CN1325157C - Method for preparing large aperture aluminium hydroxide contained titanium and silicon - Google Patents
Method for preparing large aperture aluminium hydroxide contained titanium and silicon Download PDFInfo
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- CN1325157C CN1325157C CNB2004100507440A CN200410050744A CN1325157C CN 1325157 C CN1325157 C CN 1325157C CN B2004100507440 A CNB2004100507440 A CN B2004100507440A CN 200410050744 A CN200410050744 A CN 200410050744A CN 1325157 C CN1325157 C CN 1325157C
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Abstract
The present invention discloses large-pore diameter aluminium hydroxide containing titanium and silicon composite auxiliary agents and a preparation method thereof. The preparation method not only ensures the uniform distribution of titanium and silicon on the surface of aluminium hydroxide but also enables the aluminium hydroxide containing titanium and silicon to have fine granule, large pore volume, specific surface area and average pore diameter by ultrasonic waves when the titanium and the silicon are introduced in the aluminium hydroxide. The aluminium hydroxide containing titanium and silicon has good physicochemical index and service performance when used as a catalyst carrier and a hydrogenation catalyst.
Description
Technical field
The present invention relates to aluminium hydroxide of a kind of large aperture titaniferous, silicon composite assistant and preparation method thereof, particularly relate to a kind of titanium, silicon surface of aluminum hydroxide evenly distribute and roasting after product have the titaniferous of more large pore volume, specific area and average pore size, aluminium hydroxide of silicon and preparation method thereof.
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.Therefore, develop more high activity and optionally catalyst for hydrotreatment of residual oil be development person's huge challenge.And develop more high activity and optionally the means of catalyst normally develop new catalyst carrier material and select the noble metal catalyst component.Introduce various auxiliary agents in the exploitation of new material in aluminium hydroxide is the constantly directions of research of people always.The purpose that everybody introduces one or more elements such as Si, P, Ti, B, Mg, F etc. is consistent substantially, i.e. regulating catalyst acid and/or improve active component and carrier interactions.But in catalyst preparation process, add certain or more auxiliary agent can make the catalyst preparation process complexity, or cause problem such as shaping of catalyst difficulty; In the support material production process, just add the needed auxiliary agent of preparation catalyst, can make catalyst preparation process simple, more effectively physicochemical property such as the acidity of modulation carrier, porous and then more effectively regulating catalyst acid and/or improve active component and carrier interactions also can reduce the problem of environmental pollution in the catalyst preparation process simultaneously.
The method for preparing the large aperture carrier has much been announced a kind of macropore γ-Al as CN1087289A
2O
3The preparation method of carrier places the high temperature roasting with the carrier precursor; CN1160602A adds physics and chemical enlargement agent, and high-temperature roasting obtains then; EP0097740 adopts hydro-thermal treatment method to come reaming.Their deficiency is not contain corresponding adjuvants, acidity a little less than, the physicochemical property of carrier is not improved.
EP0339640 has announced a kind of method of prepared by co-precipitation titanium-contained aluminum oxide, can prepare to disperse Ti-contained aluminium hydroxide preferably, but all there is body phase retention problems in coprecipitation, thereby can not gives full play to the facilitation of TiO2 to catalyst performance.Coprecipitation is that two kinds of materials precipitate simultaneously in addition, therefore will coordinate deposition condition, makes two kinds of materials reach certain settling velocity, will make two kinds of sediments reach certain physical and chemical performance simultaneously, to satisfy user demand.But identical deposition condition can not be the best deposition condition of two kinds of materials simultaneously, especially concerning aluminium oxide, often to regulate its physical and chemical indexes according to instructions for use, one of them main control method is to change deposition condition, 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, has therefore caused the ineffective activity of coprecipitation, and then has used and limited to.If it is difficult more that the preparation of employing the method contains the aluminium hydroxide of two or more auxiliary agent; Its preparation process is used the soluble titanium salting liquid, produces acid mist in cost height and the preparation process, contaminated environment, etching apparatus.
CN1289636A has announced a kind of method that titanium salt prepares Ti-contained aluminium hydroxide that precipitates in aluminum hydroxide slurry, can prepare and disperse Ti-contained aluminium hydroxide preferably, but owing to contain Cl in the titanium salt solution
-And SO
4 2-Plasma, etching apparatus, and become γ-Al at Aluminium hydroxide roasting
2O
3The time can produce gaseous contamination environment such as chlorine and sulfur dioxide; CN1350882A has announced that a kind of carbonizatin method adds the method for levigate metatitanic acid and silicon-containing compound formulations prepared from solutions titaniferous, silicon aluminium hydroxide for this reason, although reduced environmental pollution, 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, and titanium and the distribution of silicon in aluminium hydroxide also can be uneven, can cause its serviceability to reduce.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of titanium and silicon surface of aluminum hydroxide evenly distribute and roasting after product have the titaniferous of more large pore volume, specific area and bigger average pore size, aluminium hydroxide of silicon and preparation method thereof.
Product contains titanium dioxide 1～20w% behind the Aluminium hydroxide roasting of titaniferous of the present invention, silicon, is preferably 5～15w%, contains silica 1～20w%, is preferably 2～15w%, and pore volume is 0.9～1.2ml/g, and specific surface is 360～450m
2/ g, average pore size is 10～15nm, the decentralization I of titanium on aluminium oxide
Ti/ I
AlBe more than 0.3, be generally 0.3～0.4, the decentralization I of silicon on aluminium oxide
Si/ I
AlBe more than 0.2, to be generally 0.2～0.3.
The preparation of aluminium hydroxide process of titaniferous of the present invention, silicon is as follows:
Sodium aluminate solution, titanium-containing compound slurries, silicon-containing compound solution and carbon dioxide are reacted into glue under stirring condition, the aluminium hydroxide product that filter, drying can make titaniferous of the present invention, silicon, characteristics such as have behind the Aluminium hydroxide roasting of this titaniferous, silicon that titanium, silicon are evenly distributed, average pore size, specific area and pore volume are big.Wherein become the glue process under the ultrasonic wave effect, to carry out.Frequency of ultrasonic is 10～180kHz, and preferred 20～100kHz, ultrasonic power proportionately glue volume of material count 0.01～20W/mL, preferred 0.05～10W/mL.
Use ultrasonic wave to introduce cheap titanium and silicon compound in the process of the aluminium hydroxide employing Carbonization Preparation aluminium hydroxide of titaniferous of the present invention, silicon.Preparation process does not have the discharge of pollutant, non-environmental-pollution; When ultrasonic wave was propagated in medium, because concentration of energy, sound wave and medium effect can make medium that many physical changes take place simultaneously.For example, the sawtooth waveforms effect that produces owing to the non-linearity of ultrasonic vibration has pulverization, can make alumine hydroxide colloid and titanium-containing compound particle become thinner, titanium in prepared titaniferous, the aluminium hydroxide of silicon and silicon distribute more even in surface of aluminum hydroxide.In addition, because action of ultrasonic waves, changed size, shape and accumulation mode that aluminium hydroxide becomes primary particle in the glue course of reaction, made final products have bigger pore volume, specific area and average pore size, character is more even.Because titanium and silicon are evenly distributed in surface of aluminum hydroxide, carrier has higher acidity and average pore size, be preparing carriers hydro-conversion and/or hydrodenitrogeneration, take off the competition that the carbon residue catalyst will weaken titanium, silicon and reactive metal dramatically with this raw material, improved the utilization rate of reactive metal, thereby catalyst activity is higher.
The specific embodiment
The material and the operating condition of the use in the concrete preparation process of the aluminium hydroxide of titaniferous of the present invention and silicon can be same as the prior art, and the main distinction is into the glue process carries out under the ultrasonic wave effect, and concrete steps comprise:
(1) preparation sodium aluminate solution, titanium-containing compound slurries, silicon-containing compound solution;
(2) sodium aluminate solution, titanium-containing compound slurries, silicon-containing compound solution and carbon dioxide are reacted into glue under stirring condition, material solution or slurries mix the back feed carbon dioxide become glue or wherein a kind of, two or three when feeding carbon dioxide, add into glue continuously, close ultrasonic transducer and stop to feed carbon dioxide after becoming glue to finish, become the glue process under the ultrasonic wave effect, to carry out;
(3) the liquid-solid mixture of (2) step gained is filtered filter cake washing, drying.
The concentration of above-mentioned sodium aluminate solution is 5～60g Al
2O
3/ l.Above-mentioned titanium-containing compound slurries become granularity less than 65 μ m slurry like material by titanium-containing compounds such as metatitanic acid, titanium dioxide through adding water mill, and thin up is 5～40gTiO then
2/ l, its pH value is adjusted to 7～11, is preferably 7～8, and carries out under stirring condition, and its pH value is suitable regulates with ammoniacal liquor, and ammonia concn is preferably 0.1～20w%.The addition of titanium-containing compound slurries is benchmark with final products, and wherein containing titanium dioxide is 0.1～20w%, is preferably 4～15w%.Above-mentioned silicon-containing compound solution is sodium silicate solution or silicon sol solution, and concentration is 5～40gSiO
2/ l.Silicon-containing compound solution addition is benchmark with final products, and wherein containing silica is 1～20w%, is preferably 2～15w%.Become the glue temperature to be controlled at 10～45 ℃ according to the porous of the aluminium hydroxide of needed titaniferous and silicon, concentration of carbon dioxide is controlled at 10～50v%.Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbon dioxide.Can wear out and also can not wear out, ageing time is no more than 2 hours at most.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.
The adding mode of various material solutions and slurries can specifically be selected as required, and as can be in the following ways: (1) feeds sodium aluminate solution with carbon dioxide, adds titanium-containing compound slurries and/or silicon-containing compound solution with certain flow simultaneously; (2) with sodium aluminate solution with after titanium-containing compound slurries and/or silicon-containing compound solution mix, feed carbon dioxide and become glue; (3) carbon dioxide is fed in titanium-containing compound slurries and/or the silicon-containing compound solution, add sodium aluminate solution simultaneously continuously.
With the titaniferous of the inventive method preparation and the aluminium hydroxide of silicon is raw material, make hydrogenation catalyst, be specially adapted to residual hydrocracking through moulding-roasting-dipping-roasting process or through mixed pinching-moulding-roasting process or through mixed pinching-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
With concentration is 30gAl
2O
3The sodium aluminate solution 500mL of/l places ultrasonic transducer, and control ultrasonic transducer transmitting power is 25kHz for the 200W frequency, 15 ℃ of temperature, and feeding concentration is the carbon dioxide of 40v%, the concentration that adds pulp under continuous stirring is 20gTiO
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; Adding concentration is 20SiO
2The sodium silicate solution of/l, making carrier contain silica is 8.0% by weight.Continue feeding carbon dioxide, is to stop logical carbon dioxide at 10 o'clock until slurry pH value, and aging 1.0 hours of slurries are closed ultrasonic transducer.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, it is 25kHz that the ultrasonic transducer transmitting power is become the 50W frequency, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product B.
Embodiment 3
Compare with embodiment 1, it is 50kHz that the ultrasonic transducer transmitting power is become the 800W frequency, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example products C.
Embodiment 4
Compare with embodiment 1, improve the TiO in the carrier
2Content is 15%, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product D.
Embodiment 5
Compare with embodiment 1, improve the SiO in the carrier
2Content is 15%, and the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product E.
Comparative example 1
This comparison example is to prepare carrier by the method that CN1289636A describes.
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, Dropwise 5 % ammoniacal liquor and 2.8% is (with TiO in above-mentioned slurries
2Meter) titanium sulfate solution, the pH value of solution value is fluctuation between 7.5～9 in the process; When the titanium sulfate solution addition reaches 635 cm
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, be crushed to 180 orders again, i.e. cost example product F.
Comparative example 2
This comparison example is to prepare carrier by the method that CN1350882A describes.
Compare with embodiment 1, stop ultrasonic transducer emission ultrasonic wave, the unclassified stores consumption is identical with embodiment 1 with operating condition, i.e. cost example product G.
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 | Average pore size/nm | Meleic acid mmol/g | Decentralization I Ti/I Al | Decentralization I Si/I Al | TiO 2 w％ | SiO 2 w％ |
| A | 1.12 | 365 | 12.3 | 0.35 | 0.33 | 0.23 | 10.4 | 8.1 |
| B | 1.08 | 356 | 12.2 | 0.38 | 0.35 | 0.25 | 10.3 | 8.0 |
| C | 1.04 | 345 | 12.1 | 0.36 | 0.37 | 0.26 | 10.4 | 8.2 |
| D | 0.99 | 337 | 11.8 | 0.35 | 0.33 | 0.22 | 15.3 | 7.9 |
| E | 1.05 | 342 | 12.3 | 0.42 | 0.32 | 0.23 | 10.2 | 15.1 |
| F | 0.71 | 328 | 9.0 | 0.15 | 0.21 | - | 9.4 | - |
| G | 0.91 | 317 | 11.5 | 0.34 | 0.19 | 0.18 | 10.3 | 8.1 |
As can be seen from Table 1, in the process of Carbonization Preparation aluminium hydroxide, use ultrasonic wave to introduce titanium and silicon, the pore volume of aluminium hydroxide, specific area all and average pore size become big; The infrared acid number of carrier also becomes big; Titanium and silicon also become greatly in the decentralization value of surface of aluminum hydroxide simultaneously, illustrate that titanium and silicon disperse more even on the surface of aluminium hydroxide.
The assay method of metal dispersity is an X-ray photoelectron spectroscopy among the present invention, and decentralization numerical value is big more, illustrates that the dispersion of metal in aluminium oxide is even more.
Claims (14)
1, the aluminium hydroxide of a kind of titaniferous and silicon is characterized in that containing titanium dioxide 1～20w% behind the Aluminium hydroxide roasting of this titaniferous and silicon, and silica 1～20w%, pore volume are 0.9～1.2ml/g, and specific surface is 360～450m
2/ g, average pore size is 10～15nm, the decentralization I of titanium on aluminium oxide
Ti/ I
AlBe more than 0.3, the decentralization I of silicon on aluminium oxide
Si/ I
AlBe more than 0.2.
2, according to the described aluminium hydroxide of claim 1, it is characterized in that described content of titanium dioxide is 5～15w%, dioxide-containing silica is 2～15w%, the decentralization I of titanium on aluminium oxide
Ti/ I
AlBe 0.3～0.4, the decentralization I of silicon on aluminium oxide
Si/ I
AlBe 0.2～0.3.
3, the preparation method of the aluminium hydroxide of described titaniferous of a kind of claim 1 and silicon, it is characterized in that adopting following process: sodium aluminate solution, titanium-containing compound slurries, silicon-containing compound solution and carbon dioxide are reacted into glue under stirring condition, the aluminium hydroxide product that filter then, wash, drying promptly makes final titaniferous and silicon wherein becomes the glue process to carry out under the ultrasonic wave effect.
4, in accordance with the method for claim 3, it is characterized in that described frequency of ultrasonic is 10～180kHz, ultrasonic power proportionately glue volume of material is counted 0.01～20W/mL.
5, in accordance with the method for claim 3, it is characterized in that described frequency of ultrasonic is 20～100kHz, ultrasonic power proportionately glue volume of material is counted 0.05～10W/mL.
6, in accordance with the method for claim 3, the concentration that it is characterized in that described sodium aluminate solution is 5～60g Al
2O
3/ l, the titanium-containing compound slurries become granularity less than 65 μ m slurry like material by metatitanic acid, titanium dioxide through adding water mill, and thin up is 5～40g TiO
2/ l.
7, in accordance with the method for claim 6, the pH value that it is characterized in that described titanium-containing compound slurries is 7～11, and the addition of titanium-containing compound slurries is benchmark with final products, and wherein containing titanium dioxide is 1～20w%.
8, in accordance with the method for claim 3, it is characterized in that described silicon-containing compound solution is sodium silicate solution or silicon sol solution, concentration is 5～40g SiO
2/ l.
9, in accordance with the method for claim 3, silicon-containing compound solution addition is benchmark with final products, and wherein containing silica is 1～20w%.
10, in accordance with the method for claim 3, it is characterized in that described one-tenth glue temperature is 10～45 ℃, concentration of carbon dioxide is controlled at 10～50v%, is controlled to the glue slurry pH value and is at 9～12 o'clock and stop logical carbon dioxide.
11, in accordance with the method for claim 3, it is characterized in that described washing for spending deionised water 1～5 time, contains Na to the aluminium hydroxide of preparation
+By weight＜0.05%, drying is following dry 2～12 hours at 80～180 ℃.
12, in accordance with the method for claim 7, the addition that it is characterized in that described titanium compound slurries is benchmark with final products, and wherein containing titanium dioxide is 2～15w%.
13, in accordance with the method for claim 9, it is characterized in that described silicon-containing compound solution addition is benchmark with final products, wherein containing silica is 2～15w%.
14, the application of aluminium hydroxide in hydrogenation catalyst of described titaniferous of a kind of claim 1 and silicon, it is characterized in that with this Ti-contained aluminium hydroxide be raw material, make hydrogenation catalyst through moulding-roasting-dipping-roasting process or through mixed pinching-moulding-roasting process or through mixed pinching-moulding-roasting-dipping-roasting process, wherein roasting condition is 350～800 ℃ of following roastings of air atmosphere 1～10 hour.
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| CNB2004100507440A CN1325157C (en) | 2004-10-29 | 2004-10-29 | Method for preparing large aperture aluminium hydroxide contained titanium and silicon |
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| CN1765493A CN1765493A (en) | 2006-05-03 |
| CN1325157C true CN1325157C (en) | 2007-07-11 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327453B (en) * | 2007-06-20 | 2011-05-11 | 中国石油天然气集团公司 | Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst |
| CN102151582B (en) * | 2011-02-25 | 2013-07-03 | 中国海洋石油总公司 | Preparation method of hydrodesulfurization catalyst for high-nitrogen low-quality gasoline and diesel |
| CN103769069B (en) * | 2012-10-24 | 2016-12-21 | 中国石油化工股份有限公司 | The preparation method of silicon-containing alumina dry glue |
| CN103785480B (en) * | 2012-11-03 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of carbonizatin method prepares the method for the dry glue of high-silicon amorphous silica aluminum |
| CN104445317B (en) * | 2014-11-12 | 2016-09-14 | 中国海洋石油总公司 | A kind of preparation method of modified boehmite |
| CN105056924B (en) * | 2015-08-18 | 2017-08-15 | 南京大学 | A kind of Ti3+Adulterate non-precious metal catalyst preparation and its in the application of selective hydrogenation |
| CN106000329A (en) * | 2016-06-27 | 2016-10-12 | 含山县科宇环境工程有限公司 | High-performance adsorbent and preparation method thereof |
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 |
| CN1350882A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Macroreticular alumina carrier containing Si and Ti and its preparing process |
-
2004
- 2004-10-29 CN CNB2004100507440A patent/CN1325157C/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 |
| CN1350882A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Macroreticular alumina carrier containing Si and Ti and its preparing process |
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