CN1424296A - Method for catalytical synthesis of alkoxy aluminum from alcohol and aluminum - Google Patents
Method for catalytical synthesis of alkoxy aluminum from alcohol and aluminum Download PDFInfo
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- CN1424296A CN1424296A CN 02159143 CN02159143A CN1424296A CN 1424296 A CN1424296 A CN 1424296A CN 02159143 CN02159143 CN 02159143 CN 02159143 A CN02159143 A CN 02159143A CN 1424296 A CN1424296 A CN 1424296A
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Abstract
A process for catalytically synthesizing aloxylaluminium from alcohol and aluminium features that under the action of the compoiste catalyst consisting of iodine, organic soluble Ti salt and aloxyl aluminium compound, the C4-C10 alcohol and aluminium take part in catalytic reaction at 120-200 deg.c and -0.4 MPa for 1-6 hr. Its advantages are simple process, high output rate, and low cost.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a method for synthesizing alkoxy aluminum from alcohol and aluminum in a catalytic manner.
Background
The trialkoxy aluminum is called aluminum alkoxide for short as an important chemical intermediate, and has important application in chemical synthesis and preparation of special ceramics and high-purity alumina.
The synthesis method of alkoxy aluminium is a lot of researches carried out in the early fifties and sixties, the first Alfol method is to react ethylene with aluminium to generate triethyl aluminium, then to carry out telomerization and chain extension to generate high alkyl aluminium, to oxidize the aluminium into long-chain alkoxy aluminium in the air under a certain condition, and to realize industrialization in the seventies. If the method is used for preparing the aluminum oxide, a large amount of by-product high-carbon alcohol is generated in the subsequent process, and the method has the defects of long process flow, high investment, complex equipment and the like.
The method for producing alkoxy aluminium by aluminium reaction has the advantages of simple reaction, less investment in equipment and cyclic use of alcohol as by-product of alkoxy aluminium hydrolysis. The reaction formula is as follows:
in the above reaction, CnH2n+1OH, n is more than or equal to 6, so that the minimum dissolution of alcohol in water can be ensured. The alcohol reacts with aluminum in a strongly exothermic reaction with an exotherm of about 95Kcal per mole of aluminum. Releasing a large amount of hydrogen gas.
The use of catalysts for the preparation of aluminum alkoxides is described in detail in U.S. Pat. Nos. 263638865, 2666076, etc. Rex et al, the inventors added 1% mercuric chloride to alcohol and added large particles of aluminum to react in order to remove the oxide film on the metal surface. He also used FeCl in the experiments3、SnCl2、CuCl2、BrO3、I2The catalyst has certain effect. The invention of the U.S. patent 4745204 discloses that the reaction of 5-10 carbon alcohol with gallium or alloy of gallium and aluminum in a certain proportion as catalyst has higher reactivity, but the defect is that gallium metal is expensive and difficult to obtain, and simultaneously the reaction activity is increasedThe separation cost is increased, and the method is not suitable for large-scale industrial production.
Kobetz et al in US3717666 have invented the use of an alkoxy alcohol as a catalyst which is characterized by the absence of the need to mix metallic aluminum with mercury compounds, halogens, titanium, silicon, zirconium, sodium, etc., but which reacts well by physically cutting and pulverizing the aluminum sufficiently fine to avoid the inclusion of impurity elements.
In US3963482 Kondis et al, using a reactant alcohol as a medium, ball milling metallic aluminum powder to remove an oxide layer on the aluminum surface for activation, and filling an inert gas into a ball milling container to protect the metallic aluminum from reoxidation, points out: the oxidation of oxygen to the aluminum surface is fast, and a trace amount of oxygen can oxidize and bond the aluminum powder, so that the reaction is not fast performed.
At UGreco et al in S4670573 improved ball milling activation by directly ball milling activation of metal aluminum powder, charging inert gas into ball mill bottle, and adding trace amount of catalyst, such as HgCl2Butyl carbitol or sodium butyl carbitol. The aluminum surface is also coated by the catalyst while the aluminum surface is activated, and the aluminum surface is put into a reactor under the protection of inert gas to react with alcohol, so that the conversion rate is high and is about 90%.
The reaction of hexanol with aluminum made the reaction difficult to complete due to the oxide film on the aluminum. A comprehensive review ofthe patents shows that the conversion rate is low, and the purification of the reaction product is difficult, which directly influences the use effect of the aluminum alkoxide.
Disclosure of Invention
The invention provides a composite high-efficiency catalyst for solving the problems in the prior art, so that the reaction is carried out under a mild condition, the occurrence of side reactions is reduced to improve the yield of the product, and meanwhile, the components of the catalyst have little influence on the product of the aluminum alkyl.
The invention aims to prepare high-quality alkoxy aluminum by adopting a composite catalyst and enabling the reaction to be smoothly carried out at a lower temperature and a lower pressure. The final product can obtain high-quality alumina.
The metal aluminum used in the invention can be cut pin aluminum scraps, aluminum beans, aluminum powder and the like, and the purity of the metal aluminum is preferably more than 99%, so that the product can have lower impurity content. Hexanol is a common industrial product, such as natural alcohol, petrochemical fraction alcohol, etc., with a purity greater than 99%. The raw materials of the reaction are calculated according to the chemicalThe quantity ratio of aluminium to alcohol is 1: 1.1-1.8, the best is 1: 1.2-1.5, the reaction temperature is controlled at 120-200 deg.C, the best is 150-180 deg.C, the reaction pressure is controlled at 0.03-0.2MPa, the reaction time is 1-6 hours, the catalyst component can be formed from iodine element, organic soluble titanium salt and alkoxy compound. The titanium salt may be a titanium carboxylate, a titanium alkoxide, and other organic titanium. The alkoxy compound may be an aluminum alkoxide or the like. The ratio of them is 1: 0.01-0.1: 2-8. The addition amount of the catalyst is 5X10-3-5×10-1g/mol alcohol. The yield can reach 95 to 98 percent. If no effective catalyst is available, the reaction temperature is raised by 20-60 deg.C, the pressure is raised by 0.1-0.5MPa, and at the same time, many side reactions and carbonization phenomena are produced, so that the quality of the product is greatly reduced.
The invention adopts the following technical scheme:
the alcohol and aluminum catalyzed alkoxy aluminum synthesizing process features that alcohol and aluminum are reacted catalytically4-C10Alcohol and metal aluminium, iodine, organic soluble titanium salt and alkoxy aluminium compound are used as composite catalyst, the reaction temperature is 120-200 deg.C, reaction pressure is normal pressure-0.4 MPa, and the alkoxy aluminium is produced by catalytic reaction.
The invention can also adopt the following technical measures:
the method for synthesizing alkoxy aluminum by catalyzing alcohol and aluminum is characterized in that the organic soluble titanium salt of the composite catalyst is carboxylic acid titanium and alkoxy titanium.
The method for synthesizing the alkoxy aluminum by catalyzing the alcohol and the aluminum is characterized in that the alcohol is hexanol, and the ratio of the hexanol to the metal aluminum is 10-40% of the excess of the chemical reaction amount.
The method for synthesizing alkoxy aluminum by catalyzing alcohol and aluminum is characterized in that the ratio of hexanol to metallic aluminum is 15-25% of the excess of chemical reaction.
The method for synthesizing alkoxy aluminum by catalyzing alcohol and aluminum is characterized in that the metal aluminum is metal aluminum scraps, metal aluminum powder, aluminum ingots and recycled aluminum materials.
The method for synthesizing alkoxy aluminium by catalyzing alcohol and aluminium is characterized in that the component of the composite catalyst is iodine, the ratio of organic soluble titanium salt to alkoxy aluminium compound is 1: 0.01-0.1: 2-8, and the adding amount of the catalyst is 0.005-0.5g/mol alcohol.
The method for synthesizing the alkoxy aluminum by catalyzing the alcohol and the aluminum is characterized in that the reaction temperature is 150-180 ℃.
The method for synthesizing the alkoxy aluminum by catalyzing the alcohol and the aluminum is characterized in that the reaction pressure is 0.03-0.2 MPa.
The method for synthesizing the alkoxy aluminum by catalyzing the alcohol and the aluminum is characterized in that the reaction time is 1 to 6 hours.
The method for synthesizing the alkoxy aluminum by catalyzing the alcohol and the aluminum is characterized in that the reaction time is 2-4 hours.
The invention has the advantages and positive effects that:
the method has the advantages of carrying out the reaction under milder conditions, reducing the occurrence of side reactions, obtaining higher yield, having simple process, reducing the operation cost of product purification, and realizing the industrial production of the alkoxy aluminum synthesized by the alcohol and the aluminum in a catalytic manner.
Detailed Description
To further clarify the disclosure, features and advantages of the present invention, the following examples are set forth in the appended claims:
example 1
In a 2 liter autoclave with a stirrer and a condenser, 420 g of hexanol with the content of 99.5 percent is added, 28g of reagent metallic aluminum sheet is added, and 0.08g of composite catalyst with the weight ratio of iodine, titanium carboxylate and alkoxy aluminum of 1: 0.05: 5 is added. Heating to 120 ℃ to start reaction, maintaining the temperature at 180 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 99.2 percent based on the conversion calculation of the metal aluminum.
Example 2
In a 2 liter autoclave with a stirrer and a condenser, 420 g of hexanol with the content of 99.5 percent is added, 28g of metal aluminum powder is added, and 0.08g of composite catalyst with the weight ratio of iodine, titanium carboxylate and alkoxy aluminum being 1: 0.04: 4 is added. Heating to 160 ℃ to start reaction, maintaining the temperature at 180 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 96.1 percent based on the conversion calculation of the metal aluminum.
Example 3
In a 2 liter autoclave with a stirrer and a condenser, 420 g of hexanol with the content of 99.5 percent is added, 28g of metal aluminum powder is added, and 0.1g of composite catalyst with the weight ratio of iodine, titanium carboxylate and alkoxy aluminum of 1: 0.03: 5 is added. Heating to 160 ℃ to start reaction, maintaining the temperature at 180 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 98.0 percent based on the conversion calculation of the metal aluminum.
Example 4
In a 2 liter autoclave with a stirrer and a condenser, 420 g of hexanol with the content of 99.5 percent is added, 28g of metal aluminum powder is added, and 0.3g of composite catalyst with the weight ratio of iodine, titanium carboxylate and alkoxy aluminum being 1: 0.05: 4 is added. Heating to 140 ℃ to start reaction, maintaining the temperature at 180 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 98.7 percent based on the conversion calculation of the metal aluminum.
Example 5
Comparative example
Into a 2 liter autoclave equipped with a stirrer and a condenser, 420 g of hexanol having a content of 99.5% was charged, 28g of metal aluminum powder was added, and 0.1g of iodine was added. Heating to 180 ℃ to start reaction, maintaining the temperature at 200 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 78.8 percent based on the conversion calculation of the metal aluminum.
Example 6
Comparative example
Into a 2 liter autoclave equipped with a stirrer and a condenser, 420 g of hexanol having a content of 99.5% was charged, 28g of metal aluminum powder was added, and 0.5g of titanium butoxide was added. And (3) heating to 190 ℃ to start reaction, maintaining the temperature at 200 ℃, controlling the pressure at 0.04MPa, continuously reacting for 2 hours after hydrogen is amplified and measured out, cooling, and analyzing the reaction conversion rate to 71.9 percent based on the conversion calculation of the metal aluminum.
Claims (10)
1. The method for synthesizing the alkoxy aluminum by catalyzing alcohol and aluminum is characterized in that the alcohol and the aluminum are subjected to catalytic reaction, and the method comprises the following steps: c4-C10Alcohol and metallic aluminium, iodine, organic soluble titanium salt and alkoxy aluminium compound as composite catalyst, reaction temp. is 120-200 deg.C,the reaction pressure is normal pressure-0.4 Mpa, and the alkoxy aluminum is generated by catalytic reaction.
2. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the organic soluble titanium salt of the composite catalyst is titanium carboxylate and alkoxy titanium.
3. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the alcohol is hexanol, and the ratio of hexanol to metallic aluminum is 10-40% of the excess of the chemical reaction.
4. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 3, wherein: the ratio of hexanol to metallic aluminum is 15-25% excess of chemical reaction.
5. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the metal aluminum is metal aluminum scraps, metal aluminum powder, aluminum ingots and recycled aluminum materials.
6. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the composite catalyst consists of iodine, organic soluble titanium salt and alkoxy aluminum compound in the ratio of 1 to 0.01-0.1 to 2-8, andhas catalyst amount of 0.005-0.5g/mol alcohol.
7. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the reaction temperature is 150-180 ℃.
8. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the reaction pressure is 0.03-0.2 MPa.
9. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 1, wherein: the reaction time is 1-6 hours.
10. The alcohol and aluminum catalyzed process for the synthesis of aluminum alkoxides according to claim 9, wherein: the reaction time is 2-4 hours.
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| CN 02159143 CN1424296A (en) | 2002-12-30 | 2002-12-30 | Method for catalytical synthesis of alkoxy aluminum from alcohol and aluminum |
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| CN 02159143 CN1424296A (en) | 2002-12-30 | 2002-12-30 | Method for catalytical synthesis of alkoxy aluminum from alcohol and aluminum |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318363C (en) * | 2003-09-27 | 2007-05-30 | 章浩龙 | Method for fabricating aluminum alkoxide |
| CN111747825A (en) * | 2020-06-28 | 2020-10-09 | 云南靖创液态金属热控技术研发有限公司 | Preparation method of aluminum ethoxide |
-
2002
- 2002-12-30 CN CN 02159143 patent/CN1424296A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318363C (en) * | 2003-09-27 | 2007-05-30 | 章浩龙 | Method for fabricating aluminum alkoxide |
| CN111747825A (en) * | 2020-06-28 | 2020-10-09 | 云南靖创液态金属热控技术研发有限公司 | Preparation method of aluminum ethoxide |
| CN111747825B (en) * | 2020-06-28 | 2022-12-20 | 云南靖创液态金属热控技术研发有限公司 | Preparation method of aluminum ethoxide |
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