CN103100379B - Production method of titanium oxide-alumina composite - Google Patents
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- CN103100379B CN103100379B CN201110358513.6A CN201110358513A CN103100379B CN 103100379 B CN103100379 B CN 103100379B CN 201110358513 A CN201110358513 A CN 201110358513A CN 103100379 B CN103100379 B CN 103100379B
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Abstract
The invention provides a production method of titanium oxide-alumina composite. The preparation method comprises the following steps: dissolving soluble aluminum salt into deionized water to obtain solution A; dissolving soluble titanium compound into organic solvent to obtain solution B; preparing ammonium bicarbonate and thick ammonia water into mixed ammonia water solution C; converging the solution A, B and C to form and precipitate mixed liquor to obtain a product D; and washing, filtering, drying and roasting the product D to obtain the titanium oxide-alumina composite. The preparation method is simple in technique, easily available in raw materials, the titanium oxide-alumina composite is large in specific surface area, large in pore volume, and high in mechanical strength. The titanium oxide-alumina composite can be separately used as a catalyst or a catalyst carrier. A hydrodesulfurization catalyst prepared by adopting the titanium oxide-alumina composite as the carrier has the advantages of being high in low-temperature activity and high in hydrodesulfurization rate.
Description
Technical field
The present invention relates to a kind of preparation method of Titanium oxide-aluminum oxide compound, in particular, relate to a kind of directly as the preparation method of the Titanium oxide-aluminum oxide compound of the double hole channel special construction of catalyst or catalyst carrier for hydrgenating.
Background technology
Titanium oxide is separately as carrier and traditional alumina phase ratio, and its specific area is less, and (BET specific surface area is about 50m
2/ g), bad mechanical strength, is about γ-Al
2o
31/5th, poor heat stability.Titanium dioxide-aluminum oxide composite carrier, namely keeps Al
2o
3carrier high-ratio surface, high strength, Heat stability is good, the advantages such as suitable pore-size distribution, have TiO again
2special performance, after using titanium oxide modified support simultaneously, creates impact to the structures and characteristics of the active phase of catalyst, improves the catalytic activity of catalyst, resistance to carbon formation and anti-poisoning ability.
Titanium oxide-aluminum oxide compound and preparation method thereof has many reports, Titanium oxide-aluminum oxide compound can directly be used in gram Lloyd's (Clause) Catalytic processes as catalyst, also can as the carrier of petrochemical industry hydrorefining catalyst for hydrocarbon.
Traditional Titanium oxide-aluminum oxide compound preparation method adopts alumina dry glue to add appropriate peptizing agent again with the solution of titanium chloride and water fully mixes aftershaping, dry, roasting obtains, as European patent document EP0199399 discloses the preparation method of Titanium oxide-aluminum oxide compound.The preparation method of this Titanium oxide-aluminum oxide compound is by a certain proportion of titanium oxide, aluminium oxide, and acetic acid and water mix extruded, then high-temperature roasting and obtaining.The catalyst that this titanium dioxide-aluminum oxide is prepared as carrier, has the feature that initial activity is high, but the decentralization of titanium oxide, mechanical strength is not high.
Disclose in European patent document EP0399640 and prepare Titanium oxide-aluminum oxide compound with titanium trichloride, titanyl sulfate or titanium oxychloride and sodium aluminate solution co-precipitation, the catalyst prepared as carrier by this Titanium oxide-aluminum oxide compound in Clause Catalytic processes to CS
2desulphurizing activated height, the advantage such as the high and resistance to SO_2 of stability is strong.But its industrial production cost is high, the specific area of Titanium oxide-aluminum oxide compound and pore size distribution need to be improved further.
Disclose a kind of preparation method of titanium dioxide-aluminum oxide bi-component in Chinese patent literature CN1273878A, adopt solubility titanium salt to add mixture and the NaAlO of aluminum soluble salt
2prepared by solution co-precipitation.This Ti-Al bi-component has that preparation method is simple, and raw material is easy to get, the decentralization advantages of higher of the large and titanium of specific area.But the pore size distribution of this Ti-Al bi-component needs to improve.
A kind of preparation method of titania-alumina compound is disclosed in Chinese patent literature CN101204671A, adopt and metatitanic acid is dissolved in acid condition titanium solution and receives with meta-aluminic acid or the inorganic salt solution of aluminium mixes under vigorous stirring, regulate the pH value of mixture to 6.5 ~ 9.5, drying, roasting obtains Titanium oxide-aluminum oxide compound.The Titanium oxide-aluminum oxide compound that the method obtains has high titanium content and high specific area, but the pore size distribution of Titanium oxide-aluminum oxide compound is wayward, cannot obtain the Titanium oxide-aluminum oxide compound of the pore size distribution be suitable for.
The present inventor's preparation of Titanium oxide-aluminum oxide compound in Chinese patent literature CN1429890A is with specific surface 100 ~ 200m
2/ g, pore volume is 0.5 ~ 1.5ml/g, and most probable pore size is that 80-200 dust obtains aluminium oxide dipping compound titanium solution, and dry, roasting obtains Titanium oxide-aluminum oxide compound.The specific area of this compound is 80 ~ 180m
2/ g, preferably 120 ~ 150m
2/ g; Pore volume is 0.4 ~ 1.3ml/g, is preferably 0.5 ~ 1.0ml/g; Most probable pore size is 90 ~ 150 dusts, preferably 110 ~ 140 dusts.Titanium oxide-aluminum oxide compound floods appropriate active component palladium again, and the catalyst made is for drippolene selective hydrogenation refining process, and the existing catalyst of liquid air speed ratio improves 30 ~ 40%, is selectively greater than 99%, and running 1500 hours is activity stabilized continuously.But the specific area of this titanium dioxide-aluminum oxide composite carrier and pore size distribution still need to improve.
Summary of the invention
In view of above prior art situation, the present inventor conducts in-depth research the preparation method of Titanium oxide-aluminum oxide compound and hydrogenation catalyst thereof, provide a kind of method preparing Titanium oxide-aluminum oxide compound, the Titanium oxide-aluminum oxide compound of suitable pore size distribution can be obtained, the catalyst prepared with this titanium dioxide-aluminum oxide is for pyrolysis gasoline hydrogenation sweetening process, there is low temperature active high, the feature that desulfurization degree is high.
The invention provides a kind of preparation method of Titanium oxide-aluminum oxide compound, comprise the following steps:
Aluminum soluble salt is dissolved in deionized water and obtains solution A by a;
Soluble titanium compound is dissolved in organic solvent and obtains solution B by b;
C is by carbonic hydroammonium and concentrated ammonia liquor preparation mixing aqueous ammonium C;
D is by A, B and C tri-strands of solution and stream forms mixed liquor and co-precipitation, obtains product D;
E, by product D washing, filtration, dry, roasting, obtains Titanium oxide-aluminum oxide compound.
In above-mentioned preparation method, the pH value of the mixed liquor in described steps d changes between faintly acid and alkalescent.The pH value of described mixed liquor makes it change between faintly acid and alkalescent by the flow of control solution C.In a specific embodiment, pH value timing variation between faintly acid and alkalescent of described mixed liquor, the interval time of described timing variation is 5 ~ 15 minutes, preferably 8 ~ 10 minutes.In another specific embodiment, described faintly acid preferably refers to that pH value is 5.0 ~ 6.0, and described alkalescent preferably refers to that pH value is 8.5 ~ 9.5.
In above-mentioned preparation method, in steps d, preferably under temperature 70 ~ 90 DEG C, stirring, carry out co-precipitation.
In above-mentioned preparation method, in described step a, the concentration of described aluminum soluble salt is 0.2 ~ 3.0mol/l, preferably 0.5 ~ 2.5mol/l.Described aluminum soluble salt can be understood as and can obtain all aluminium salt of alundum (Al2O3) as catalyst carrier, includes but not limited to: the inorganic aluminates such as organic aluminium salt and aluminum sulfate, aluminium chloride and aluminum nitrate such as aluminum dialkyl, dialkylaluminum chloride, alkyl al dichloride and dialkyl group alchlor.
In above-mentioned preparation method, in described step b, described soluble titanium compound is appreciated that and can obtains the titanium salt of titanium oxide as catalyst carrier, wherein preferred titanium tetrachloride; Described organic solvent can be understood as all organic solvents that can dissolve titanium compound.In a preferred embodiment, described titanium compound is titanium tetrachloride, and described organic solvent is isopropyl alcohol; The volume ratio of titanium tetrachloride and isopropyl alcohol is 1: 3 ~ 1: 10, preferably 1: 5 ~ 1: 8.
In above-mentioned preparation method, in described step c, the concentration of described carbonic hydroammonium is 0.05 ~ 0.4mol/l, preferably 0.1 ~ 0.3mol/l.Described ammonia concn is 24 ~ 28wt%, described concentrated ammonia liquor addition 10 ~ 30v%, preferred 15-25v%.
In above-mentioned preparation method, the described product D deionized water cyclic washing of 10 ~ 20 times, filters four times, removing acid ion; Filter cake was in 100 ~ 120 DEG C of dryings 10 ~ 12 hours.Filter cake roasting at 300 ~ 700 DEG C, obtains Titanium oxide-aluminum oxide compound.Filter cake is preferably 400 ~ 600 DEG C of roasting temperatures 4 ~ 6 hours.
In the Titanium oxide-aluminum oxide compound of said method gained, titanium oxide content is 0.5 ~ 25wt%.The specific area of described Titanium oxide-aluminum oxide compound is 200 ~ 300m
2/ g, pore volume is 0.4 ~ 1ml/g.The micropore of Titanium oxide-aluminum oxide compound is double hole channel distribution.In the particular embodiment, aperture is that the content of the micropore of 20 ~ 40 dusts is greater than 37%, and aperture is that the content of the micropore of 80 ~ 130 dusts is greater than 37%, and aperture is that the total content of the micropore of 20 ~ 40 dusts and 80 ~ 130 dusts is greater than 80%.
Titanium oxide-aluminum oxide compound of the present invention can manufacture any known shape, such as bar shaped, spherical or cloverleaf pattern.
Preparation method's technique provided by the invention is simple, raw material is easy to get, and obtained Titanium oxide-aluminum oxide compound micropore is double hole channel structure, and specific area is large, and pore volume is large, and mechanical strength is high.Titanium oxide-aluminum oxide compound can be used alone as catalyst or as catalyst carrier.With the Hydrobon catalyst that Titanium oxide-aluminum oxide compound of the present invention is prepared for carrier, there is low temperature active high, the advantage that hydrodesulfurization rate is high.
Detailed description of the invention
Below by example, the preferred embodiments of the present invention are further elaborated, should be understood to embodiment herein only for instruction and explanation of the present invention, in no case any restriction is formed to the present invention.
Embodiment 1
Get the analytically pure AlCl of 201.3g
36H
2o is dissolved in obtained solution A in the deionized water of 1000ml
1.Get the analytically pure TiCl of 17.8g
4be dissolved in (volume ratio of titanium tetrachloride and isopropyl alcohol is 1: 7) obtained solution B in the aqueous isopropanol of 300ml
1.Get the analytically pure NH of 18g
4hCO
3be dissolved in the deionized water of 600ml, then the concentration adding 250ml is 24 ~ 28wt% ammoniacal liquor, is uniformly mixed, adds deionized water and be mixed with 1000ml and obtain solution C
1.Under normal pressure, temperature 70 ~ 75 DEG C of conditions, A
1, B
1and C
1three kinds of solution drip and flow and form mixed liquor and precipitate, and control solution C
1flow, the pH value of mixed liquor is kept 8 minutes in 5.0 ~ 6.0 scopes, then strengthens solution C
1flow makes the pH value of mixed liquor keep 8 minutes in 8.5 ~ 9.5 scopes, then reduces solution C
1flow makes ph value of mixture keep 8 minutes in 5.0 ~ 6.0 scopes, then strengthens solution C
1flow makes the pH value of mixed liquor in 8.5 ~ 9.5 scopes, until A
1and B
1solution all drips, and obtains product D
1.At 70 DEG C of temperature, product D
1sedimentation 30 minutes, filter, wash 30 minutes by the deionized waters of 15 times, refilter, then wash, this process repeats four times.Filter cake, in 100 ~ 120 DEG C of dryings 8 ~ 12 hours, obtains 48.5g Titanium oxide-aluminum oxide compound P in 5 hours in 450 DEG C of roastings
1.Data are in table 1.
Embodiment 2
Repeat the titanium dioxide-aluminum oxide preparation process in embodiment 1, difference is that getting 277.6g analyzes pure Al
2(SO
4)
318H
2o sample is dissolved in deionized water and obtains 1000ml solution A
2, obtained 48.6g Titanium oxide-aluminum oxide compound P
2.Data are in table 1.
Embodiment 3
Repeat the preparation process of embodiment 1, difference is that getting 235.7g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
3, get the analytically pure TiCl of 0.6g
4be dissolved in the isopropyl alcohol of 15ml and obtain solution B
3, obtained 48.4g Titanium oxide-aluminum oxide compound P
3.Data are in table 1.
Embodiment 4
Repeat the preparation process of embodiment 1, difference is that getting 221.1g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
4, get the analytically pure TiCl of 2.4g
4, be dissolved in the isopropyl alcohol of 60ml and obtain solution B
4, obtained 48.7g Titanium oxide-aluminum oxide compound P
4.Data are in table 1.
Embodiment 5
Repeat the preparation process of embodiment 1, difference is that getting 214.3g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
5, get the analytically pure TiCl of 5.9g
4, be dissolved in the isopropyl alcohol of 144ml and obtain solution B
5, obtained 48.6g Titanium oxide-aluminum oxide compound P
5.Data are in table 1.
Embodiment 6
Repeat the preparation process of embodiment 1, difference is that getting 213.1g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
6, get analytically pure TiCl
411.9g, is dissolved in the isopropyl alcohol of 250ml and obtains solution B
6, obtained 48.5g Titanium oxide-aluminum oxide compound P
6.Data are in table 1.
Embodiment 7
Repeat the preparation process of embodiment 1, difference is that getting 189.5g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
7, get analytically pure TiCl
423.8g, is dissolved in the isopropyl alcohol of 500ml and obtains solution B
7, obtained 48.7g Titanium oxide-aluminum oxide compound P
7.Data are in table 1.
Embodiment 8
Repeat the preparation process of embodiment 1, difference is that getting 177.6g analyzes pure AlCl
36H
2o to be also dissolved in deionized water obtaining 1000ml solution A
8, get analytically pure TiCl
429.7g, is dissolved in the isopropyl alcohol of 625ml and obtains solution B
8, obtained 48.6g Titanium oxide-aluminum oxide compound P
8.Data are in table 1.
Comparative example 1
Prepare Titanium oxide-aluminum oxide compound according to method disclosed in European patent prospectus (EP0,339,6407), get 70g NaAlO
2being dissolved in deionized water and being diluted to 1000ml, elimination insoluble matter, obtains solution A
9, by 13g TiOCl
2the aqueous solution be diluted to 1000ml and obtain solution B
9, control reaction temperature 68-72 DEG C, regulate pH value to 9.0 ~ 9.5, A with the ammoniacal liquor that concentration is 10% (wt)
9and B
9solution adds in reactor with the speed of 25ml/ minute simultaneously, sedimentation 30 minutes, filters, 30 minutes are washed by 20 times of deionized waters of filter cake volume, refilter, then wash, this process repeats four times, filter cake was in 110 DEG C of dryings 8 hours, add the salpeter solution kneading of 5% (wt), be extruded into cloverleaf pattern with banded extruder, in 110 DEG C of dryings 8 hours, in 450 DEG C of roastings 4 hours, obtained 49.7g Titanium oxide-aluminum oxide compound P
9, its data are in table 1.
Comparative example 2
Get 14ml concentration be 85% sulfuric acid solution under constantly stirring, join 11g H
2tiO
3in, be heated to 130 DEG C and make it dissolve completely, be diluted to 1000ml by deionized water, obtain Ti (SO
4)
2solution B
10.
Get 70g NaAlO
2being dissolved in deionized water and being diluted to 1000ml, elimination insoluble matter obtains solution A
10.
At normal pressure, under reaction temperature 68 ~ 72 DEG C of conditions, pH value is regulated to be 9.0-9.5 with the ammoniacal liquor that concentration is 25% (wt), under agitation, A
10and B
10solution is with the flow velocity co-precipitation of 25ml/min, and sedimentation 30 minutes at 70 DEG C of temperature, filters, 30 minutes are washed by 20 times of deionized waters of filter cake volume, refilter, then wash, this process repeats four times, filter cake was in 110 DEG C of dryings 8 hours, add the salpeter solution kneading of 5% (wt), be extruded into cloverleaf pattern with banded extruder, in 110 DEG C of dryings 8 hours, in 450 DEG C of roastings 4 hours, obtained 49.3g Titanium oxide-aluminum oxide compound P
10, its data are in table 1.
Embodiment 9
Catalyst preparing:
The Titanium oxide-aluminum oxide compound P of Example 1
1carrier 40g, adds MoO
3concentration is the ammonium molybdate aqueous solution 23ml of 0.351g/ml, normal temperature, atmospheric agitation 30 minutes, 110 DEG C of dryings 8 hours, and 500 DEG C of roastings 5 hours, obtain 47.2g catalyst precarsor H
1.
Get the catalyst precarsor H of the above-mentioned preparation of 40g
1, 40g, adds the cobalt nitrate solution 24ml that CoO concentration is 0.08g/ml, normal temperature, atmospheric agitation 30 minutes, 110 DEG C of dryings 8 hours, and 500 DEG C of roastings 5 hours, obtain 49.2g catalyst precarsor H
2.The character of catalyst is in table 2.
Comparative example 3
Repeat embodiment 11 preparation process, unlike, use the Titanium oxide-aluminum oxide compound P of comparative example 1
9, obtained 49.1g catalyst K
2.The character of catalyst is in table 2.
Comparative example 4
Repeat embodiment 11 preparation process, unlike, use the Titanium oxide-aluminum oxide compound P of comparative example 2
10, obtained 49.2g catalyst S
2.The character of catalyst is in table 2.
Embodiment 10
The present embodiment is the application of catalyst in pyrolysis gasoline hydrogenation desulphurization reaction.
The catalyst H of Example 11
210g, the hydrogenation plant being seated in 30ml reactor is evaluated continuously.
The conditions of vulcanization of catalyst is, temperature 280 DEG C, Hydrogen Vapor Pressure 2.5Mpa, hydrogen gas-oil ratio 400: 1.Sulfurized oil 1.5%. carbon disulfide and kerosene, cure time 8 hours, hydrogen flowing quantity 150ml/ hour.The boiling range of drippolene raw material is 83-163 DEG C, and sulfur content is 310ppm, and bromine valency is 26.8 grams of bromine/100 gram oil.
Reaction condition: pressure is 3.0Mpa, temperature is 250 DEG C, and air speed is 3.0h
-1, hydrogen-oil ratio (volume ratio) is 400: 1.
After three kinds of catalyst vulcanizations, pass into drippolene at reaction conditions and carry out hydrodesulfurization.The results are shown in Table 3.
Hydrodesulfurization rate is calculated as follows:
Hydrodesulfurization rate=(in feed sulphur content-product sulfur content)/feed sulphur content × 100%
Comparative example 5
Repeat embodiment 10, difference is to use catalyst K
2.Data are in table 3.
Comparative example 6
Repeat embodiment 10, difference is to use catalyst S
2.Data are in table 3.
The data of table 1 Titanium oxide-aluminum oxide compound
Note: in table, pore volume and specific area nitrogen adsorption method (BET) measure.
The data of table 2 catalyst
The hydrodesulfurization data of table 3 drippolene
As can be seen from Table 3, three kinds of catalyst are used for pyrolysis gasoline hydrogenation and refine, catalyst H prepared by carrier provided by the invention
2hydrodesulfurization activity when refining for pyrolysis gasoline hydrogenation and desulfurization degree are apparently higher than the K using the carrier of prior art to prepare
2and S
2catalyst.
Claims (14)
1. prepare a method for Titanium oxide-aluminum oxide compound, comprise the following steps:
Aluminum soluble salt is dissolved in deionized water and obtains solution A by a;
Soluble titanium compound is dissolved in organic solvent and obtains solution B by b;
C is by carbonic hydroammonium and concentrated ammonia liquor preparation mixing aqueous ammonium C;
D is by A, B and C tri-strands of solution and stream forms mixed liquor and co-precipitation, controls the flow of solution C, the pH value of mixed liquor is changed between faintly acid and alkalescent, obtains product D;
E, by product D washing, filtration, dry, roasting, obtains Titanium oxide-aluminum oxide compound.
2. method according to claim 1, is characterized in that, in described steps d, pH value timing variation between faintly acid and alkalescent of described mixed liquor, the time interval of described timing variation is 5 ~ 15 minutes.
3. method according to claim 2, is characterized in that, in described steps d, the time interval of described timing variation is 8 ~ 10 minutes.
4. according to the method in claim 1-3 described in any one, it is characterized in that, described faintly acid refers to that pH value is 5.0 ~ 6.0, and described alkalescent refers to that pH value is 8.5 ~ 9.5.
5. method according to claim 1, is characterized in that, in described step a, the concentration of described aluminum soluble salt is 0.2 ~ 3.0mol/L.
6. method according to claim 5, is characterized in that, in described step a, the concentration of described aluminum soluble salt is 0.5 ~ 2.5mol/L.
7. method according to claim 1, is characterized in that, in described step b, described titanium compound is titanium tetrachloride, and described organic solvent is isopropyl alcohol, and the volume ratio of titanium tetrachloride and isopropyl alcohol is 1:3 ~ 1:10.
8. method according to claim 7, is characterized in that, in described step b, the volume ratio of titanium tetrachloride and isopropyl alcohol is 1:5 ~ 1:8.
9. method according to claim 1, is characterized in that, in described step c, the concentration of described carbonic hydroammonium is 0.05 ~ 0.4mol/L.
10. method according to claim 9, is characterized in that, in described step c, the concentration of described carbonic hydroammonium is 0.1 ~ 0.3mol/L.
11. methods according to claim 1, is characterized in that, in described step c, described ammonia concn is 24 ~ 28wt%, and described concentrated ammonia liquor addition is 10 ~ 30v%.
12. methods according to claim 11, is characterized in that, in described step c, described concentrated ammonia liquor addition is 15-25v%.
13. methods according to claim 1, is characterized in that, in described Titanium oxide-aluminum oxide compound, the content of titanium oxide is 0.5 ~ 25wt%.
14. methods according to claim 1 or 13, it is characterized in that, the specific area of described Titanium oxide-aluminum oxide compound is 200 ~ 300m
2/ g, pore volume is 0.4 ~ 1ml/g.
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| CN104437571B (en) * | 2013-09-16 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst, preparation method and applications |
| CN104941639B (en) * | 2014-03-27 | 2018-06-12 | 中国石油化工股份有限公司 | A kind of selective hydrogenation catalyst and its preparation method and application |
| CN104971706B (en) * | 2014-04-09 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method and its application for preparing titanium oxide alumina compound |
| CN107486201B (en) * | 2016-06-12 | 2020-07-21 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of pyrolysis gasoline and preparation and application thereof |
| CN112007626A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Preparation method and application of alumina-titanium oxide composite carrier |
| CN111500141A (en) * | 2020-06-05 | 2020-08-07 | 黄�俊 | Antibacterial emulsion paint and preparation method thereof |
| CN113817978A (en) * | 2021-09-23 | 2021-12-21 | 南京金鲤新材料有限公司 | Plasma spraying Al2O3-TiO2Method for preparing composite powder |
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| CN1837138A (en) * | 2006-04-11 | 2006-09-27 | 浙江大学 | Process for preparing aluminum titanium composite oxide with high specific surface |
| CN1951818A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Titanium-containing aluminium hydroxide preparation method |
| CN101234358A (en) * | 2008-03-05 | 2008-08-06 | 浙江大学 | Method for preparing TiO2/gamma-Al2O3 composite carrier |
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| EP0339640A1 (en) * | 1988-04-28 | 1989-11-02 | The Harshaw Chemical Company | Alumina-titania composition |
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| C06 | Publication | ||
| PB01 | Publication | ||
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