CN1325166C - Method for preparing titanium containing aluminium hydroxide - Google Patents
Method for preparing titanium containing aluminium hydroxide Download PDFInfo
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- CN1325166C CN1325166C CNB2004100507436A CN200410050743A CN1325166C CN 1325166 C CN1325166 C CN 1325166C CN B2004100507436 A CNB2004100507436 A CN B2004100507436A CN 200410050743 A CN200410050743 A CN 200410050743A CN 1325166 C CN1325166 C CN 1325166C
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- aluminium hydroxide
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Abstract
The present invention discloses a preparation method of titanium containing aluminium hydroxide, which introduces titanium in the modes of adding an organic titanium salt solution, etc. by drops in the process of gelatinization during the preparation of aluminium hydroxide by a carbonization method. Thus, the preparation method not only ensures the uniformly diffusion of the titanium on the surface of the aluminium hydroxide but also has no influence on the characteristics of large specific surface area and large hole capacity of the preparation of the aluminium hydroxide by the carbonization method, and simultaneously, has no environment pollution in the preparation process. When used for a catalyst carrier and a hydrogenation catalyst, the titanium containing aluminium hydroxide of the present invention has good physicochemical index and service performance.
Description
Technical field
The present invention relates to a kind of preparation method of Ti-contained aluminium hydroxide.
Background technology
In recent years, residual hydrocracking technology is subject to people's attention always.Along with the more and more high requirement of needs and environmental protection aspect of residual oil deep processing, must carry out more extensive research to catalyst for hydrotreatment of residual oil, with continuous developing new catalyst, satisfy actual needs.
In catalyst, introduce the performance that the auxiliary agent titanium can the Effective Raise catalyst, therefore, all contain the auxiliary agent titanium in many heavy, residual oil hydrocatalysts, but the difference of titanium is introduced mode catalyst preparation cost and catalyst serviceability are all had certain impact.The method of introducing titanium in catalyst or the catalyst raw material aluminium oxide is more, and selected to contain titanium species also varied, even have the people directly to add TiO in aluminium oxide
2, rely on then the high temperature migration in the hope of its Uniform Dispersion at alumina surface.
These class methods are feasible to the carrier preparation process of most catalyst, because carrier does not contain active component in the process, namely do not have competition when titanium and alumina phase mutual effect.And in some Catalyst Production, such as kneading method and " mix-soaking " combined techniques (CN 1098433A; US 5089453) etc., since the intervention of active component, the predecessor-aluminium hydroxide of each species and aluminium oxide, the competition during interaction is inevitably, this will weaken TiO
2To the facilitation of catalyst performance, so be necessary to prepare homodisperse Ti-contained aluminium hydroxide.
US4312785 discloses a kind of method of introducing titanium in aluminium oxide, and its process is processed in indifferent gas divides then for organic solvent and inorganic titanium tetrafluoride impregnated alumina.This method has also been introduced fluorine when introducing the auxiliary agent titanium, its use can be restricted in the situation of fluorine not wishing to have.
CN1255405A relates to a kind of preparation of titanium-contained aluminum oxide, will add ammoniacal liquor hydrolysis, filtration, washing, roasting behind the titanium tetrachloride solution impregnated alumina again.Its weak point is because the acidity of titanium tetrachloride solution is stronger, and the structure of aluminium oxide is had certain destruction.
EP0339640 discloses the method that a kind of coprecipitation prepares titanium-contained aluminum oxide, mixes with aluminum soluble salts such as aluminium chloride with solubility titanium salts such as titanium trichlorides, regulates pH value with alkaline solution then, and titanium and aluminium are precipitated simultaneously.This method can not be applicable in the carbonizatin method production alumina process, because, the aluminum salt solution that carbonizatin method is produced the aluminium oxide use is the sodium aluminate solution of alkalescence, as if the titaniferous salt solution mix with acidity precipitation reaction takes place at first then, and this course of reaction obtains product titanium skewness.
CN 1289636A has announced a kind of method that titanium salt prepares Ti-contained aluminium hydroxide that precipitates in aluminum hydroxide slurry, can prepare and disperse preferably Ti-contained aluminium hydroxide, but because the acidity of titanium salt solution is stronger, etching apparatus needs special anti-corrosive apparatus during use.And become γ-Al at Aluminium hydroxide roasting
2O
3The time can produce the gaseous contamination environment such as chlorine and sulfur dioxide; CN 1324687A has announced the method for introducing the auxiliary agent titanium in a kind of carbonizatin method, is specially levigate metatitanic acid, TiO
2Mix with sodium aluminate solution, pass into then carbon dioxide and carry out precipitation reaction.The Ti-contained aluminium hydroxide that this method obtains, the titanium distribution uniform, but when becoming glue with carbon dioxide reaction, sodium aluminate solution can produce aggregation owing to add solid particle (although its granularity is extremely less than 65 μ m), influence the granularity of aluminium hydroxide, the distribution of titanium in aluminium hydroxide simultaneously also is affected.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method of producing introducing auxiliary agent titanium in the alumina process at carbonizatin method, guaranteeing further to improve the performance of titanium-contained aluminum oxide under the situation that titanium is evenly distributed.
Ti-contained aluminium hydroxide process of the present invention is as follows:
Prepare earlier sodium aluminate solution and organic titanium salt solution, then sodium aluminate solution and the carbon dioxide for preparing is reacted into glue under stirring condition, and meanwhile with organic titanium salt solution with drip, stream adds or Sprayable adds.Solution filter, washing, drying namely make final Ti-contained aluminium hydroxide product after the cemented into bundles.
Product contains titanium dioxide 0.1～20w% after the roasting of Ti-contained aluminium hydroxide of the present invention, is preferably 5～15w%, and pore volume is 0.8～1.2ml/g, and specific surface is 350m
2More than/the g, the decentralization I of titanium on aluminium oxide
Ti/ I
AlBe more than 0.3, to be generally 0.3～0.4.
Ti-contained aluminium hydroxide of the present invention adopt in the process of Carbonization Preparation aluminium hydroxide with organic titanium salt solution by drip, stream adds or mode such as spraying is introduced, method is simple; Because titanium adds with ionic species, titanium distributes more even in surface of aluminum hydroxide behind the one-tenth glue simultaneously; The present invention introduces the titanium non-environmental-pollution with the organic solution form of organic titanium salt, is the ideal scheme that carbonizatin method is produced Ti-contained aluminium hydroxide.With this raw material is the competition that the preparing carriers catalyst will weaken titanium and reactive metal dramatically, improved the utilization rate of reactive metal, thereby catalyst activity is higher.
The specific embodiment
Material and the operating condition of the use in the concrete preparation process of Ti-contained aluminium hydroxide of the present invention can be same as the prior art, the main distinction be into the glue process with organic titanium salt by drip, stream adds or the form such as spraying is introduced, concrete steps comprise:
(1) preparation sodium metaaluminate and organic titanium salt solution;
(2) sodium aluminate solution for preparing and carbon dioxide are reacted into glue on one side under stirring condition, on one side by drip, stream adds or the form such as spraying is introduced organic titanium salt solution.
(3) solution filter, washing, drying namely make final Ti-contained aluminium hydroxide product after the cemented into bundles.
The concentration of above-mentioned sodium aluminate solution is 5～60g Al
2O
3/ l, Na and Al atomic ratio are 1.2～2.0.Above-mentioned organic titanium salt solution is selected from Ti (OC
4H
9)
4, Ti (OC
3H
7)
4, Ti (OC
2H
5)
4Ethanol or aqueous isopropanol, perhaps its their mixed solution.The organic titanium salt solution concentration is in titanium dioxide weight 10～100g/l.The addition of organic titanium salt solution is benchmark with final products, and wherein containing titanium dioxide is 0.1～20w%, is preferably 5～15w%.Become the glue temperature to be controlled at 10～45 ℃ according to the porous of needed Ti-contained aluminium hydroxide, concentration of carbon dioxide is controlled at 10～50v%.Be controlled to the glue slurry pH value and be at 7.5～12 o'clock and stop logical carbon dioxide, the control slurry pH value is higher than the titanium salt solution interpolation in 0～3 o'clock of final one-tenth glue rear slurry pH value and finishes.Stop can to wear out behind the logical carbon dioxide and also can not wear out, ageing time is no more than at most 2 hours.The filter cake that obtains behind the dope filtration spends deionised water 1～5 time, contains Na in the aluminium hydroxide of preparation
+By weight＜0.05%, following dry 2～12 hours 80～180 ℃ of temperature then.Drip and add and above becoming the glue jar, to add with stream, organic titanium salt solution after spray pattern preferably will atomize is dispersed in into glue with in the carbon dioxide containing gas, and the organic titanium salt solution after the atomizing becomes glue to react with carbon dioxide with sodium aluminate solution in becoming the glue jar.
Take the Ti-contained aluminium hydroxide of the inventive method preparation as raw material, make hydrogenation catalyst, be specially adapted to residual hydrocracking through moulding-roasting-dipping-roasting process or through kneading-moulding-roasting process or through kneading-moulding-roasting-dipping-roasting process through conventional method.Roasting condition is usually 350～800 ℃ of following roastings of air atmosphere 1～10 hour.
Further describe technical characterictic of the present invention below by comparative example and embodiment, but be not limited to embodiment.
Embodiment 1
Be 30g Al with concentration
2O
3/ l, Na and Al atomic ratio are that 1.4 sodium aluminate solution 500mL places reactor, and 25 ℃ of temperature pass into the carbon dioxide that concentration is 40v%, and in logical carbon dioxide, dripping concentration under stirring is 50g TiO
2Ti (the OC of/l
4H
9)
4Aqueous isopropanol 35ml, be 11 o'clock Ti (OC at slurry pH value
4H
9)
4Aqueous isopropanol dropwise, be to stop logical carbon dioxide at 10 o'clock to slurry pH value.Aging 1.0 hours of slurries.Filter then, spend deionised water, in carrier, contain Na
+By weight＜during 0.05w% till, dry (120 ℃) 4 hours are crushed to 180 orders again, promptly make product A of the present invention.
Embodiment 2
Compare with embodiment 1, sodium aluminate solution concentration is become 20g Al
2O
3/ l, dropping concentration is 50gTiO
2The organic titanium salt solution 23ml of/l, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product B.
Embodiment 3
Compare with embodiment 1, sodium aluminate solution concentration is become 10g Al
2O
3/ l adds concentration as 50g TiO take spray pattern
2The organic titanium salt solution 12ml of/l, the organic titanium salt solution atomization is dispersed in into glue with in the carbon dioxide containing gas, carbon dioxide enters into glue reactor and sodium aluminate solution reaction jointly with organic titanium salt solution, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example products C.
Embodiment 4
Compare with embodiment 1, sodium aluminate solution concentration is become 5g Al
2O
3/ l, dropping concentration is 50gTiO
2Ti (the OC of/l
3H
7)
4Aqueous isopropanol 6ml, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product D.
Embodiment 5
Compare with embodiment 1, it is 50g TiO that stream adds concentration
2Ti (the OC of/l
2H
5)
4Aqueous isopropanol 55ml, becoming the glue temperature is 35 ℃, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. the routine product E of cost.
Embodiment 6
Compare with embodiment 1, sodium aluminate solution Na and Al atomic ratio are become 1.6, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product F.
Embodiment 7
Compare with embodiment 1, becoming glue slurry during pH value is to stop logical carbon dioxide, while Ti (OC at 9 o'clock
4H
9)
4Aqueous isopropanol dropwise, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product G.
Embodiment 8
Compare with embodiment 1, becoming glue slurry during pH value is to stop to lead to carbon dioxide in 8 o'clock, is 10 o'clock Ti (OC at slurry pH value
4H
9)
4Aqueous isopropanol dropwise, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product H.
Embodiment 9
Compare with embodiment 1, becoming glue slurry during pH value is to stop to lead to carbon dioxide in 7.5 o'clock, is 9 o'clock Ti (OC at slurry pH value
4H
9)
4Aqueous isopropanol dropwise, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product I.
Comparative example 1
This comparison example is to prepare carrier by the method that CN1324687A describes.
Be 30g Al with concentration
2O
3The sodium aluminate solution 500mL of/l places reactor, and 25 ℃ of temperature pass into the carbon dioxide that concentration is 40v%, and the concentration that adds pulp under continuous stirring is 20g TiO
2/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ m) make carrier contain TiO
2Be 10% by weight, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product J.
Above-mentioned material sees Table 1 through the character of 500 ℃ of roastings after 3 hours.
Each routine product physicochemical property of table 1
| Physicochemical property | Pore volume ml/g | Specific surface m 2/g | Decentralization I Ti/I Al | TiO 2w％ |
| A | 0.98 | 368 | 0.34 | 10.4 |
| B | 1.01 | 369 | 0.35 | 10.3 |
| C | 1.08 | 375 | 0.35 | 10.7 |
| D | 0.97 | 370 | 0.34 | 10.7 |
| E | 0.99 | 362 | 0.33 | 15.5 |
| F | 0.98 | 365 | 0.34 | 10.3 |
| G | 1.07 | 378 | 0.14 | 10.4 |
| H | 1.15 | 376 | 0.19 | 10.4 |
| I | 1.01 | 365 | 0.35 | 10.4 |
| J | 0.85 | 364 | 0.19 | 10.3 |
As can be seen from Table 1, in the process of Carbonization Preparation aluminium hydroxide, drip mode such as organic titanium salt solution and introduce titanium, can make titanium become big in the decentralization value of surface of aluminum hydroxide, it is more even to illustrate that titanium disperses on the surface of aluminium hydroxide, and the pore volume of Ti-contained aluminium hydroxide and Bi Biao are long-pending simultaneously all improves.The assay method of metal dispersity is X-ray photoelectron spectroscopy among the present invention, and decentralization numerical value is more big, illustrates that the dispersion of metal in aluminium oxide is more even.
Claims (7)
1, a kind of preparation method of Ti-contained aluminium hydroxide, prepare sodium aluminate solution and organic titanium salt solution earlier, then sodium aluminate solution and the carbon dioxide for preparing is reacted into glue under stirring condition, it is characterized in that sodium aluminate solution becomes glue reaction with carbon dioxide when with organic titanium salt solution with drip, stream adds or Sprayable adds, solution filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product after the cemented into bundles;
Wherein said organic titanium salt solution is selected from Ti (OC
4H
9)
4, Ti (OC
3H
7)
4, Ti (OC
2H
5)
4Ethanol or aqueous isopropanol, perhaps their mixed solution; The concentration of organic titanium salt solution is counted 10～100g/l with titanium dioxide weight; The addition of organic titanium salt solution is take final products as benchmark, and wherein containing titanium dioxide is 0.1～20w%.
2, in accordance with the method for claim 1, the concentration that it is characterized in that described sodium aluminate solution is 5～60g Al
2O
3/ l, Na and Al atomic ratio are 1.2～2.0.
3, in accordance with the method for claim 1, it is characterized in that described one-tenth glue temperature is 10～45 ℃.
4, in accordance with the method for claim 1, the concentration that it is characterized in that described carbon dioxide is 10～50v%.
5, in accordance with the method for claim 1, it is characterized in that it is to stop logical carbon dioxide at 7.5～12 o'clock that the process control of described one-tenth glue becomes the glue slurry pH value.
6, in accordance with the method for claim 1, it is characterized in that described organic titanium salt solution is higher than the interpolation in 0～3 o'clock of final one-tenth glue rear slurry pH value at slurry pH value and finishes.
7, in accordance with the method for claim 1, it is characterized in that described the washing to aluminium hydroxide contains Na
+By weight＜0.05%, drying condition is following dry 2～12 hours at 80～180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100507436A CN1325166C (en) | 2004-10-29 | 2004-10-29 | Method for preparing titanium containing aluminium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100507436A CN1325166C (en) | 2004-10-29 | 2004-10-29 | Method for preparing titanium containing aluminium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1765514A CN1765514A (en) | 2006-05-03 |
| CN1325166C true CN1325166C (en) | 2007-07-11 |
Family
ID=36741753
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100507436A Active CN1325166C (en) | 2004-10-29 | 2004-10-29 | Method for preparing titanium containing aluminium hydroxide |
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289069B (en) * | 2013-06-06 | 2015-05-13 | 东华大学 | Aluminum-titanium composite catalyst for polyester polycondensation and preparation method of same |
| CN110639484B (en) * | 2019-09-25 | 2020-12-29 | 山东金滢新材料有限公司 | Preparation method of pseudo-boehmite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312785A (en) * | 1979-04-06 | 1982-01-26 | Uop Inc. | Process for the conversion of aromatic hydrocarbons |
| CN1324687A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of titanium-containing aluminium bydroxide |
-
2004
- 2004-10-29 CN CNB2004100507436A patent/CN1325166C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312785A (en) * | 1979-04-06 | 1982-01-26 | Uop Inc. | Process for the conversion of aromatic hydrocarbons |
| CN1324687A (en) * | 2000-05-19 | 2001-12-05 | 中国石油化工集团公司 | Prepn. of titanium-containing aluminium bydroxide |
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|---|---|
| CN1765514A (en) | 2006-05-03 |
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