ammonia is fed in the above-mentioned system, carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
Method three:
After precipitation agent and all or part of inorganic melts mixed, be heated to fusion, slowly join then in the mixture of step (1) gained, be mixed to and form evenly super solubilising micelle, the more inorganic melts of remainder is added in the above-mentioned system; Under airtight condition, under 70～200 ℃, carry out the precipitation from homogeneous solution reaction, the reaction times is 2～8 hours, aging 0～30 hour then, obtains containing nanometer oxyhydroxide micelle.
Method four:
The inorganic melts of fused slowly adds in the mixture of step (1) gained, is mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; Under airtight condition, add precipitation agent, under 50～120 ℃ of temperature, carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
Method five:
The inorganic melts of fused slowly adds in the mixture of step (1) gained, is mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; In confined conditions, below the ammonia critical temperature, add precipitation agent liquefied ammonia, or in confined conditions,, feed ammonia and carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle at 30～300 ℃;
Method six:
After inorganic melts and precipitant mix were even, heating and melting slowly joined in the mixture of step (1) gained, was mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; Under airtight condition, resulting mixture is carried out the precipitation from homogeneous solution neutralization reaction under 70～200 ℃ of temperature, in 4～8 hours reaction times, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
(3) with step (2) gained contain nanometer oxyhydroxide micelle through roasting, obtain nano composite oxide.
Wherein water can add with crystal water and/or free-water form in step (1) and/or step (2).
Wherein, the nano combined hydroxide gel of step (2) gained can through the described calcination steps of step (3), obtain the nano level composite oxides more earlier after washing, oven dry.
Among the present invention, inorganic melts can be a kind of material, mixture that also can multiple material.Inorganic melts is preferably selected the inorganic salt that contain crystal water or do not contain crystal water for use.Wherein said inorganic melts comes from two or more in aluminium source, magnesium source, lanthanum source, the calcium source, the combination in perhaps at least a titanium source, zirconium source, source of iron, manganese source and at least a aluminium source, magnesium source, lanthanum source, calcium source, the combination in perhaps at least a aluminium source, magnesium source, lanthanum source, titanium source, zirconium source, source of iron, manganese source, calcium source and at least a silicon source, phosphorus source and boron source.Wherein the aluminium source is selected from one or more in aluminum nitrate, Tai-Ace S 150, the aluminum chloride; The titanium source is selected from one or more in titanous chloride, titanium tetrachloride, chlorination oxygen titanium and the titanyl sulfate; The zirconium source is selected from one or more in zirconium oxychloride, the zirconium nitrate; Source of iron is selected from one or more in iron nitrate, Iron nitrate, iron(ic) chloride, ferric sulfate and the ferrous sulfate; The magnesium source is selected from one or more in magnesium nitrate, magnesium chloride and the sal epsom; The lanthanum source is selected from Lanthanum trichloride; The calcium source is selected from calcium chloride and/or nitrocalcite; The manganese source is selected from one or more in manganous nitrate, Manganous chloride tetrahydrate, manganese sulfate and the permanganic anhydride; The silicon source is selected from silicon sol; The phosphorus source is selected from one or more in phosphoric acid, metaphosphoric acid, the Tripyrophosphoric acid; The boron source is selected from boric acid.
The fusing point of the inorganic melts of described low melting point is-100 ℃～50 ℃, such as titanous chloride, titanium tetrachloride and six platinum chlorides.
In the present invention, can adopt aqueous inorganics, but will guarantee that the Total Water in the whole system satisfies the Total Water that the present invention requires.This moment, aqueous inorganics was considered as the alleged inorganic melts of the present invention.Aqueous inorganics is except the inorganic salt that contain crystal water, also has the aqueous solution or colloidal sol, such as the silicon sol in the used silicon source, though contain a large amount of water in the silicon sol, but as long as can guarantee that the Total Water in the whole system satisfies the Total Water that the present invention requires, can be considered as inorganic melts in the present invention,, can adopt the method for removing portion water earlier to satisfy requirement of the present invention if when institute's water content exceeds the Total Water of requirement of the present invention in the used silicon sol.The aqueous inorganics of this kind is particularly suitable for that the form with the inorganic melts of low melting point joins in the system in method four, method five and the method six, except silicon sol, the moisture inorganics that also has other is such as high concentrations of phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid, boric acid etc.
Weight with the mixture of step (2) gained is benchmark, the consumption of melts (butt), precipitation agent and water is 60wt%～95wt%, be preferably 80wt%～95wt%, the water yield is the 100wt%～350wt% as the theoretical water requirement of reaction water, be preferably 100wt%～300wt%, most preferably be 100wt%～200wt%, the consumption of precipitation agent is the 100wt%～300wt% of theoretical requirement, the consumption of tensio-active agent is 0.1wt%-8wt%, better be 0.5wt%-4wt%, preferably 0.8wt%-2wt%; The consumption of hydrocarbon component is 3wt%～30wt%, better is 3wt%～15wt%, preferably 4wt%～8wt%; The consumption of cosurfactant is 0～2wt%, better is 0～1wt%, preferably 0～0.5wt%.
The theoretical requirement of precipitation agent is meant to be had in the presence of enough reaction water, makes inorganics just in time generate the weight of the required precipitation agent of corresponding oxyhydroxide fully.
Owing to will make the reaction of melts and precipitation agent generate precipitation of hydroxide, need water and participate in chemical reaction, stoichiometric water is that reaction is desired.Contain the inorganics of crystal water for great majority, the chemically combined water of crystallization of itself has satisfied and has formed the oxyhydroxide requirement, for the low or water-free melts of crystal water content, needs to add enough reaction water.Theoretical water requirement as reaction water is meant under the certain situation of inorganic melts amount, inorganic melts is precipitated fully generate the required water yield of corresponding oxyhydroxide.Water can adopt following one or more modes to add: a, add entry in step (1), b, adopt the form of the inorganic salt that contain crystal water to add in step (2), c, add entry in the melts melting process.The adding mode of water is not limited to aforesaid way, adopt the precipitation agent aqueous solution such as method one and method four, can also form at the mixture of inorganic molten salt and step (1) gained in method one, method two, method four and the method five in the even colloidal process and to add or to add after forming even colloid, method three and method six also can form at the mixture of melts and precipitation agent eutectic and step (1) gained in the even colloidal process or behind the even colloid of formation and add or the like.Method one and method four preferably adopt the precipitation agent aqueous solution, and contain the inorganic salt of crystal water and/or add entry in the melts melting process; Method two, method three, method five and method six preferably adopt the inorganic salt that contain crystal water and/or add entry in the melts melting process.
In the step of the present invention (2), inorganic melts is heated to 50～300 ℃ in method one, method two, method four, the method five, is preferably 50～200 ℃, is preferably 50～120 ℃; Mixture heating up to 50～300 of inorganic melts and precipitation agent ℃ in method three and the method six are preferably 50～200 ℃.In general the fusing point of two or more inorganic melts is all lower than the fusing point of itself, but the fusing point of some inorganic melts is very high, and its eutectic fusing point is still very high, and this just needs fusing assistant to reduce its fusing point.Flux selection low mass molecule alcohol or water.Low mass molecule alcohol is a kind of or mixture of methyl alcohol, ethanol, propyl alcohol and butanols.Water is distilled water or deionized water.Weight with the mixture of step (2) gained is benchmark, and the consumption of fusing assistant is 0～20wt%, is preferably 0.1～10wt%.Low-melting inorganic melts in method four, method five and the method six also can adopt the method that adds fusing assistant earlier its fusing point to reduce to below 50 ℃, is added in the micelle system again.
Precipitation agent described in the step of the present invention (2) is selected from one or more in sodium hydroxide, potassium hydroxide, ammonia, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate.Method one, method four used alkaline precipitating agents are one or more in sodium hydroxide, potassium hydroxide, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia and the ammonia, add with saturated or oversaturated aqueous solution form, be preferably ammonia, add with saturated ammoniacal liquor form.Method two, method five used precipitation agents are liquefied ammonia or ammonia.Method three, method six used precipitation agents are one or more in volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate.
The used VB value of the present invention is the water-in-oil-type tensio-active agent less than 1 tensio-active agent.Relevant VB value notion please refer to " A Study of Identifying Emulsion Type of Surfactant--VolumeBalance Value " paper that this patent people is published in the Journal of colloid and interface science2002 fourth phase.The VB value is a kind of constant of hydrophilic and oleophilic performance of more effective judgement tensio-active agent than the HLB value, both have following difference: 1) the VB value of HLB value 3-6 water-in-oil-type tensio-active agent is less than 1, but the HLB to many tensio-active agents is difficult for measuring, many tensio-active agents do not have the HLB value, and any tensio-active agent all can directly calculate the VB value according to the chemical structure of tensio-active agent; 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 wetting ability.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 tensio-active agent 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 glycol ether monostearate, propyleneglycoles list dodecyl ester, polyisobutenyl toxilic acid glycol ether ester, polyisobutenyl toxilic acid triethyleneglycol ester, polyisobutenyl toxilic acid triethanolamine ester, polyisobutenyl toxilic acid glycol ether ester and succimide class (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 hangs succimide more, T-155 hangs succimide more) in one or more.
The used hydrocarbon component of the present invention can be selected petroleum component for use, the not volatile heavy distillate of the general selection of petroleum hydrocarbon components, also can select animal-plant oil, be one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables 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 naphthenic 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 asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil.Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil, lard and the fish oil.
Also can be in tensio-active agent with cosurfactant, the effect of cosurfactant can reduce the consumption of tensio-active agent, can form more stable complexed surfactant film, helps the stability of tensio-active agent film.Cosurfactant comes from one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
Among the present invention, mixture heating up to 50～300 of step (1) gained ℃, wherein method one and method four preferably are heated to 50～120 ℃, method two and method five preferably are heated to 50～200 ℃, method three and method six preferably are heated to 50～200 ℃, and method one to method six preferably is heated to melt temperature ± 20 ℃ of inorganic melts or inorganic melts and precipitation agent congruent melting.
Described aging, be to become under the glue temperature and pressure to wear out generally speaking.
Among the present invention, whether the reaction product aftertreatment needs washing, depends on the requirement to product performance, the super solubilising micelle of complex hydroxide, and high-temperature roasting can directly obtain composite oxides.For specification of quality high, need washing remove stray crystal, at first use organic solvent such as ethanol or acetone, washed product 0～3 time.Wash with water then throw out to the soluble salt weight concentration less than 0.5wt%.Described drying condition is: dried 5～24 hours for 80～110 ℃.Described roasting condition is: 250～300 ℃ of bubbling airs or inert gas (preferred nitrogen) roasting 1～3 hour, be warming up to 350～650 ℃ of bubbling airs or inert gas (preferred nitrogen) then 5～24 hours.
The throw out of the above-mentioned reaction gained of separation described in the step (3) can adopt the method for any separation solidliquid mixture of the prior art, such as filtration, centrifugation, vacuum-evaporation, supercritical extraction etc.
Nano composite oxide specific surface area by gained of the present invention is big, pore volume is big, and its specific nature is as follows: specific surface is 200～600m
2/ g is preferably 300～500m
2/ g, pore volume 0.4～1.5ml/g is preferably 0.4～1.0ml/g, and mean pore size is 4～15nm, and median size is 1～100nm, is preferably 20～50nm.Surface-area among the present invention and pore structure are with U.S. ASAP2400 type low temperature liquid nitrogen absorption instrument, calculate by the BET method.Median size wherein is the mean diameter of measuring with transmission electron microscope (TEM).
The composite oxides of the inventive method gained can be used for that hydrofining, hydrocracking, isomerization, alkylation, catalytic cracking, alkene are saturated, alkene oligomerization, catalytic reforming, hydrogenation dearomatization, Aromatizatian catalytic agent carrier, be especially suitable for use as hydrofining catalyst carrier, especially the carrier of Hydrobon catalyst.
The prepared nano composite oxide of the inventive method has the following advantages:
1, the inventive method is to utilize oil bag melts can form the character of disperseing super solubilising micelle in the height mutually.Utilize the nanometer character of micelle, the oxyhydroxide that melts and precipitation agent form carries out original position in micelle synthetic, avoided the increase of oxide diameter sizes, and particle diameter is monodisperse status.
2, outstanding feature is with high-temperature molten in the inventive method, rather than is that the liquid phase method of solvent prepares nano composite oxide with water.
3, adopt the composite molten thing in the inventive method, the productive rate height of nano-oxide, the purity height, and used tensio-active agent and hydrocarbon component consumption are little, cost is low.
4, the inventive method technology is simple, can carry out industrial production in enormous quantities.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the nanometer aluminum titanium composite oxide of embodiment 2 gained.
Embodiment
In the step of the present invention (2), the preferred preparation method that contains nanometer oxyhydroxide micelle is as follows.
Method one:
A, under normal pressure, inorganic melts is heated to fusion, be preferably 50～120 ℃, slowly join in 50～120 ℃ the mixture of hydrocarbon component, tensio-active agent and cosurfactant, be mixed to and form evenly super solubilising micelle, general mixing time is 1～60 minute, is preferably 5～30 minutes, is preferably 10～20 minutes;
B, the direct precipitation agent that adds in above-mentioned system react; Control reaction temperature is 50～120 ℃, and aging under this temperature condition then, digestion time is 3～24 hours; Wherein used precipitation agent is one or more in sodium hydroxide, potassium hydroxide, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia and the ammonia, and this precipitation agent is with saturated or oversaturated aqueous solution form adding.Precipitation agent preferably adopts ammonia, adds with saturated ammoniacal liquor form.
Method two:
A, inorganic melts is heated to fusion, be generally 50～300 ℃, be preferably 50～200 ℃, slowly join in 50～300 ℃ the mixture of hydrocarbon component, tensio-active agent and cosurfactant, make it form evenly super solubilising micelle, generally speaking, mixing time is 1 minute～60 minutes, be preferably 5 minutes～30 minutes, be preferably 10 minutes～20 minutes;
B, in confined conditions, below the ammonia critical temperature, the critical temperature of preferred 30 ℃～ammonia, precipitation agent liquefied ammonia is added in the described system of steps A, or in confined conditions, under 30 ℃～300 ℃ conditions, in the described system of steps A, feed ammonia and carry out neutralization reaction, aging 0～30 hour then, be preferably 0～8 hour, obtain containing nanometer oxyhydroxide micelle;
Method three:
A, precipitation agent and inorganic melts mixed after, be heated to fusion, be preferably 50～120 ℃, slowly join then in 30～120 ℃ the mixture of hydrocarbon component, tensio-active agent and cosurfactant, be mixed to and form evenly super solubilising micelle;
B, under airtight condition, the micelle that steps A is obtained carries out the precipitation from homogeneous solution reaction under 70～200 ℃, the reaction times is 4～8 hours, aging 0～30 hour then, be preferably 0～8 hour, obtain containing nanometer oxyhydroxide micelle.
Wherein used precipitation agent is one or more in volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate, preferred urea, hexamethylenetetramine and/or ammonium citrate.
Method four:
Under A, the normal pressure, inorganic melts slowly adds in the mixture of 50～120 ℃ of hydrocarbon components, tensio-active agent and cosurfactants at 60～120 ℃ of heating and meltings, is mixed to form evenly super solubilising micelle; The inorganic melts of low melting point drips in the above-mentioned system, mixes.
B, under airtight condition, add precipitation agent, under 50～120 ℃ of temperature, carry out neutralization reaction, aging 0～30 hour then, be preferably 0～8 hour, obtain containing nanometer oxyhydroxide micelle;
Wherein the inorganic melts of low melting point can be a fusing point at-100 ℃～50 ℃ inorganics, such as titanous chloride, titanium tetrachloride and six platinum chlorides, also can be that fusing point drops to-100 ℃～50 ℃ inorganics (adding fusing assistant water such as boric acid) after adding fusing assistant, can also be the aqueous solution (such as silicon sol, phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid etc.) of high density.Used precipitation agent is one or more in sodium hydroxide, potassium hydroxide, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia and the ammonia, and this precipitation agent is with saturated or oversaturated aqueous solution form adding.Precipitation agent preferably adopts ammonia, adds with saturated ammoniacal liquor form.
Method five:
A, inorganic melts slowly add in the mixture of 40～120 ℃ of hydrocarbon components, tensio-active agent and cosurfactants at 60～120 ℃ of heating and meltings, are mixed to form even solubilising micelle; The inorganic melts of low melting point drips in the above-mentioned system, mixes.
B, in confined conditions, below the ammonia critical temperature, be generally the critical temperature of 30 ℃～ammonia, add precipitation agent liquefied ammonia, or in confined conditions, under 30 ℃～300 ℃ conditions, feed ammonia and carry out neutralization reaction, aging 0～30 hour then, be preferably 0～8 hour, obtain containing nanometer oxyhydroxide micelle;
Wherein the inorganic melts of low melting point can be a fusing point at-100 ℃～50 ℃ inorganics, such as titanous chloride, titanium tetrachloride and six platinum chlorides, also can be that fusing point drops to-100 ℃～50 ℃ inorganics (adding fusing assistant water such as boric acid) after adding fusing assistant, can also be the aqueous solution (such as silicon sol, phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid etc.) of high density.
Method six:
After A, inorganic melts and precipitant mix are even,, slowly add in the mixture of 40～120 ℃ of hydrocarbon components, tensio-active agent and cosurfactants, be mixed to and form evenly super solubilising micelle at 60～120 ℃ of heating and meltings; The inorganic melts of low melting point drips in the above-mentioned system, mixes.
B, under airtight condition, resulting mixture is carried out the precipitation from homogeneous solution neutralization reaction under 70～200 ℃ of temperature, 4～8 hours reaction times, aging then 0～30 hour, be preferably 0～8 hour, obtain containing nanometer oxyhydroxide micelle;
Wherein the inorganic melts of low melting point can be a fusing point at-100 ℃～50 ℃ inorganics, such as titanous chloride, titanium tetrachloride and six platinum chlorides, also can be that fusing point drops to-100 ℃～50 ℃ inorganics (adding fusing assistant water such as boric acid) after adding fusing assistant, can also be the aqueous solution (such as silicon sol, phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid etc.) of high density.Wherein used precipitation agent is one or more in volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate, preferred urea, hexamethylenetetramine and/or ammonium citrate.
Method one to the mixture of method six described inorganic melts or inorganic melts and precipitation agent is added in the mixture of step (1) gained, can once slowly add, and also can slowly add several times.Can mixed melting when described inorganic melts is multiple material, also can distinguish fusion, divide once to add or repeatedly add.
The present invention is further described below in conjunction with embodiment.
Used hydrocarbon component picks up from the general petrochemical works, Lanzhou in the embodiment of the invention, and its character sees Table 1.
The character of table 1 hydrocarbon component
| Condensation point, ℃ | Oleaginousness, wt% | Viscosity (100 ℃), mm 2/s | Penetration degree (25 ℃), 1/10mm | |
| Atmosphere 3rd side cut oil | 5 | 90 | 2.01 | / |
| First vacuum side stream | 30 | 80 | 4.98 | / |
| Second line of distillation oil | 35 | 75 | 5.02 | / |
| Subtract three-way pressed oil | 37 | 68 | 5.55 | / |
| Subtract four line oil | 42 | 56 | 8.58 | 46 |
| The second line of distillation slack wax | 50 | 7.5 | 4.82 | 20 |
| Subtract three-way slack wax | 53 | 8.5 | 5.02 | 19 |
| Subtract four line slack waxs | 56.5 | 22 | 6.08 | 25 |
| The residual oil slack wax | 69 | 32.5 | 19.3 | 40 |
| Frivolous asphalt oil | 38 | 72 | 8.82 | / |
| Heavy deasphalted oil | 40 | 69 | 12.1 | 65 |
Embodiment 1
50g second line of distillation oil and 8g SP-80 are mixed, and 80 ℃ of heating for dissolving mix; 249g six nitric hydrate iron are heated to 80 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 15 minutes.The 300g Aluminum chloride anhydrous adds in the 90g ethanol and dissolves, and adds in the above-mentioned colloid to mix.Drip 20 ℃ of saturated ammoniacal liquor 303g, aging 10 hours, obtain nanometer iron-aluminium oxide gel.The composite oxides gel feeds 550 ℃ of roastings of nitrogen 8 hours, i.e. present embodiment nanometer iron aluminium composite oxide through feeding 300 ℃ of roastings of nitrogen 2 hours.BET specific surface: 320m
2/ g, pore volume: 0.52ml/g, mean pore size: 5nm, median size: 32nm.
Embodiment 2
56g is subtracted four line oil, the frivolous asphalt oil of 4g and 2g SP-60 100 ℃ of heating for dissolving, mix; The 650g ANN aluminium nitrate nonahydrate is heated to 100 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 30 minutes, the 143g titanium tetrachloride of room temperature is added above-mentioned super solubilising colloid mixing 18 minutes.Closed reactor adds the 145g ammonia when 120 ℃ of temperature, obtain nanometer titanium alumina gel.The titanium alumina gel is through 280 ℃ of roastings of bubbling air 2.5 hours, 580 ℃ of roastings 10 hours, i.e. present embodiment nanometer aluminum titanium composite oxide.BET specific surface: 260m
2/ g, pore volume: 0.44ml/g, mean pore size: 4.2nm, median size: 45nm.
Embodiment 3
With 35g atmosphere 3rd side cut oil, 5g subtract three-way slack wax, 15g polyisobutenyl toxilic acid glycol ether ester mixes 120 ℃ of heating for dissolving; 248g aluminum chloride, 225g eight hydration zirconium oxychlorides, 260g urea and 212g water are mixed and heated to 120 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 20 minutes.Closed reactor, 80 ℃ of reactions 4 hours, wearing out obtained the nano zirconia-alumina hydroxide gel in 5 hours.250 ℃ of roastings of zirconium aluminium hydroxide gel bubbling air 2 hours, 600 ℃ of roastings 5 hours, i.e. present embodiment nano zirconia-alumina composite oxide.BET specific surface: 300m
2/ g, pore volume: 0.58ml/g, mean pore size: 5nm, median size: 30nm.
Embodiment 4
The nanometer iron aluminium hydroxide gel that obtains among the embodiment 1 with washing with alcohol once, is washed till ammonium nitrate concn less than 0.5wt% with distilled water then, the 5000r/min centrifugation, at 110 ℃ of oven dry 10 hours, 550 ℃ of roastings 8 hours, i.e. present embodiment nanometer iron-aluminium oxide.BET specific surface: 360m
2/ g, pore volume: 0.90ml/g, mean pore size: 13nm, median size: 35nm.
Embodiment 5
The nanometer titanium aluminium hydroxide gel that obtains among the embodiment 2, be washed till ammonium nitrate concn less than 0.5wt% with distilled water, 12000r/min centrifugation 1 hour, 50 ℃ ,-0.07MPa vacuum-drying 2 hours, 600 ℃ of roastings 4 hours, i.e. present embodiment nanometer aluminum titanium composite oxide.BET specific surface: 310m
2/ g, pore volume: 0.92ml/g, mean pore size: 13nm, median size: 40nm.
Embodiment 6
The nano zirconia-alumina hydroxide gel that obtains among the embodiment 3 is washed till ammonium nitrate concn less than 0.5wt% with distilled water, and 16000r/min centrifugation 30 minutes is used CO at 60 ℃
2Carry out supercritical drying, 600 ℃ of roastings 4 hours, i.e. present embodiment nano zirconia-alumina composite oxide.BET specific surface: 340m
2/ g, pore volume: 0.85ml/g, mean pore size: 10nm, median size: 38nm.
Embodiment 7
55g is subtracted four lines oil and 27gT-154 mixing, and 90 ℃ of heating for dissolving mix; 668g six nitric hydrate iron are heated to 90 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 25 minutes.The 170g silicon sol (is contained 28wt%SiO
2) dewatering at 100 ℃ adds above-mentioned super solubilising colloid to 150g and mixed 10 minutes.Reduce temperature to 65 ℃, add 100g liquefied ammonia, closed reactor reacted 5 hours, obtained the nanometer iron silicon hydroxide gel.Be washed till sodium nitrate concentration less than 0.5wt% with distilled water, 12000r/min centrifugation 30 minutes is used CO at 60 ℃
2Carry out supercritical drying, compound iron silicon hydroxide gel feeds 300 ℃ of roastings of nitrogen 2 hours, feeds 550 ℃ of roastings of nitrogen 8 hours, i.e. present embodiment nanometer iron silicon composite oxides.BET specific surface: 400m
2/ g, pore volume: 0.75ml/g, mean pore size: 11nm, median size: 20nm.
Embodiment 8
90g is subtracted four line oil, 7g subtract four line slack waxs and 25g T-152, mix 100 ℃ of heating for dissolving; The 660g ANN aluminium nitrate nonahydrate is heated to 100 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 30 minutes,, be solubilized in the colloid and mixed 18 minutes 68g boric acid and 45g water heating and melting.Add 105g liquefied ammonia when being cooled to 50 ℃ of temperature, closed reactor 80 ℃ of reactions 3 hours, obtains nanometer boron aluminium hydroxide gel.The boron alumina gel is through 250 ℃ of roastings of bubbling air 2 hours, 600 ℃ of roastings 4 hours, i.e. present embodiment nanometer boron aluminium composite oxide.BET specific surface: 218m
2/ g, pore volume: 0.41ml/g, mean pore size: 4nm, median size: 40nm.
Embodiment 9
40g is subtracted four line oil, 5g heavy deasphalted oil and 25gT-154 mix, 80 ℃ of heating for dissolving mix; 375g ANN aluminium nitrate nonahydrate, 280g hexamethylenetetramine and 40g water are mixed and heated to 80 ℃ of fusions, slowly add in the said mixture, mix forming evenly super solubilising colloid in 15 minutes.The 235g titanous chloride dripped in the above-mentioned super solubilising colloid mix 60 minutes to uniform state.100 ℃ of constant temperature 6 hours, aging 10 hours, obtain nanometer titanium aluminium hydroxide gel.Be washed till sodium nitrate concentration less than 0.5wt% with distilled water, 12000r/min centrifugation 30 minutes is used CO at 60 ℃
2Carry out supercritical drying, the composite titanium-aluminum hydroxide gel feeds 300 ℃ of roastings of nitrogen 2 hours, feeds 550 ℃ of roastings of nitrogen 8 hours, i.e. present embodiment nanometer aluminum titanium composite oxide.BET specific surface: 298m
2/ g, pore volume: 0.85cc/g, mean pore size: 15nm, median size: 48nm.
Embodiment 10
55g first vacuum side stream and 35g SP-80 are mixed, and 90 ℃ of heating for dissolving mix; The 520g manganese nitrate hexahydrate is heated to 90 ℃ of fusions, slowly adds in the said mixture, mix forming evenly super solubilising colloid in 25 minutes.The 370g silicon sol (is contained 26wt%SiO
2) dewatering at 100 ℃ adds above-mentioned super solubilising colloid to 290g and mixed 10 minutes.Reduce temperature to 35 ℃, encloses container feeds 100g liquefied ammonia, is warming up to 120 ℃ of reactions 6 hours, aging 30 hours, obtains nanostructured manganese silicon hydroxide gel.Be washed till ammonium nitrate concn less than 0.5wt% with distilled water, 12000r/min centrifugation 30 minutes is used CO at 40 ℃
2Carry out supercritical drying, compound manganese silicon hydroxide gel feeds 300 ℃ of roastings of nitrogen 2 hours, feeds 550 ℃ of roastings of nitrogen 10 hours, i.e. present embodiment nanostructured manganese Si composite oxide.BET specific surface: 420m
2/ g, pore volume: 0.71ml/g, mean pore size: 12nm, median size: 80nm.
Embodiment 11
80g is subtracted three-way pressed oil and 30g SP-60 mixing, and 70 ℃ of heating for dissolving mix; 500g ANN aluminium nitrate nonahydrate and 200g urea are heated to 70 ℃ of fusions, to dissolve in the 125g Lanthanum trichloride adding 65g ethanol, even with aluminum nitrate and urea blended melts mixed melting then, slowly add in the above-mentioned hydrocarbon mixture, mix forming evenly super solubilising colloid in 35 minutes.Encloses container is warming up to 100 ℃ of reactions 8 hours, obtains nanometer lanthanum aluminium hydroxide gel.Be washed till ammonium nitrate and ammonium chloride concentration less than 0.5wt% with distilled water, 12000r/min centrifugation 30 minutes, 100 ℃ of dryings 10 hours feed 300 ℃ of roastings of nitrogen 2 hours, feeding 550 ℃ of roastings of nitrogen 10 hours, promptly is present embodiment nanometer lanthanum aluminium composite oxide.BET specific surface: 245m
2/ g, pore volume: 0.98ml/g, mean pore size: 10nm, median size: 35nm.
Claims (22)
1, a kind of preparation method of nano composite oxide, wherein composite oxides comprise two kinds of different oxide compounds at least, comprise the steps:
(1) hydrocarbon component, VB value are mixed less than 1 tensio-active agent and cosurfactant;
(2) micelle that contains nanometer oxyhydroxide is made by one of following method at least:
Method:
Under normal pressure, inorganic melts is heated to fusion, slowly join in the mixture of step (1) gained, be mixed to and form evenly super solubilising micelle; Add precipitation agent in above-mentioned system, 50 ℃～120 ℃ are carried out precipitin reaction; Aging 0～30 hour then, obtain the nanometer oxyhydroxide micelle that contains of the present invention;
Method two:
Inorganic melts is heated to fusion, slowly joins in the mixture of step (1) gained, make it form evenly super solubilising micelle; In confined conditions, below the ammonia critical temperature, precipitation agent liquefied ammonia is joined in the above-mentioned system, or in confined conditions,, ammonia is fed in the above-mentioned system at 30 ℃～300 ℃, carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
Method three:
After precipitation agent and all or part of inorganic melts mixed, be heated to fusion, slowly join then in the mixture of step (1) gained, be mixed to and form evenly super solubilising micelle, the more inorganic melts of remainder is added in the above-mentioned system; Under airtight condition, under 70 ℃～200 ℃, carry out the precipitation from homogeneous solution reaction, the reaction times is 2～8 hours, aging 0～30 hour then, obtains containing nanometer oxyhydroxide micelle;
Method four:
The inorganic melts of fused slowly adds in the mixture of step (1) gained, is mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; Under airtight condition, add precipitation agent, under 50～120 ℃ of temperature, carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
Method five:
The inorganic melts of fused slowly adds in the mixture of step (1) gained, is mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; In confined conditions, below the ammonia critical temperature, add precipitation agent liquefied ammonia, or in confined conditions,, feed ammonia and carry out neutralization reaction, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle at 30～300 ℃;
Method six:
After inorganic melts and precipitant mix were even, heating and melting slowly joined in the mixture of step (1) gained, was mixed to form evenly super solubilising micelle; The inorganic melts of fused low melting point is dripped in the above-mentioned micelle, mix; Under airtight condition, resulting mixture is carried out the precipitation from homogeneous solution neutralization reaction under 70～200 ℃ of temperature, in 4～8 hours reaction times, aging 0～30 hour then, obtain containing nanometer oxyhydroxide micelle;
(3) with step (2) gained contain nanometer oxyhydroxide micelle through roasting, obtain nano composite oxide;
Wherein water can add with crystal water and/or free-water form in step (1) and/or step (2);
Weight with the mixture of step (2) gained is benchmark, the consumption of melts (butt), precipitation agent and water is 60wt%～95wt%, the water yield is the 100wt%～350wt% as the theoretical water requirement of reaction water, the consumption of precipitation agent is the 100wt%～300wt% of theoretical requirement, and the consumption of tensio-active agent is 0.1wt%-8wt%; The consumption of hydrocarbon component is 3wt%～30wt%; The consumption of cosurfactant is 0～2wt%;
Described inorganic melts comes from two or more in aluminium source, magnesium source, lanthanum source, the calcium source, the combination in perhaps at least a titanium source, zirconium source, source of iron, manganese source and at least a aluminium source, magnesium source, lanthanum source, calcium source, the combination in perhaps at least a aluminium source, magnesium source, lanthanum source, titanium source, zirconium source, source of iron, manganese source, calcium source and at least a silicon source, phosphorus source and boron source; Described aluminium source is selected from one or more in aluminum nitrate, Tai-Ace S 150, the aluminum chloride; The magnesium source is selected from one or more in magnesium nitrate, magnesium chloride and the sal epsom; The lanthanum source is selected from Lanthanum trichloride; The calcium source is selected from calcium chloride and/or nitrocalcite; The titanium source is selected from one or more in titanous chloride, titanium tetrachloride, chlorination oxygen titanium and the titanyl sulfate; The zirconium source is selected from one or more in zirconium oxychloride, the zirconium nitrate; Source of iron is selected from one or more in iron nitrate, Iron nitrate, iron(ic) chloride, ferric sulfate and the ferrous sulfate; The manganese source is selected from one or more in manganous nitrate, Manganous chloride tetrahydrate, manganese sulfate and the permanganic anhydride; The silicon source is selected from silicon sol; The phosphorus source is selected from one or more in phosphoric acid, metaphosphoric acid, the Tripyrophosphoric acid; The boron source is selected from boric acid; The fusing point of the inorganic melts of described low melting point is-100 ℃～50 ℃, is selected from following at least a: silicon sol, phosphoric acid, metaphosphoric acid and the Tripyrophosphoric acid of titanous chloride, titanium tetrachloride, six platinum chlorides, the boric acid that adds fusing assistant water and high density.
2, preparation method according to claim 1, it is characterized in that the weight with the mixture of step (2) gained is benchmark, the consumption of melts (butt), precipitation agent and water is 80wt%～95wt%, the water yield is that the consumption of described tensio-active agent is 0.5wt%-4wt% as the 100wt%～300wt% of the theoretical water requirement of reaction water; The consumption of hydrocarbon component is 3wt%～15wt%; The consumption of cosurfactant is 0～1wt%.
3, preparation method according to claim 1, it is characterized in that the weight with the mixture of step (2) gained is benchmark, the water yield is that the consumption of described tensio-active agent is 0.8wt%-2wt% as the 100wt%～200wt% of the theoretical water requirement of reaction water; The consumption of hydrocarbon component is 4wt%～8wt%; The consumption of cosurfactant is 0～0.5wt%.
4, preparation method according to claim 1, it is characterized in that described hydromining adds with following one or more modes: a, in step (1), add entry, b, in step (2), adopt the form of the inorganic salt contain crystal water to add, c, in the melts melting process, add entry, d, form with the mixture of step (1) gained and to add in the even colloidal process or after forming even colloid, to add.
5, preparation method according to claim 1 is characterized in that described water, and method one and method four are to adopt the precipitation agent aqueous solution, and contain the inorganic salt of crystal water and/or add entry in the melts melting process; Method two, method three, method five and method six are to adopt to contain the inorganic salt of crystal water and/or add entry in the melts melting process.
6, preparation method according to claim 1, the melt temperature scope that it is characterized in that method one and method four is 50～120 ℃, the melt temperature scope of method three and method six is 50～200 ℃, 50～200 ℃ of the melt temperature scopes of method two and method 5.
7, preparation method according to claim 1 is characterized in that adding fusing assistant in the melts melting process, and used fusing assistant is low mass molecule alcohol or water, and wherein low mass molecule alcohol is a kind of or mixture of methyl alcohol, ethanol, propyl alcohol and butanols; Weight with the mixture of step (2) gained is benchmark, and the consumption of fusing assistant is 0.1～20wt%.
8, preparation method according to claim 1 is characterized in that the precipitation agent described in the step (2) is selected from one or more in sodium hydroxide, potassium hydroxide, ammonia, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate.
9, preparation method according to claim 1, it is characterized in that in the step (2), method one, method four used precipitation agents are one or more in sodium hydroxide, potassium hydroxide, volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia and the ammonia, add with saturated or oversaturated aqueous solution form; Method two, method five used precipitation agents are liquefied ammonia or ammonia; Method three, method six used precipitation agents are one or more in volatile salt, salt of wormwood, yellow soda ash, sodium bicarbonate, bicarbonate of ammonia, urea, hexamethylenetetramine and the ammonium citrate.
10, preparation method according to claim 1 is characterized in that in the step (2), and method one, method four used precipitation agents are ammonia, adds with saturated ammoniacal liquor form; Method three, method six used precipitation agents are one or more in urea, hexamethylenetetramine and the ammonium citrate.
11, preparation method according to claim 1 is characterized in that used tensio-active agent is selected from one or more in SP-40, SP-60, SP-65, SP-80, SP-85, M-201, fatty acid monoglyceride, two sweet esters, ethylene glycol monostearate, glycol ether monostearate, polyisobutenyl toxilic acid glycol ether ester, polyisobutenyl toxilic acid triethyleneglycol ester, polyisobutenyl toxilic acid triethanolamine ester, polyisobutenyl toxilic acid glycol ether ester and the succimide class.
12, preparation method according to claim 1 is characterized in that used hydrocarbon component is one or more of atmosphere 3rd side cut distillate, vacuum distillate, decompression slack wax, residual oil slack wax, deasphalted oil, vegetables oil, animal oil.
13, preparation method according to claim 12 is characterized in that used 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; 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; The residual oil slack wax is frivolous asphalt oil and/or heavy deasphalting slack wax; Deasphalted oil is frivolous asphalt oil and/or heavy deasphalted oil; Vegetables oil is one or more in soya-bean oil, peanut oil, rape seed oil, Viscotrol C, Oleum Helianthi, Oleum Cocois and the plam oil; Animal oil is one or more in butter, sheep oil, lard and the fish oil.
14, preparation method according to claim 1, it is characterized in that used cosurfactant, cosurfactant is one or more in petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate and the dodecyl alcohol acyl phosphoric acid ester.
15, preparation method according to claim 1 is characterized in that mixture heating up to 50～300 ℃ of step (1) gained.
16, preparation method according to claim 1, the mixture heating up that it is characterized in that step (1) gained are to melt temperature ± 20 of inorganic melts or inorganic melts and precipitant mix thing ℃.
17, preparation method according to claim 1, it is characterized in that in the step (2), the digestion time of method one and method four is 3～24 hours, and the digestion time of method two and method five is 0～8 hour, and the digestion time of method three and method six is 0～8 hour.
18, preparation method according to claim 1 is characterized in that the nano combined hydroxide gel of step (2) gained is first after washing, oven dry, through the described calcination steps of step (3), obtains the nano level composite oxides again.
19, according to claim 1 or 18 described preparation methods, it is characterized in that described roasting condition is as follows:, be warming up to 350～650 ℃ of roastings 5～24 hours then 250～300 ℃ of roastings 1～3 hour.
20, preparation method according to claim 18 is characterized in that described washing process is as follows: at first use the organic solvent washing product 0～3 time, wash with water then throw out to the soluble salt weight concentration less than 0.5wt%; Described drying condition is as follows: dried 5～24 hours under 80～110 ℃ of conditions.
21, according to claim 1 or 18 described preparation methods, it is characterized in that the combined oxidation properties of gained is as follows: specific surface is 200～600m
2/ g, pore volume 0.4～1.5ml/g, mean pore size is 4～15nm, median size is 1～100nm.
22, preparation method according to claim 21, it is characterized in that the combined oxidation properties of gained is as follows: specific surface is 300～500m
2/ g, pore volume 0.4～1.0ml/g, median size is 20～50nm.
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| CN101890377B (en) * | 2009-05-19 | 2012-08-29 | 中国石油化工股份有限公司 | Zirconia-alumina composite oxide carrier and method for preparing same |
| CN103816928B (en) * | 2014-02-20 | 2017-01-04 | 煤炭科学技术研究院有限公司 | A kind of Hydrobon catalyst and its preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1316486A (en) * | 2001-05-09 | 2001-10-10 | 石油大学(北京) | Hydrocatalyst arrier and its preparing process |
| CN1334243A (en) * | 2001-08-27 | 2002-02-06 | 清华大学 | Process for prepairng granularity controllable nm-class zirconium oxide |
-
2005
- 2005-05-18 CN CNB2005100464806A patent/CN100345763C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| CN1316486A (en) * | 2001-05-09 | 2001-10-10 | 石油大学(北京) | Hydrocatalyst arrier and its preparing process |
| CN1334243A (en) * | 2001-08-27 | 2002-02-06 | 清华大学 | Process for prepairng granularity controllable nm-class zirconium oxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451673A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of nanometer silicon hydroxide-aluminum hydroxide powder |
| CN102451673B (en) * | 2010-10-15 | 2014-07-23 | 中国石油化工股份有限公司 | Preparation method of nanometer silicon hydroxide-aluminum hydroxide powder |
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