CN104355967A - Self-catalyzed one-step synthesis method of high-purity aluminum isopropoxide - Google Patents
Self-catalyzed one-step synthesis method of high-purity aluminum isopropoxide Download PDFInfo
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- CN104355967A CN104355967A CN201410631616.9A CN201410631616A CN104355967A CN 104355967 A CN104355967 A CN 104355967A CN 201410631616 A CN201410631616 A CN 201410631616A CN 104355967 A CN104355967 A CN 104355967A
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- 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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Abstract
The invention discloses a self-catalyzed one-step synthesis method of high-purity aluminum isopropoxide. The high-purity aluminum isopropoxide is synthesized in an autocatalysis manner by use of the high-purity aluminum isopropoxide as the catalyst. The high-purity aluminum isopropoxide is taken as the catalyst instead of HgCl2, AlCl3, I2, CuCl2 and the like to realize the autocatalysis of the aluminum isopropoxide synthesis process, and no impurity element is introduced so that the purity of the aluminum isopropoxide can be improved; and as a result, reliable raw material guarantee is provided for subsequent production of related high-purity materials by use of the aluminum isopropoxide.
Description
Technical field
The present invention relates to a kind of synthetic method of high puring aluminium isopropoxide, the synthetic method of a particularly a kind of step high puring aluminium isopropoxide autocatalysis, belongs to organo-aluminium alcoholate and catalyzes and synthesizes field.
Background technology
In recent years, metal alkoxide chemosynthesis development rapidly, has in the periodic table of elements and can synthesize alkoxide more than 60 elements, wherein has the alkoxide of 41 element synthesis to be applied to sol-gel method and prepares advanced ceramics material.Aluminium-alcohol salt, also known as aluminum alkoxide, can be divided into again according to the number of the carbon forming aluminium alcoholates alcohol used: low-carbon (LC) aluminium alcoholates is generally the low-carbon alcohol of 1 ~ 4 carbon atom; And be referred to as high-carbon aluminium alcoholates higher than 4 carbon atoms.Wherein by the low-carbon (LC) aluminium alcoholates for aluminum isopropylate extensively synthesized, it can be widely used in dewatering agent, catalyzer etc., in recent years, along with the development of catalytic chemistry, the Alumina gel prepared by aluminum isopropylate is widely used in the preparation of support of the catalyst activated alumina, and the high purity alumina powder purity being hydrolyzed preparation by high puring aluminium isopropoxide can reach 99.999%, is produce the effective method of laser crystals grade aluminum oxide at present, for aluminum isopropylate opens new Application Areas.
The building-up process of aluminum isopropylate is generally aluminium and Virahol generates aluminum isopropylate under the effect of catalyzer, and wherein conventional catalyzer has HgCl
2, AlCl
3, I
2deng, also there is report CuCl in recent years
2the synthesis of aluminum isopropylate is carried out as catalyzer.Publication number CN 1478767A(application number 02132824.2) Chinese patent literature disclose a kind of continuous production method of high puring aluminium isopropoxide, that aluminium and catalyst aid are added in synthesis reaction vessel, the aluminium wherein in batches added accounts for the 20-50% of material total amount, the add-on of catalyst aid accounts for material always 70-80%, in synthesis reaction vessel, Virahol is added with substantially invariable speed, wherein the add-on of Virahol accounts for the 20-30% of material total amount, reflux exchanger effluent air temp is at 27-29 DEG C, and reflux exchanger enters gas temperature at 72-75 DEG C.Application publication number CN 102826579 A(application number 201210350176.0) Chinese patent literature disclose one and prepare high-purity, superfine alumina powder method; the steps include: high-purity aluminium flake, Virahol and catalyzer to be injected in building-up reactions tower, generate gaseous state aluminum isopropylate; Liquid aluminum isopropylate is cooled to through condenser; (2) liquid aluminum isopropylate is injected underpressure distillation purification tank, flash to steam, enter liquefy ultra-high purity isopropanol aluminium after splice jug; (3) liquid ultra-high purity isopropanol aluminium is added in vacuum stirring-up drying machine, inject high purity water, issue raw hydrolysis reaction in circulating water condition, obtain ultra-pure aluminium hydroxide and isopropanol water solution; Dry in vacuum stirring-up drying machine; (4) ultra-pure aluminium-hydroxide powder is loaded in corundum crucible, calcination in electric pushed bat kiln.Application publication number CN 102992959 A(application number 201210466493.9) Chinese patent literature disclose a kind of method utilizing high water content Virahol to prepare aluminum isopropylate, comprise: in a kettle. drop into water-content higher than 0.3% Virahol, appropriate aluminum isopropylate is dropped in Virahol, abundant stirring 0.5 hour-1.0 hours, drop into metal aluminium flake, drop into catalyzer again, be heated to 82-100 DEG C, be back to after evaporant condensation in reactor, then continue fully to stir, make metal aluminium flake and isopropanol reaction.After metal aluminium flake complete reaction, heat up and excessive Virahol evaporated.Namely high puring aluminium isopropoxide is obtained.
Autocatalysis process is that reaction product has the catalytic process of promoter action to speed of response.The synthetic method of high puring aluminium isopropoxide autocatalysis rarely has report, and complicated operation, security is poor.
Summary of the invention
The invention provides a kind of synthetic method of a step high puring aluminium isopropoxide autocatalysis, the speed of reaction of building-up process can be improved with the method petrohol aluminium, improve catalytic efficiency, the high purity aluminum isopropylate of purity >=99.996% can be obtained simultaneously, and the method is simple to operate, be easy to industrialization, environmental friendliness, safe and reliable.
The solution of the present invention is: the method for autocatalysis one-step synthesis high puring aluminium isopropoxide, adopts high puring aluminium isopropoxide as catalyzer autocatalysis synthesis high puring aluminium isopropoxide.
Foregoing method, preferred scheme is, joins in reactor by high-purity aluminium flake and Virahol, adds high puring aluminium isopropoxide as catalyzer; Temperature of reaction kettle is heated to 100 ~ 110 DEG C (preferably, temperature of reaction kettle being heated to 105 DEG C) constant temperature 1.5-3.0h(is preferred, constant temperature 2.0h), reaction starts, and it is preferred to carry out condensing reflux 4 ~ 6h(to evaporant, condensing reflux 5h is carried out to evaporant), after question response terminates, temperature of reaction system is increased to 120 ~ 150 DEG C (preferred, temperature of reaction system to be increased to 135 DEG C), remaining Virahol is fully reacted, gets final product a step and obtain high puring aluminium isopropoxide.
Foregoing method, preferred scheme is, the high puring aluminium isopropoxide as catalyzer is after high-purity aluminium flake and anhydrous isopropyl alcohol catalyze and synthesize, the aluminum isopropylate of purity >=99.999% obtained of being purified by underpressure distillation mode again.
Foregoing method, preferred scheme is, the described high-purity isopropanol aluminum concentration as catalyzer is that 3 ~ 5mol/L(is preferred, and the described high-purity isopropanol aluminum concentration as catalyzer is 4mol/L).
Foregoing method, preferred scheme is, purity >=99.996% of described high-purity aluminium flake.
Foregoing method, preferred scheme is, described Virahol removes impurity through rectifying.
Foregoing method, preferred scheme is, end product high puring aluminium isopropoxide purity reaches 99.999%.
The invention provides a kind of synthetic method of a step high puring aluminium isopropoxide autocatalysis, high-purity aluminium flake and Virahol joined in reactor by a certain percentage, and add concentration be 3 ~ 5mol/L underpressure distillation purify after high puring aluminium isopropoxide as catalyzer; Thermotonus still heating temperatures is carried out constant temperature 2h to 80 ~ 90 DEG C, reaction turns off heating after starting, and condensing reflux 4 ~ 6h is carried out to evaporant, after question response terminates, temperature of reaction system is increased to 120 ~ 150 DEG C, remaining Virahol is fully reacted, and get final product a step and obtain high puring aluminium isopropoxide, its purity can reach 99.996%.
Concrete steps: the rafifinal taking certain mass is placed in three mouthfuls of round-bottomed flasks, add anhydrous isopropyl alcohol according to a certain ratio, according to molarity be 3 ~ 5mol/L add pressure distillation purify after high puring aluminium isopropoxide as catalyzer, after heating temperatures being carried out constant temperature 2h to 100 ~ 110 DEG C with electric heating cover, reaction starts, and to after reactive evaporation thing condensing reflux 4 ~ 6h, system temperature declines, reaction terminates, temperature of reaction system is increased to 120 ~ 150 DEG C, remaining Virahol is fully reacted, can obtain.
The invention discloses a kind of synthetic method of a step high puring aluminium isopropoxide autocatalysis, comprise the following steps: high-purity aluminium flake (purity >=99.996%) and Virahol are joined in reactor by a certain percentage, and add concentration be 3 ~ 5mol/L underpressure distillation purify after high puring aluminium isopropoxide as catalyzer; Thermotonus still heating temperatures is carried out constant temperature 2h to 100 ~ 110 DEG C, reaction starts, and condensing reflux 4 ~ 6h is carried out to evaporant, after question response terminates, temperature of reaction system is increased to 120 ~ 150 DEG C, remaining Virahol is fully reacted, get final product a step and obtain high puring aluminium isopropoxide, its purity can reach 99.996%.If carry out underpressure distillation operation to it, then can obtain the aluminum isopropylate of purity >=99.999%.
The present invention is from the different of conventional art:
Use high puring aluminium isopropoxide as catalyzer, realize the autocatalysis of aluminum isopropylate building-up process, instead of HgCl
2, AlCl
3, I
2, CuCl
2deng, self there is toxicity in these traditional catalyst, harmful on the one hand; Impurity element can be introduced in system on the other hand, reduce the purity of aluminum isopropylate.And in industrialization process, Cl
-to 304 stainless steel cauldron seriously corrodeds, not only can shorten the work-ing life of reactor, and impurity F e element can be introduced, reduce quality product further.The synthetic method of an a kind of step high puring aluminium isopropoxide autocatalysis of the present invention, adopt high puring aluminium isopropoxide as catalyzer, do not introduce impurity element, improve the purity of aluminum isopropylate, relevant high-purity material is produced to later use aluminum isopropylate, provides reliable raw material and ensure.And it is simple to operate, safe and reliable.
Embodiment
Now describe in detail to the present invention, protection domain is not by this restriction in conjunction with the embodiments:
Embodiment 1: the method for autocatalysis one-step synthesis high puring aluminium isopropoxide
(1) take the high-purity Al of 24g and be placed in there-necked flask;
(2) in 200ml anhydrous isopropyl alcohol, 130g Al (OPr is added
iso), be heated to 60 DEG C stir after, join in three mouthfuls of round-bottomed flasks;
(3) with electric heating cover, temperature is adjusted to 100 DEG C, question response system temperature reaches 85 DEG C of insulation 2h, and reaction stops heating after starting.
(4) reaction continues to carry out, and carries out condensing reflux 6h to evaporant, and system temperature declines, and reaction terminates.
Described reaction is thermopositive reaction, and after reaction starts, himself liberated heat, can meet reaction completely and continue to carry out.
(5) after reaction terminates, reopen heating jacket, temperature of reaction system is improved 120 DEG C, insulation 2h, has reacted fully.
Whole building-up process 12h consuming time completes, and building-up reactions transformation efficiency is 96%, and obtained high puring aluminium isopropoxide purity is 99.996%, and after carrying out underpressure distillation to it, aluminum isopropylate purity can reach 99.9992%.
The method of embodiment 2 autocatalysis one-step synthesis high puring aluminium isopropoxide
(1) take 24g and be placed in there-necked flask;
(2) in 200ml anhydrous isopropyl alcohol, 200g Al (OPr is added
iso), be heated to 80 DEG C stir after, join in three mouthfuls of round-bottomed flasks;
(3) temperature of electric mantle is adjusted to 110 DEG C, question response system temperature reaches 85 DEG C, carries out backflow 4h to evaporant, and reaction terminates.
(4), after reaction terminates, temperature of reaction system is brought up to 140 DEG C, reacted fully.
Whole building-up process 8h consuming time, building-up reactions transformation efficiency is 98%, and obtained high puring aluminium isopropoxide purity is 99.996%, and after carrying out underpressure distillation to it, aluminum isopropylate purity can reach 99.9994%.
The method of embodiment 3 autocatalysis one-step synthesis high puring aluminium isopropoxide
High-purity aluminium flake (purity >=99.996%) and Virahol (through rectifying removing impurity) are joined in reactor, add high puring aluminium isopropoxide (, high puring aluminium isopropoxide as catalyzer is after high-purity aluminium flake and anhydrous isopropyl alcohol catalyze and synthesize, purified by underpressure distillation mode again the aluminum isopropylate of purity >=99.999% obtained, concentration is 4mol/L) as catalyzer; Temperature of reaction kettle is heated to 105 DEG C, constant temperature 2.0h, reaction starts, and carries out condensing reflux 5h to evaporant, after question response terminates, temperature of reaction system is increased to 135 DEG C, remaining Virahol is fully reacted, get final product a step and obtain high puring aluminium isopropoxide.
Whole building-up process 6h consuming time, building-up reactions transformation efficiency is 99.2%, and obtained high puring aluminium isopropoxide purity is 99.996%, and after carrying out underpressure distillation to it, aluminum isopropylate purity can reach 99.9994%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the method for autocatalysis one-step synthesis high puring aluminium isopropoxide, is characterized in that, adopts high puring aluminium isopropoxide as catalyzer autocatalysis synthesis high puring aluminium isopropoxide.
2. method according to claim 1, is characterized in that, joins in reactor by high-purity aluminium flake and Virahol, adds high puring aluminium isopropoxide as catalyzer; Temperature of reaction kettle is heated to 100 ~ 110 DEG C (preferably, temperature of reaction kettle being heated to 105 DEG C) constant temperature 1.5 ~ 3.0h(is preferred, constant temperature 2.0h), reaction starts, and it is preferred to carry out condensing reflux 4 ~ 6h(to evaporant, condensing reflux 5h is carried out to evaporant), after question response terminates, temperature of reaction system is increased to 120 ~ 150 DEG C (preferred, temperature of reaction system to be increased to 135 DEG C), remaining Virahol is fully reacted, gets final product a step and obtain high puring aluminium isopropoxide.
3. method according to claim 2, is characterized in that, the high puring aluminium isopropoxide as catalyzer is after high-purity aluminium flake and anhydrous isopropyl alcohol catalyze and synthesize, the aluminum isopropylate of purity >=99.999% obtained of being purified by underpressure distillation mode again.
4. method according to claim 3, is characterized in that, the described high-purity isopropanol aluminum concentration as catalyzer is that 3 ~ 5mol/L(is preferred, and the described high-purity isopropanol aluminum concentration as catalyzer is 4mol/L).
5. method according to claim 2, is characterized in that, purity >=99.996% of described high-purity aluminium flake.
6. method according to claim 2, is characterized in that, described Virahol removes impurity through rectifying.
7. method according to claim 2, is characterized in that, end product high puring aluminium isopropoxide purity reaches more than 99.999%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673960A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of high-purity aluminum alkoxide |
| CN106673038A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Aluminum alkoxide preparation method |
| CN109317164A (en) * | 2018-09-27 | 2019-02-12 | 扬州中天利新材料股份有限公司 | The preparation method of amorphous metal catalyst and aluminium alcoholates |
| CN111039758A (en) * | 2019-12-31 | 2020-04-21 | 大连理工大学 | Liquid mixed alkoxy aluminum and synthetic method thereof |
| CN112898127A (en) * | 2021-01-25 | 2021-06-04 | 浙江爱科新材料有限公司 | Continuous preparation method of high-purity aluminum isopropoxide |
| CN113248345A (en) * | 2021-06-11 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
| CN113735687A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of high-purity alkoxy aluminum |
| CN115872838A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | Method for preparing high-purity aluminum isopropoxide by continuous method |
| CN115872837A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | Method for preparing high-purity aluminum isopropoxide by autocatalysis of high-pressure fixed bed |
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| CN106673038A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Aluminum alkoxide preparation method |
| CN106673038B (en) * | 2015-11-11 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation method of aluminium-alcohol salt |
| CN106673960A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of high-purity aluminum alkoxide |
| CN109317164B (en) * | 2018-09-27 | 2021-05-04 | 扬州中天利新材料股份有限公司 | Amorphous metal catalyst and preparation method of aluminum alkoxide |
| CN109317164A (en) * | 2018-09-27 | 2019-02-12 | 扬州中天利新材料股份有限公司 | The preparation method of amorphous metal catalyst and aluminium alcoholates |
| CN111039758A (en) * | 2019-12-31 | 2020-04-21 | 大连理工大学 | Liquid mixed alkoxy aluminum and synthetic method thereof |
| CN113735687A (en) * | 2020-05-28 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of high-purity alkoxy aluminum |
| CN112898127A (en) * | 2021-01-25 | 2021-06-04 | 浙江爱科新材料有限公司 | Continuous preparation method of high-purity aluminum isopropoxide |
| CN113248345A (en) * | 2021-06-11 | 2021-08-13 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
| CN113248345B (en) * | 2021-06-11 | 2021-10-26 | 江苏华盛锂电材料股份有限公司 | Preparation method of 2-butenol |
| CN115872838A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | Method for preparing high-purity aluminum isopropoxide by continuous method |
| CN115872837A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | Method for preparing high-purity aluminum isopropoxide by autocatalysis of high-pressure fixed bed |
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