CN101912786A - Method for preparing aluminum hydroxide powder containing lanthanum-phosphorus elements - Google Patents
Method for preparing aluminum hydroxide powder containing lanthanum-phosphorus elements Download PDFInfo
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- CN101912786A CN101912786A CN 201010265982 CN201010265982A CN101912786A CN 101912786 A CN101912786 A CN 101912786A CN 201010265982 CN201010265982 CN 201010265982 CN 201010265982 A CN201010265982 A CN 201010265982A CN 101912786 A CN101912786 A CN 101912786A
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- lanthanum
- phosphorus
- aluminum hydroxide
- hydroxide powder
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Abstract
The invention relates to a method for preparing aluminum hydroxide powder containing lanthanum and phosphorus elements. The method is characterized by comprising the following steps of: preparing a sodium meta-aluminate solution; preparing a compound aqueous solution containing a phosphorus element; preparing a compound aqueous solution containing a lanthanum element; leading carbon dioxide gas into a mixed solution formed by the sodium metaaluminate solution, the compound aqueous solution containing the phosphorus element and the compound aqueous solution containing the lanthanum element for reacting to generate a precipitate; filtering a generated solid-liquid mixture; and washing, drying and pulverizing filtered solid to prepare the aluminum hydroxide powder containing the lanthanum and the phosphorus elements. In the prepared aluminum hydroxide powder containing the lanthanum and the phosphorus elements, because the elements of the lanthanum, the phosphorus and the aluminum are uniformly combined, a prepared aluminum hydroxide catalyst carrier containing the lanthanum and the phosphorus elements has moderate acid strength, higher heat resistance and larger pore volume and specific surface area compared with an aluminum xide catalyst carrier without the lanthanum and the phosphorus elements.
Description
Technical field
The present invention relates to a kind of preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements, belong to chemical catalyst area.
Background technology
Make the field at petrochemical catalyst, especially face hydrogen class catalyst, the high-purity hydrogen that adopts sodium aluminate solution and carbon dioxide reaction to produce is alumina powder jointed, is very general as the basic raw material of its catalyst carrier.Because the alumina powder jointed inherent characteristics of high-purity hydrogen, poor by its alumina catalyst carrier heat endurance that manufactures, under the normal pressure heating status, along with the raising of sintering temperature, its pore volume and specific area can be the trend that reduces along with the raising of temperature.The alumina support that major part is faced hydrogen class catalyst all requires through higher temperature roasting, to satisfy catalyst to its carrier surface acid strength and thing requirement mutually, and less pore volume and the specific area of alumina support, bigger again restriction the reactivity of catalyst and operation steady in a long-term.
In addition, when catalyst keeps higher catalytic activity, wish that more catalyst has good selectivity, in the Catalytic processes process of selecting hydrogenation, good selectivity even much more important than high activity.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of aluminum hydroxide powder containing lanthanum-phosphorus elements is provided, in preparation aluminium hydroxide powder course of reaction, a certain amount of lanthanum element and P elements have been introduced, contain lanthanum-phosphorus oxidation alumina supporter and have moderate surface acid intensity, it is under the normal pressure heating status, its heat endurance has also had bigger improving, promptly satisfied catalyst to alumina carrier surface acid strength and thing requirement mutually, satisfied it again the bigger pore volume of alumina support and the needs of specific area.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements is provided, and its feature may further comprise the steps:
(1) compound concentration is 10～45gAl
2O
3The sodium aluminate solution of/l;
(2) preparation phosphorus element-containing concentration is the compound water solution of the phosphorus element-containing of 0.1～10gP/l;
(3) preparation contains the compound water solution that contains lanthanum element that lanthanum element concentration is 0.1～10gLa/l;
(4) under stirring condition, carbon dioxide fed the compound water solution of sodium aluminate solution, phosphorus element-containing and contain in the mixed solution that the compound water solution of lanthanum element forms and react, generate sediment, this sedimentary consisting of: Al
2O
384～97.8wt%; La
2O
30.2～6.0wt%; P
2O
52～10wt%, in the course of reaction, feeding the carbon dioxide volumetric concentration is 10～40%, and after reaction finished, the pH value of mixed liquor was 8～12, and it is 5～40 ℃ that entire reaction course keeps reaction temperature;
(5) solid-liquid mixtures that produces in the step (4) is filtered, and wash leaching solid, dry, pulverize, make aluminum hydroxide powder containing lanthanum-phosphorus elements.
Phosphorus element-containing concentration is that the compound water solution of the phosphorus element-containing of 0.1～10gP/l is the phosphatic aqueous solution in the described step (2).The aqueous solution of preferably phosphoric acid ammonium dihydrogen or ammonium hydrogen phosphate wherein.Wherein phosphorus-containing compound solution preferably only joins in the sodium aluminate solution solution before feeding carbon dioxide.The adding that contains lanthanum compound solution is carried out joining in the reaction solution in the process in reaction, preferably at last stage reaction, joins in the reaction solution before the reaction terminating.
The compound water solution of phosphorus element-containing is made benchmark with product in the described step (2), and the content of P elements calculates according to phosphorus pentoxide, accounts for 2～10% of gross mass.Wherein phosphorus element content preferred 2～10%.
The compound water solution that contains lanthanum element in the described step (3) is the sulfate of lanthanum element, nitrate, acetate or the muriatic aqueous solution.
Described step contains in the compound water solution of lanthanum element in (3), makes benchmark with product, and the content of lanthanum element calculates according to lanthana, accounts for 0.2～6.0% of gross mass.Wherein lanthanum element content is preferably between 0.3～4%.
The compound water solution of phosphorus element-containing adds in carbon dioxide feeding process with the compound water solution that contains lanthanum element in the described step (4).
Wash temperature in the described step (5) is 50～80 ℃.Wherein preferred temperature is 60～75 ℃.
Sodium oxide content after the washing in the described step (5) in the product is less than 0.2wt%.Wherein sodium oxide content is preferably 0.03～0.1w%.
Drying mode in the described step (5) is that normal pressure is dynamically dry, and baking temperature is 50～150 ℃, and be 0.5～1.5 hour drying time.Wherein baking temperature is preferably 100～130 ℃, is preferably 0.7～1.2 hour drying time.
Pulverizing in the described step (5) is that air-flow is pulverized, and pulverizing the back product granularity is 80～300 orders.Wherein granularity is preferably the 120-200 order.
The concentration of above-mentioned sodium aluminate solution is 10～45gAl
2O
3/ l preferably is controlled at 15～35gAl
2O
3/ l.
The concentration of P elements is 0.1～10gP/l in the above-mentioned phosphorus element-containing compound water solution.
Keeping the carbon dioxide volumetric concentration in the above-mentioned reaction is 10～40%, wherein is preferably 15～35%.
It is 5～40 ℃ that entire reaction course keeps reaction temperature, wherein is preferably 15～30 ℃, and the pH value of reaction end is controlled at 8～12, is preferably 9～11.
The invention has the beneficial effects as follows: aluminum hydroxide powder containing lanthanum-phosphorus elements is to introduce the phosphorous lanthanum compound that contains in sodium aluminate solution and carbon dioxide reaction process, and preparation process technology is simple, and easy operating does not have contaminant exclusion, non-environmental-pollution; The aluminum hydroxide powder containing lanthanum-phosphorus elements of manufacturing is owing to lanthanum-phosphorus-aluminium element combination is very even, make the lanthanum-phosphorus elements alumina catalyst carrier of making that contains have moderate acid strength than the alumina catalyst carrier that does not contain lanthanum-phosphorus elements, higher hear resistance has bigger pore volume and specific area.
The specific embodiment
Embodiment 1
In reactor, add 10gAl
2O
3The sodium aluminate solution of/l is controlled at 40 ℃ with solution temperature.Stir down, adding concentration is the ammonium dihydrogen phosphate aqueous solution of 10gP/l.Leading to into, concentration is 10% (carbon dioxide v).When the pH value of reactant liquor to 12 the time, adding concentration is the lanthanum acetate aqueous solution of 0.1gLa/l.Stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
384wt%; La
2O
36.0wt%; P
2O
510wt% filters the sediment that generates, and washs at 50 ℃ with deionized water, and the sodium oxide content in the product of washing back is 0.2wt%.Under the temperature with 50 ℃ in dynamic drier, dry 1.5 hours.Dried product is crushed to 300 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 2
In reactor, add 45gAl
2O
3The sodium aluminate solution of/l is controlled at 5 ℃ with solution temperature.Stir down, adding concentration is the ammonium dibasic phosphate aqueous solution of 0.1gP/l.Leading to into, concentration is 40% (carbon dioxide v).When the pH value of reactant liquor to 9 the time, adding concentration is the lanthanum nitrate aqueous solution of 10gLa/l.Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 8 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
397.8wt%; La
2O
30.2wt%; P
2O
52wt% filters the sediment that generates, and 80 ℃ of washings, the sodium oxide content in the product of washing back is 0.03wt% with deionized water.Under the temperature with 150 ℃ in dynamic drier, dry 0.5 hour.Dried product is crushed to 80 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 3
In reactor, add 30gAl
2O
3The sodium aluminate solution of/l is controlled at 15 ℃ with solution temperature.Stir down, adding concentration is the ammonium dibasic phosphate solution of 7gP/l.Leading to into, concentration is 30% (carbon dioxide v).When the pH value of reactant liquor to 11 the time, adding concentration is the lanthanum acetate aqueous solution of 5gLa/l.Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 10 the time, stop reaction.The sediment that generates is consisting of of benchmark: Al with the product
2O
390wt%; La
2O
35.0wt%; P
2O
55wt% filters the sediment that generates, and 70 ℃ of washings, the sodium oxide content in the product of washing back is under the temperature of 0.07wt% with 120 ℃ in dynamic drier, dry 1.2 hours with deionized water.Dried product is crushed to 200 orders with airslide disintegrating mill, has both obtained product of the present invention.
Embodiment 4
In reactor, add 20gAl
2O
3The sodium aluminate solution of/l is controlled at 25 ℃ with solution temperature.Stir down, adding concentration is the ammonium dihydrogen phosphate of 3gP/l.Leading to into, concentration is 26% (carbon dioxide v).When the pH value of reactant liquor to 10 the time, adding concentration is the lanthanum nitrate aqueous solution of 2gLa/l.Continue to lead to into that carbon dioxide reacts, when the pH value of reactant liquor to 9 the time, stop reaction.The sediment that generates is the Al that consists of of benchmark with the product
2O
395wt%; La
2O
32.0wt%; P
2O
53wt% filters the sediment that generates, and 70 ℃ of washings, the sodium oxide content in the product of washing back is under the temperature of 0.05wt% with 110 ℃ in dynamic drier, dry 0.8 hour with deionized water.Dried product is crushed to 150 orders with airslide disintegrating mill, has both obtained product of the present invention.
Comparative Examples 1
In embodiment 1, except that do not phosphorate, the aqueous solution of lanthanum element compound, other course of reaction and controlled condition all remain unchanged.
Adopt the pure cerium hydroxide aluminium powder body that contains lanthanum-phosphorus aluminium hydroxide powder and Comparative Examples 1 preparation of embodiment 1～4 preparation respectively, be prepared into the alumina support sample.Take by weighing oxide weight respectively and be the aluminium hydroxide powders of 100 grams, add 4 gram sesbania powder, 3 gram glacial acetic acid and proper amount of deionized water, after mediating, cylindrical little of extrusion Φ 2.0.Little 120 ℃ of dryings placed 750 ℃ of roastings of Muffle furnace 4 hours after 4 hours.Have a power failure, reduce to normal temperature naturally, corresponding making contains lanthanum-phosphorus or pure alumina support sample.Under the same conditions, measure acid strength, pore volume and the specific area of these samples, the result lists in the table 1.
Table 1: the acid strength of alumina support, pore volume and specific area
| Sample number into spectrum | Total acid strength, mmolpy/g | Pore volume, ml/g | Specific area, m2/g |
| Embodiment 1 | 0.285 | 0.723 | 362 |
| Embodiment 2 | 0.213 | 0.715 | 358 |
| Embodiment 3 | 0.257 | 0.628 | 345 |
| Embodiment 4 | 0.235 | 0.696 | 346 |
| Comparative Examples 1 | 0.122 | 0.595 | 273 |
As can be seen from Table 1, under identical preparation condition, the aluminum hydroxide powder containing lanthanum-phosphorus elements production of the present invention preparation contain lanthanum-phosphorus oxidation alumina supporter, have bigger total acid strength, pore volume and specific area than pure alumina carrier.
Adopt infusion process, under the identical operations condition, on the alumina support of embodiment 1 and Comparative Examples 1, load 15 gram molybdenum oxides and 3 gram cobalt oxides are prepared into two clumsy hydrogenation catalysts respectively.With the clumsy fraction of coal tarization is raw material, in the hydrogen dividing potential drop of 2.5Mpa, and liquid air speed 1.0 o'clock
-1, hydrogen-oil ratio (v/v) 1000, under the process conditions that reaction temperature is 270 ℃, the gross activity of embodiment 1 catalyst is 92%, selectivity is 95%; The gross activity of Comparative Examples 1 catalyst is 83%, and selectivity is 78%.The catalyst that adopts aluminum hydroxide powder containing lanthanum-phosphorus elements of the present invention to make is described, has advantages of high catalytic activity and selectivity really.
Claims (10)
1. the preparation method of an aluminum hydroxide powder containing lanthanum-phosphorus elements, its feature may further comprise the steps:
(1) compound concentration is 10～45gAl
2O
3The sodium aluminate solution of/l;
(2) preparation phosphorus element-containing concentration is the compound water solution of the phosphorus element-containing of 0.1～10gP/l;
(3) preparation contains the compound water solution that contains lanthanum element that lanthanum element concentration is 0.1～10gLa/l;
(4) under stirring condition, carbon dioxide fed the compound water solution of sodium aluminate solution, phosphorus element-containing and contain in the mixed solution that the compound water solution of lanthanum element forms and react, generate sediment, this sedimentary consisting of: Al
2O
384～97.8wt%; La
2O
30.2～6.0wt%; P
2O
52～10wt%, in the course of reaction, feeding the carbon dioxide volumetric concentration is 10～40%, and after reaction finished, the pH value of mixed liquor was 8～12, and it is 5～40 ℃ that entire reaction course keeps reaction temperature;
(5) solid-liquid mixtures that produces in the step (4) is filtered, and wash leaching solid, dry, pulverize, make aluminum hydroxide powder containing lanthanum-phosphorus elements.
2. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the compound water solution that the middle phosphorus element-containing concentration of described step (2) is the phosphorus element-containing of 0.1～10gP/l is the phosphatic aqueous solution.
3. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1, it is characterized in that the compound water solution of phosphorus element-containing in the described step (2), make benchmark with product, the content of P elements, calculate according to phosphorus pentoxide, account for 2～10% of gross mass.
4. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1, the compound water solution that it is characterized in that containing in the described step (3) lanthanum element is sulfate, nitrate, acetate or the muriatic aqueous solution of lanthanum element.
5. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1, it is characterized in that containing in the compound water solution of lanthanum element in the described step (3), make benchmark with product, the content of lanthanum element, calculate according to lanthana, account for 0.2～6.0% of gross mass.
6. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the compound water solution of phosphorus element-containing in the described step (4) and the compound water solution that contains lanthanum element add in carbon dioxide feeding process.
7. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the wash temperature in the described step (5) is 50～80 ℃.
8. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the sodium oxide content in the product is less than 0.2wt% after the washing in the described step (5).
9. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the drying mode in the described step (5) is that normal pressure is dynamically dry, and baking temperature is 50～150 ℃, and be 0.5～1.5 hour drying time.
10. the preparation method of aluminum hydroxide powder containing lanthanum-phosphorus elements according to claim 1 is characterized in that the pulverizing in the described step (5) is that air-flow is pulverized, and pulverizing the back product granularity is 80～300 orders.
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| CN 201010265982 CN101912786A (en) | 2010-08-30 | 2010-08-30 | Method for preparing aluminum hydroxide powder containing lanthanum-phosphorus elements |
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|---|---|---|---|
| CN 201010265982 CN101912786A (en) | 2010-08-30 | 2010-08-30 | Method for preparing aluminum hydroxide powder containing lanthanum-phosphorus elements |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187705A (en) * | 2017-12-04 | 2018-06-22 | 天津大学 | A kind of Al of rare earth metal and phosphorus modified synergic2O3Particle and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033285A (en) * | 1987-11-22 | 1989-06-07 | 齐鲁石油化工公司研究院 | Low-voltage hydrogenation denitrification catalyst and uses thereof |
| JPH03146133A (en) * | 1989-11-02 | 1991-06-21 | Showa Shell Sekiyu Kk | Catalyst for dehydrogenating hydrocarbon and method of its manufacture |
| CN1448215A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Silicon-containing aluminium hydroxide and prep. thereof |
| CN1915485A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Alumina of containing additive |
-
2010
- 2010-08-30 CN CN 201010265982 patent/CN101912786A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033285A (en) * | 1987-11-22 | 1989-06-07 | 齐鲁石油化工公司研究院 | Low-voltage hydrogenation denitrification catalyst and uses thereof |
| JPH03146133A (en) * | 1989-11-02 | 1991-06-21 | Showa Shell Sekiyu Kk | Catalyst for dehydrogenating hydrocarbon and method of its manufacture |
| CN1448215A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Silicon-containing aluminium hydroxide and prep. thereof |
| CN1915485A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Alumina of containing additive |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187705A (en) * | 2017-12-04 | 2018-06-22 | 天津大学 | A kind of Al of rare earth metal and phosphorus modified synergic2O3Particle and preparation method thereof |
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Open date: 20101215 |