CN111153770A - Method for preparing high-purity aluminum alkoxide - Google Patents
Method for preparing high-purity aluminum alkoxide Download PDFInfo
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- CN111153770A CN111153770A CN202010032009.6A CN202010032009A CN111153770A CN 111153770 A CN111153770 A CN 111153770A CN 202010032009 A CN202010032009 A CN 202010032009A CN 111153770 A CN111153770 A CN 111153770A
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- aluminum
- aluminum alkoxide
- alkoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
Abstract
The invention belongs to the technical field of chemical industry, and provides a method for preparing high-purity aluminum alkoxide, which comprises the following steps of C3～C8The monohydric alcohol and the metal aluminum are synthesized into aluminum alkoxide under the catalysis of aluminum trichloride or aluminum isopropoxide, a solvent and a settling agent are added into the crude aluminum alkoxide, and then centrifugal separation is carried out at more than 1000 r/min; and distilling the clear liquid obtained by centrifugal separation, and distilling out unreacted substances and the solvent to obtain a product, namely the high-purity aluminum alkoxide. Said addition to the crude aluminum alkoxideThe solvent is C3～C8Monohydric alcohol of (1), C5～C8One of an alkane or petroleum ether; the settling agent added into the crude aluminum alkoxide is one or a mixture of pseudo-boehmite, aluminum sol and deionized water. The preparation process is not affected by the easy hydrolysis and easy decomposition of aluminum alkoxide, and can be stably operated for a long time.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a method for preparing high-purity aluminum alkoxide.
Background
Aluminum alkoxide is a very important chemical intermediate, and is mostly used for preparing high-purity alumina and nano-grade alumina; it can also be used as a reducing agent, a dehydrating agent, a catalyst, etc. Research on a preparation method of aluminum alkoxide has been carried out for more than one hundred years by researchers, and the method is approximately as follows: alcohol reacts with metal aluminum under the catalytic action of alkoxide, mercury, mercuric chloride or aluminum chloride and the like to generate aluminum alkoxide; since the metal aluminum used contains impurities such as iron and silicon, the crude aluminum alkoxide produced by the reaction needs to be purified by removing the impurities. There are many purification methods of aluminum alkoxide, including distillation under reduced pressure, filtration, magnetic separation-assisted filtration, and the like. Such as:
CN1238253C proposes a method for removing trace iron in aluminum alkoxide by boiling point modulation vacuum distillation, which comprises using industrial aluminum ingot as raw material, and reacting with alcohol to generate aluminum alkoxide. Adding a trace amount of conversion agent in the alkoxide synthesis process, converting low-boiling-point iron-containing impurities generated in the alkoxide synthesis process into high-boiling-point iron-containing compounds, then carrying out reduced pressure distillation by utilizing the low boiling point property of the alkoxide, and achieving the purpose of removing the iron impurities by collecting 80-90 wt.% of fractions. Vacuum distillation is the most conventional purification method of aluminum alkoxide, but under the condition of vacuum distillation, the temperature of the aluminum alkoxide material in a distillation kettle is more than 180 ℃; under the high-temperature condition, aluminum alkoxide can be decomposed and polymerized, and the generated light components enter a vacuum system to influence the sealing property and the service life of a vacuum pump; the polymer formed forms a scale at the bottom of the still, which seriously affects the heat transfer efficiency and productivity.
JP04-244037 (Kyoho chemical industry Co., Ltd.) discloses a method of producing high purity aluminum isopropoxide by reacting isopropanol with metallic aluminum using toluene, xylene and benzene as solvents and then filtering. The filtering method overcomes the inconvenience brought by the distillation method, but the used aromatic hydrocarbon is harmful to human bodies and has higher requirements on labor protection conditions.
CN1046526C proposes a preparation method of low-carbon alkoxy aluminum, which is characterized in that 30-50% of excessive C is added1～C4Reacting low-carbon alcohol and metal aluminum at 80-180 ℃ for 4-24 h in the presence of aluminum chloride, mercury chloride or a low-carbon alkyl aluminum catalyst, evaporating excessive low-carbon alcohol, and filtering while keeping the reactant in a liquid state, so that the problems of long-term stable production, low product yield and the like caused by a distillation method are solved.
CN106673038B discloses a preparation method of aluminum alkoxide, which comprises the step of reacting alcohol with aluminum to generate corresponding aluminum alkoxide, wherein the alcohol, the aluminum and trimethylbenzene are subjected to synthesis reaction under the condition of an external magnetic field, and the external magnetic field intensity is 5-100 kA/m, preferably 10-50 KA/m. And filtering by using a ceramic filter after the reaction is finished, thereby obtaining the high-purity aluminum alkoxide.
The filtering method can overcome the problem of thermal decomposition of aluminum alkoxide in the distillation method, but the aluminum alkoxide is easily hydrolyzed when meeting water or moist gas, so that the filter needs to be under the anhydrous condition for a long time, otherwise, nano particles generated by alkoxide hydrolysis easily block the filter; in addition, the crude aluminum alkoxide contains a large amount of solid particles (aluminum, silicon, iron, etc.) which also easily cause clogging of the filter; therefore, the filtration operation requires frequent acid washing to clean the filter. In addition to the distillation and filtration methods described above, there are also crystallization and extraction methods, both of which are very time consuming and are not suitable for popularization in industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the traditional aluminum alkoxide purification method and invent a method for preparing high-purity aluminum alkoxide.
The technical scheme of the invention is as follows:
a process for preparing high-purity aluminium alkoxides C3～C8The monohydric alcohol and the metallic aluminum are heated and refluxed to synthesize aluminum alkoxide under the catalytic action of aluminum trichloride or aluminum isopropoxide; adding a solvent and a settling agent into the crude aluminum alkoxide, and then carrying out centrifugal separation at a centrifugal separation speed of more than 1000 revolutions per minute.
The settling agent added into the crude aluminum alkoxide is one or a mixture of more than two of pseudo-boehmite, aluminum sol and deionized water, and the addition amount is less than 0.01 time of the mass of the crude aluminum alkoxide.
The solvent added into the crude aluminum alkoxide is C3～C8Monohydric alcohol of (1), C5～C8Is added in an amount of less than 2 times the mass of the crude aluminum alkoxide.
The invention has the beneficial effects that: after the synthesis of the crude aluminum alkoxide is finished, a solvent and a settling agent are added, and high-speed centrifugal separation is adopted to remove solid impurities such as iron, silicon and the like in the crude alkoxide.
Detailed Description
The following detailed description of the invention will be made in conjunction with the accompanying drawings
Example 1
Putting 50g of aluminum sheet, 180g of isopropanol and 3g of aluminum isopropoxide into a three-neck flask with the volume of 0.5L, heating and refluxing, adding 90g of petroleum ether with the boiling range of 60-90 ℃ and 1g of pseudo-boehmite into a product after refluxing for 8h, uniformly mixing, averagely transferring the mixture to 4 100mL centrifuge tubes, putting the centrifuge tubes into a centrifuge, centrifuging for 5 min at 10000 r/min, quickly transferring a clear solution into the 0.5L three-neck flask after the centrifugation is stopped, heating and distilling at normal pressure, controlling the temperature of materials in the three-neck flask to be not higher than 120 ℃, carrying out reduced pressure distillation (the absolute pressure is not higher than 0.01MPa) after no fraction below 100 ℃ flows out, controlling the temperature of materials in the three-neck flask to be not higher than 120 ℃, stopping heating and reducing pressure after no fraction below 100 ℃ flows out, and obtaining a high-purity aluminum isopropoxide in the three-neck flask.
Example 2
Putting 25g of aluminum sheet, 111g of sec-butyl alcohol and 0.5g of anhydrous aluminum trichloride into a three-neck flask with the volume of 0.5L, heating and refluxing, adding 120g of sec-butyl alcohol and 0.5g of water into a product after refluxing for 12h, uniformly mixing, averagely transferring the product into 4 100mL centrifuge tubes, putting the centrifuge tubes into a centrifuge, centrifuging for 5 minutes at 2000 r/min, quickly transferring a clear solution into the three-neck flask with the volume of 0.5L after the centrifugation is stopped, heating and distilling at normal pressure, controlling the temperature of materials in the three-neck flask to be not higher than 150 ℃, performing reduced pressure distillation (the absolute pressure is not higher than 0.01MPa) after no distillate flow at the temperature of below 100 ℃, stopping heating and reducing pressure after no distillate flow at the temperature of below 100 ℃, and obtaining the high-purity aluminum sec-butoxide in the three-neck flask.
Example 3
25g of aluminum sheet, 195g of isooctanol and 0.5g of anhydrous aluminum trichloride are taken and put into a three-neck flask with the volume of 0.5L, then heating reflux is carried out, 300g of isooctanol and 1g of pseudo-boehmite are added into the product after reflux is carried out for 12h, the mixture is evenly mixed and averagely transferred into 8 centrifuge tubes with the volume of 100mL, then the centrifuge tubes are put into a centrifuge for 5 minutes at 6000 r/min, clear liquid is rapidly transferred into the three-neck flask with the volume of 1L after the centrifugation is stopped, reduced pressure distillation is carried out (the absolute pressure is not higher than 0.01MPa), the temperature of materials in the three-neck flask is controlled to be not higher than 180 ℃, when no distillate with the temperature of below 100 ℃ flows out, the heating and the pressure reduction are stopped, and the product in the three-neck flask is high-purity.
Example 4
50g of aluminum sheet, 222g of sec-butyl alcohol and 0.5g of anhydrous aluminum trichloride are taken and put into a three-neck flask with the volume of 0.5L, then heating reflux is carried out, 200g of isopropanol, 1g of pseudoboehmite and 0.5g of water are added into a product after reflux is carried out for 12h, the mixture is evenly mixed and averagely transferred into 8 100mL centrifuge tubes, then the centrifuge tubes are put into a centrifuge for centrifuging for 5 min at 1200 r/min, clear liquid is rapidly transferred into the 1L three-neck flask after the centrifugation is stopped, heating and normal pressure distillation are carried out, the temperature of materials in the three-neck flask is controlled to be not higher than 150 ℃, reduced pressure distillation (the absolute pressure is not higher than 0.01MPa) is carried out after no fraction below 100 ℃ is discharged, heating and reduced pressure are stopped after no fraction below 100 ℃, and the product in the three-neck flask is high-purity aluminum alkoxide.
Example 5
50g of aluminum sheet, 180g of isopropanol and 3g of aluminum isopropoxide are placed into a three-neck flask with the volume of 0.5L, then heating reflux is carried out, 250g of sec-butyl alcohol and 0.2g of deionized water are added into a product after reflux is carried out for 8 hours, the mixture is evenly mixed and averagely transferred into 8 centrifuge tubes with 100mL, then the centrifuge tubes are placed into a centrifuge, centrifugation is carried out for 5 minutes at 9000 r/min, clear liquid is rapidly transferred into a 1L three-neck flask after the centrifugation is stopped, heating is carried out for normal pressure distillation, the temperature of materials in the three-neck flask is controlled to be not higher than 160 ℃, reduced pressure distillation (the absolute pressure is not higher than 0.01MPa) is carried out after no distillate with the temperature of 100 ℃ is separated out, heating and reduced pressure are stopped after no distillate with the temperature of 100 ℃ is separated out, and the product in the three-neck flask is high-purity aluminum alkoxide.
Claims (3)
1. A process for producing a high-purity aluminum alkoxide, characterized by comprising preparing a crude aluminum alkoxide, adding a solvent and a precipitant to the crude aluminum alkoxide, and then conducting centrifugal separation at a centrifugal separation rate of 1000 rpm or more.
2. The method of claim 1, wherein the precipitation promoter is one or more of pseudoboehmite and alumina sol deionized water, and the addition amount is less than 0.01 times of the mass of the crude aluminum alkoxide.
3. The method according to claim 1 or 2, wherein the solvent added to the crude aluminum alkoxide is C3～C8Monohydric alcohol of (1), C5～C8Is added in an amount of less than 2 times the mass of the crude aluminum alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010032009.6A CN111153770A (en) | 2020-01-13 | 2020-01-13 | Method for preparing high-purity aluminum alkoxide |
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| CN202010032009.6A CN111153770A (en) | 2020-01-13 | 2020-01-13 | Method for preparing high-purity aluminum alkoxide |
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Citations (5)
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|---|---|---|---|---|
| CN103145535A (en) * | 2013-03-25 | 2013-06-12 | 北京化工大学 | Diethylene glycol ferrous alkoxide with three-dimensional pattern multi-stage structure and preparation method thereof |
| CN106365188A (en) * | 2016-08-26 | 2017-02-01 | 孟玲 | Preparation device of micron-sized aluminum oxide powder |
| CN106380476A (en) * | 2016-08-29 | 2017-02-08 | 北京百灵威科技有限公司 | Filtration method for removing solid impurities in organometallic reagent or solution |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN109448998A (en) * | 2018-10-23 | 2019-03-08 | 陕西国防工业职业技术学院 | A kind of dye-sensitized solar cells are to electrode and preparation method thereof |
-
2020
- 2020-01-13 CN CN202010032009.6A patent/CN111153770A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145535A (en) * | 2013-03-25 | 2013-06-12 | 北京化工大学 | Diethylene glycol ferrous alkoxide with three-dimensional pattern multi-stage structure and preparation method thereof |
| CN106365188A (en) * | 2016-08-26 | 2017-02-01 | 孟玲 | Preparation device of micron-sized aluminum oxide powder |
| CN106380476A (en) * | 2016-08-29 | 2017-02-08 | 北京百灵威科技有限公司 | Filtration method for removing solid impurities in organometallic reagent or solution |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN109448998A (en) * | 2018-10-23 | 2019-03-08 | 陕西国防工业职业技术学院 | A kind of dye-sensitized solar cells are to electrode and preparation method thereof |
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| 刘杰等: "螯合-蒸馏法脱除异丙醇铝中痕量铁研究", 《大连理工大学学报》 * |
| 孟翔丽等: "《工科基础化学系列现代化学基础实验》", 31 December 2015 * |
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