CN1102432C - Ti-contained aluminium hydroxide and its preparing process and application - Google Patents
Ti-contained aluminium hydroxide and its preparing process and application Download PDFInfo
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- CN1102432C CN1102432C CN99113284A CN99113284A CN1102432C CN 1102432 C CN1102432 C CN 1102432C CN 99113284 A CN99113284 A CN 99113284A CN 99113284 A CN99113284 A CN 99113284A CN 1102432 C CN1102432 C CN 1102432C
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- titanium
- value
- aluminium hydroxide
- salt solution
- slurries
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Abstract
The present invention discloses a method for preparing a titanium-containing aluminium hydroxide and an application thereof. Titanium oxide is led into aluminium hydroxide monohydrate, and simultaneously, not only is the uniform distribution of titanium oxide on the surface of alumina guaranteed, but also the influence of the process on the microstructure of alumina is prevented. When used for catalyst carriers and hydrogenation catalysts, the titanium-containing aluminium hydroxide has favorable physicochemical indexes and service performance.
Description
1, technical field
The present invention relates to a kind of Ti-contained aluminium hydroxide and its production and use, particularly relate to a kind of titanium at the aluminium hydroxide table and Ti-contained aluminium hydroxide that uniform distribution and aluminium hydroxide structure are not damaged and its production and use.
2, background technology
Usually, the hydrotreating catalyst of hydrocarbon feed is all with γ～Al
2O
3Or contain γ～Al of a small amount of one or more other elements such as Si, P, Ti, B, Mg, F etc.
2O
3Be carrier.In catalyst preparation process, can in system, introduce above-mentioned element in different steps, but the purpose of introducing above-mentioned element is a basically identical, i.e. regulating catalyst acid and/or improve interaction between active ingredient and carrier.To γ～Al
2O
3In to introduce the method for titanium more, selected to contain titanium species also varied, even have the people directly to add TiO in aluminum oxide
2, rely on the high temperature migration then in the hope of its homodisperse at alumina surface.These class methods are feasible to the preparing carriers process of most catalyzer, because carrier does not contain active ingredient in the process, promptly do not have competition when titanium and aluminum oxide interaction.And in some Catalyst Production process, as kneading method and " mix-soaking " combined techniques (CN1098433A; US5089453) etc., because the intervention of active ingredient, each species and aluminum oxide precursor-aluminium hydroxide, the competition during interaction is that inevitably this will weaken TiO
2To the promoter action of catalyst performance, so be necessary to prepare homodisperse Ti-contained aluminium hydroxide.
EP0339640 has announced a kind of method of prepared by co-precipitation titanium-contained aluminum oxide, can prepare and disperse titanium-contained aluminum oxide preferably, but all there is body phase retention problems in coprecipitation method, thereby can not give full play to TiO
2Promoter action to catalyst performance.Coprecipitation method is that two kinds of materials precipitate simultaneously in addition, therefore will coordinate deposition condition, makes two kinds of materials reach certain sedimentation speed, will make two kinds of throw outs reach certain physical and chemical performance simultaneously, to satisfy service requirements.But identical deposition condition can not be the best deposition condition of two kinds of materials simultaneously, especially concerning aluminum oxide, often to regulate its physical and chemical indexes according to the requirement of using, one of them main control method changes deposition condition exactly, and another kind of material can not be before adaptation under the different deposition condition of a kind of material, can satisfy the deposition condition of himself.Briefly, the condition of co-precipitation is not the best deposition condition of two kinds of materials sometimes simultaneously, has therefore caused the ineffective activity of coprecipitation method, and then has used and limited to.
3, summary of the invention
The purpose of this invention is to provide the aluminium hydroxide that a kind of titanium is evenly distributed, supply raw materials, the Preparation method and use of the aluminium hydroxide that a kind of titanium is evenly distributed is provided simultaneously for the production of associated catalysts.
Ti-contained aluminium hydroxide of the present invention, its preparation process is for precipitating titanium salt in aluminum hydroxide slurry.
In the above-mentioned Ti-contained aluminium hydroxide, be benchmark with titanium dioxide and aluminum oxide wherein, titanium dioxide accounts for 0.1～10% by weight.
The preparation method of Ti-contained aluminium hydroxide of the present invention may further comprise the steps:
(1) it is neutral or alkaline regulating aluminum hydroxide slurry pH value;
(2) titanium salt solution is added in the above-mentioned slurries, the pH value of keeping slurries in the mixing process simultaneously is for neutral or alkaline;
(3) filter above-mentioned slurries, filter cake washing, drying.
PH value described in above-mentioned steps (1) and (2) is 7～11, be preferably 7～8, and under agitation condition, carry out, wherein pH's regulates with ammoniacal liquor, ammonia concn is preferably 0.2～10%, titanium salt solution and ammoniacal liquor add simultaneously, also can make wherein a kind ofly to add, but the pH value that will keep slurries in whole process are 7～11 in batches.Titanium salt solution is selected from the soluble titanium salts solution, as titanium trichloride aqueous solution, titanium sulfate aqueous solution, aqueous solution of titanyle sulfate, the titanium oxychloride aqueous solution or its mixing solutions, titanium salt solution concentration counts 1～5% with titanium dioxide weight, preferably continues after titanium salt solution adds to stir 0.1～2 hour.The filter cake washing that obtains behind the dope filtration 1～5 time, following dry 2～12 hours at 80～180 ℃ then.Wherein the aluminum hydroxide slurry consumption that can be mixed and made into water with commercially available aluminium hydroxide water can be 5～10 times of aluminium hydroxide weight, also can be the new life's that settling step obtains in the aluminum oxide production process aluminium hydroxide, wherein can contain 6～18% Al by weight
2O
3
With Ti-contained aluminium hydroxide of the present invention is raw material, can make titanium-contained aluminum oxide carrier through moulding, roasting, or with kneading method and mix and to pinch-flood the bonded method and make hydrogenation catalyst, be specially adapted to kneading method or mixedly pinch-flood the bonded method and make Hydrobon catalyst.Zhi Bei catalyzer consists of thus: Tungsten oxide 99.999 and or molybdenum oxide, 15～25%; Cobalt oxide and/or nickel oxide, 3～10%; Titanium oxide, 1～8%; Surplus is aluminum oxide.Can suitably adjust each components contents at different raw material (as: various distillates, secondary processing oil and residual oil etc.), or introduce proper assistant.
Titanium is evenly distributed in the Ti-contained aluminium hydroxide of the present invention, and less to the microtexture and the physico-chemical property influence of raw aluminum hydroxide, its X-ray diffraction pattern and raw aluminum hydroxide are basic identical.The support of the catalyst physico-chemical property that uses Ti-contained aluminium hydroxide of the present invention to make as raw material is close with the raw aluminum hydroxide that does not add titanium, even has further improved the physical and chemical performance of carrier, and pore distribution is concentrated more, specific surface area further strengthens.Use the catalyst for hydrotreatment of residual oil of the titaniferous preparation of aluminium hydroxide of the present invention to have good hydrodesulfurization activity.The preparation method of Ti-contained aluminium hydroxide of the present invention under the prerequisite that keeps the raw aluminum hydroxide physical and chemical performance, make titanium at the surface of aluminum hydroxide uniform distribution, this has not only maximally utilised titanium resource, and weakened the competition of titanium and reactive metal dramatically, improved the utilization ratio of reactive metal, the inventive method goes for various aluminium hydroxide raw materials in addition, has improved the scope of application of the inventive method greatly.
4, description of drawings
Fig. 1 is the x-ray diffraction style of each embodiment sample.
Further specify technical solution of the present invention by the following examples.
5, embodiment
Embodiment 1
Take by weighing 298g and contain Al
2O
3The aluminium hydrate powder of 67w% stirs down, adds 3000cm
3Water in, make slurries; Continue to stir Dropwise 5 % ammoniacal liquor 37cm in above-mentioned slurries
3, slurry pH value is 7.35; Continue to stir, in above-mentioned slurries, add 5% ammoniacal liquor and 2.8% simultaneously (with TiO
2Meter) titanium sulfate solution, pH value of solution value fluctuation between 7.5～9.0 all the time in the process; When the titanium sulfate solution add-on reaches 635cm
3The time (5% ammonia volume is 496cm
3), stop adding solution, continue to stir 0.5 hour, then with above-mentioned dope filtration, the gained filter cake is with water purification pulping and washing 4 times, 120 ℃ dry 6 hours down, pulverize dry sample, promptly make the alleged product of the present invention.Its X-ray diffraction pattern is 1.
Embodiment 2
Compare with embodiment 1, reduce the titanium sulfate solution add-on to 204cm
3(the add-on 120cm of 8% ammoniacal liquor
3), filter cake pulping and washing 2 times, 150 ℃ were descended dry 4 hours, and the unclassified stores consumption is identical with embodiment 1 with operational condition, i.e. the cost example.The X-ray diffraction pattern is 2.
Embodiment 3
Get and contain Al
2O
3One water-aluminum hydroxide slurries 3200cm of the nascent state of 6.3w%
3(water-aluminum hydroxide slurries of this routine selected nascent state are in the carbonic acid gas and sodium aluminate solution makes), slurry pH value was 9.35 (need not add weak ammonia); Continue to stir, in above-mentioned slurries, add 5% ammoniacal liquor and 3.4% simultaneously (with TiO
2Meter) titanium sulfate solution, pH value of solution value fluctuation between 8.0～10.0 all the time in the process; When the titanium sulfate solution add-on reaches 600cm
3The time (5% ammonia volume is 608cm
3), stop adding solution, continue to stir 1.5 hours, then with above-mentioned dope filtration, the gained filter cake is with water purification pulping and washing 3 times, 120 ℃ dry 6 hours down, pulverize dry sample, promptly make the alleged product of the present invention.The X-ray diffraction pattern is 3.
Comparative example 1
The charging capacity of each material is all identical with embodiment 1, just adds weak ammonia earlier, adds titanium sulfate solution (final solution pH value is 7.68) again, i.e. the cost example.The X-ray diffraction pattern is 4.
Comparative example 2
The charging capacity of each material is all identical with embodiment 1, just adds titanium sulfate solution earlier, adds weak ammonia (final solution pH value is 7.78) again, i.e. the cost example.The X-ray diffraction pattern is 5.
Comparative example 3
The charging capacity of each material is all close with embodiment 1, just with 14g (TiO
2Content is 65%) micron order metatitanic acid powder substitutes titanium sulfate solution, and adding a little weak ammonia, to make final solution pH value be 7.58, i.e. cost example.The X-ray diffraction pattern is 6.
Comparative example 4
This example is for without adding the aluminium hydrate powder that titanium is handled, and is raw materials used in promptly above each example.The X-ray diffraction pattern is 7.
Embodiment 4
Under 540 ℃, above-mentioned each sample roasting was obtained support of the catalyst in 3 hours.Its physico-chemical parameter is listed in table 1.
Table 1 data declaration by the inventive method, is introduced the process of titanium oxide in a water-aluminum hydroxide, less to the influence of aluminum oxide microtexture (micropore character).The aluminum oxide microtexture of embodiment 1,2 prepared aluminum oxide microtextures and comparative example 4 is very approaching, and the more former aluminum oxide of aluminum oxide micropore size distribution after this handles is slightly concentrated, and surface-area also slightly increases; The aluminum oxide microtexture of comparative example 1,3 and the aluminum oxide microtexture of comparative example 4 are also comparatively approaching, but its titanium is undesirable in the degree of scatter of alumina surface, and the result as shown in Figure 1.Opposite with above each example, the preparation process of comparative example 2 is bigger to the microtexture influence of aluminum oxide.The result of Fig. 1 shows, its contained dispersion state of titanium-contained aluminum oxide by the inventive method preparation is best, anatase octahedrite acromion in the x-ray diffraction style of embodiment 1,2,3 (1,2,3) (2 θ=25.200deg.) not obvious, and the anatase octahedrite acromion is comparatively remarkable in the diffraction pattern of each comparative example (4,5,6).
The physico-chemical property of each embodiment carrier of table 1
Embodiment 5
| Physico-chemical property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Pore volume, cm 3/g | 0.71 | 0.72 | 0.82 | 0.73 | 0.44 | 0.69 | 0.70 |
| Specific surface area, m 2/g | 348 | 341 | 371 | 337 | 379 | 321 | 332 |
| 6～10nm pore volume integration rate, % | 42 | 40 | 38 | 39 | 27 | 35 | 38 |
| TiO 2，w％ | 8.14 | 2.68 | 8.08 | 8.21 | 8.08 | 4.51 | 0.00 |
With Ti-contained aluminium hydroxide 300g (butt 71.5%) gram of embodiment 1, with 91gMoO
3, 65g basic nickel carbonate, 34gHAc and 6g extrusion aid mix and pinch, extruded moulding after 120 ℃ of following dryings, 560 ℃ of roastings 3 hours, obtains a kind of catalyst for hydrotreatment of residual oil.At hydrogen dividing potential drop 14.7MPa, LHSV0.33h
-1, H
2/ oil volume ratio is 1000, handles isolated island vacuum residuum (sulphur 2.5%, nitrogen 0.65%, carbon residue 15.6%) under the processing condition that temperature of reaction is 400 ℃, and its desulfurization degree is 90%, and denitrification percent is 59%, and taking off carbon yield is 65%.Illustrate that the catalyzer that uses Ti-contained aluminium hydroxide of the present invention to make as raw material has good use properties.
Claims (10)
1, a kind of preparation method of Ti-contained aluminium hydroxide may further comprise the steps:
(1) it is neutral or alkaline regulating aluminum hydroxide slurry pH value, and wherein the concentration of aluminum hydroxide slurry is to contain 6～18% Al by weight
2O
3
(2) titanium salt solution is added in the above-mentioned slurries, the pH value of keeping slurries in the mixing process simultaneously is for neutral or alkaline, wherein the concentration of titanium salt solution counts 1～5% with titanium dioxide weight, the add-on of titanium salt solution be titanium dioxide account for titanium dioxide and aluminum oxide gross weight 0.1～10%;
(3) filter above-mentioned slurries, filter cake washing, drying.
2,, it is characterized in that the pH value described in the step (1) is 7～11 according to the method for claim 1.
3,, it is characterized in that the pH value described in the step (2) is 7～11 according to the method for claim 1.
4,, it is characterized in that step (1) and (2) carry out under agitation condition according to the method for claim 1.
5,, it is characterized in that step (1) and (2) are to use ammoniacal liquor to regulate the pH value of slurries according to the method for claim 1.
6,, it is characterized in that the titanium salt solution described in the step (2) is selected from titanium trichloride aqueous solution, titanium sulfate aqueous solution, aqueous solution of titanyle sulfate, the titanium oxychloride aqueous solution or its mixing solutions according to the method for claim 1.
7,, it is characterized in that the drying conditions described in the step (3) is 80～180 ℃, 2～12 hours time of drying according to the method for claim 1.
8,, it is characterized in that described pH value is 7～8 according to the method for claim 2 or 3.
9,, it is characterized in that described ammonia concn is 0.2～10% by weight according to the method for claim 5.
10, according to the method for claim 1, it is characterized in that titanium salt solution adds in the step (2) after, continue to stir 0.1～2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113284A CN1102432C (en) | 1999-09-29 | 1999-09-29 | Ti-contained aluminium hydroxide and its preparing process and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113284A CN1102432C (en) | 1999-09-29 | 1999-09-29 | Ti-contained aluminium hydroxide and its preparing process and application |
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| Publication Number | Publication Date |
|---|---|
| CN1289636A CN1289636A (en) | 2001-04-04 |
| CN1102432C true CN1102432C (en) | 2003-03-05 |
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ID=5276491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113284A Expired - Lifetime CN1102432C (en) | 1999-09-29 | 1999-09-29 | Ti-contained aluminium hydroxide and its preparing process and application |
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| CN113828289B (en) * | 2020-06-23 | 2023-12-08 | 中国石油化工股份有限公司 | Composite oxide carrier, hydrofining catalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122772A (en) * | 1994-06-24 | 1996-05-22 | 住友化学工业株式会社 | Process for preparing fine-particulate metal, hydroxide comprising aluminum hydroxide as a major component, and fine-particulate metal oxide comprising aluminum oxide as a major component |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
-
1999
- 1999-09-29 CN CN99113284A patent/CN1102432C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122772A (en) * | 1994-06-24 | 1996-05-22 | 住友化学工业株式会社 | Process for preparing fine-particulate metal, hydroxide comprising aluminum hydroxide as a major component, and fine-particulate metal oxide comprising aluminum oxide as a major component |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
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|---|---|
| CN1289636A (en) | 2001-04-04 |
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