CN1513762A - Purification technology of removing trace iron in alfol salt using complexation-crystallization method - Google Patents
Purification technology of removing trace iron in alfol salt using complexation-crystallization method Download PDFInfo
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- CN1513762A CN1513762A CNA031337007A CN03133700A CN1513762A CN 1513762 A CN1513762 A CN 1513762A CN A031337007 A CNA031337007 A CN A031337007A CN 03133700 A CN03133700 A CN 03133700A CN 1513762 A CN1513762 A CN 1513762A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- alcohol
- alcohol salt
- salt
- complexing agent
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 238000002425 crystallisation Methods 0.000 title claims description 20
- 238000000746 purification Methods 0.000 title claims description 15
- 238000005516 engineering process Methods 0.000 title description 7
- 150000003839 salts Chemical class 0.000 title 1
- 239000008139 complexing agent Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000004698 iron complex Chemical class 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000011109 contamination Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- -1 aluminium alkoxide Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A purifying process for removing trace iron from aluminium alkoxide by complexing-crystallizing method includes reaction of industrial aluminium ingot on alcohol to obtain aluminium alkoxide as the precursor of high-purity superfine alumina, vacuum distilling dissolving in organic solvent, reacting on complexing agent to form soluble iron complex, crystallizing aluminium alkoxide and solid-liquid separation.
Description
Technical field
The invention belongs to inorganic materials purification technique field, specially refer to the purification process that a kind of complexing-crystallization process removes trace iron in the aluminium-alcohol salt.
Background technology
High-purity ultra-fine alumina demonstrates special role and superiority in fields such as luminescent material, electronic substrates, window material, far-infrared material and biological ceramicss as important inorganic materials/starting material.The aluminium-alcohol salt hydrolysis method prepares and alumina powder jointedly has that the environmental pollution of not causing, technological operation are convenient, product purity is high, granularity is ultra-fine and the manageable characteristics of particle shape.Become universally recognizedly at present both at home and abroad, had the production technology of the market competitiveness and development prospect.In this technology the purity of aluminum oxide is to utilize the lower boiling character of its hydrolysis precursor aluminium-alcohol salt, purifies by underpressure distillation and realizes.But the aluminium-alcohol salt that is equipped with industrial aluminum is after underpressure distillation and hydrolysis, drying, and iron contamination generally in 25～120ppm scope, can not satisfy the requirement of high-performance aluminum phosphate-gallate series luminescent material in the alumina product; Some alumina base specific function material is also produced certain influence.And adopt rafifinal is raw material, will improve the aluminum oxide manufacturing cost greatly.Be necessary to provide a kind of degree of depth deferrization technology of aluminium-alcohol salt for this reason.
Summary of the invention
In order to overcome the deficiency that prior art exists, the purpose of this invention is to provide a kind of simple, economic industrialized purification technology, the trace iron in the aluminium-alcohol salt is carried out degree of depth purifying, purify the back product purity at 99.99% (Al
2O
3Meter) more than, wherein iron level is at 6ppm (Al
2O
3Meter) below.
The technical solution adopted for the present invention to solve the technical problems is: a kind of complexing-crystallization process removes the purification process of trace iron in the aluminium-alcohol salt, and organic solvent, complexing agent kind selected during the aluminium-alcohol salt crystallization purifying are as follows:
Organic alcohol is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol in the prescription; Organic solvent is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol, aromatic hydrocarbons and naphthenic hydrocarbon; Complexing agent is chosen in organic molecule that contains N, S, P, O functional group or compound, can contain sense atom more than 2 kinds simultaneously in the complexing agent.Formula rate between solvent, complexing agent and the aluminium-alcohol salt (weight ratio) is as follows:
The strength of solution that aluminium-alcohol salt and organic solvent are made in the prescription changes in 40%～90%wt scope, and the concentration of complexing agent in aluminium-alcohol salt is 0.001%～1%wt.
The technical process of purification process is as follows:
With the Industrial Metal aluminium ingot is raw material, is cut into behind the fragment under normal pressure to return with organic alcohol to heat up in a steamer reaction and generate aluminium-alcohol salt; Is raw material with underpressure distillation with industrial aluminium ingot, itself and alcohol reaction are generated the alkoxide of aluminium, utilize the lower boiling character of alkoxide to carry out underpressure distillation then and reach preliminary purification, again this alkoxide is dissolved in organic solvent and makes iron and complexing agent form easy molten type complex compound with the complexing agent effect, iron complex is left in the solution in the aluminium-alcohol salt crystallisation process, reach the purpose of removing iron contamination by the solid-liquid separation, here, complexing agent, organic solvent and initial proportioning are the important factors that influences de-ferrous effect.
Effect of the present invention and benefit be, underpressure distillation and the complexing crystallization phases bonded technology of utilizing this patent to propose can make in the aluminium-alcohol salt iron level by simple decompression distillatory 25～120ppm (Al
2O
3Meter) reduces to below the 6ppm.The high-purity ultra-fine alumina purity that obtains after the hydrolysis is more than 99.99%, this low iron or the alumina powder jointed of iron-free not only are widely used on luminescent material, and, important application prospects is arranged as aspects such as functional paint, window materials in other high-tech applications.
Embodiment
Below be described in detail the specific embodiment of the present invention
Trace iron removal methods in the aluminium-alcohol salt of the present invention, organic solvent, complexing agent kind and formula rate (weight ratio) thereof selected during the aluminium-alcohol salt crystallization purifying are as follows:
Organic alcohol is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol in the prescription; Organic solvent is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol, aromatic hydrocarbons and naphthenic hydrocarbon; Complexing agent is chosen in organic molecule that contains N, S, P, O functional group or compound, can contain sense atom more than 2 kinds simultaneously in the complexing agent.
The strength of solution that aluminium-alcohol salt and organic solvent are made in the prescription changes in 40%～90%wt scope, and the concentration of complexing agent in aluminium-alcohol salt is 0.001%～1%wt.Formula rate between organic solvent, complexing agent and the aluminium-alcohol salt (weight ratio) is better in following situation effect: the strength of solution that aluminium-alcohol salt and organic solvent are made into changes in 50%～85%wt scope, and the concentration of complexing agent in aluminium-alcohol salt is 0.005%～0.5%wt.
The technical process of whole purification technique is as follows:
Step 1: the synthetic and preliminary purification of aluminium-alcohol salt: with the Industrial Metal aluminium ingot is raw material, is cut into behind the fragment under normal pressure to return with organic alcohol to heat up in a steamer reaction generation aluminium-alcohol salt; It is distilled and is collected in the container with distillation under vacuum.
Step 2: the complexing of iron and aluminium-alcohol salt crystallization: the aluminium-alcohol salt that will just distill out is dissolved in selected organic solvent, and adds complexing agent.After it is mixed, stir and control cooling rate in confined conditions at a slow speed.Stirring velocity is controlled to be 10-1000 rev/min, and churning time is 2-12 hour; Cooling rate is controlled to be 3-15 ℃/hour; Temperature is reduced to room temperature from about 70 ℃, makes crystallization complete, and at this moment, the above aluminium-alcohol salt of 95-98% is crystallized out, and most of iron contamination form the bigger complex compound of solubleness stay solution mutually in.
Step 3: crystallization phases and mother liquor separating mutually: after solution stirring 2-12 hour, static depositing 2-12 hour, make crystal and mother liquor layering, then with method of pumping filtration with mother liquor and Crystallization Separation, use a small amount of clean solvent with crystallizing and washing again, and suction filtration is clean fast, and its iron level of the aluminium-alcohol salt that stays is less than 6ppm (Al
2O
3Meter).
Step 4: the recovery of mother liquor: the mother liquor behind the suction filtration carries out air distillation, reclaims solvent, stays in the container and contain aluminium-alcohol salt saturated in iron complex and the mother liquor, can be prepared into other purposes aluminum oxide or some catalysis aluminium-alcohol salt.
Below provide most preferred embodiment of the present invention:
With 100 kilograms of Al
2O
3Be example, getting 355 kilograms of 55 kilograms of metal aluminium flakes, Virahol joins to return in the reactor that has a heating jacket and heats up in a steamer the preparation aluminum isopropylate, reaction finishes the back at this reactor or pour into and carry out vacuum distilling in another reactor, distillation is poured about 400 kilograms distillate in the crystallizer that 150 kilograms of Virahols are housed into after finishing, and add dimethylglyoxime, each 30 gram of ammonium sulfocyanate as complexing agent, stir and make the formation homogeneous solution, this moment, solution temperature should guarantee more than 70 ℃.Control stirring velocity 20-40 rev/min, cooling rate then in confined conditions and carry out slow crystallizing for about 5 ℃/hour.Stop after 16 hours stirring, static 8 hours, carry out suction filtration then, the crystal that filter is done is got express developed with suction filtration clean with a small amount of pure Virahol, just obtain high-purity aluminium-alcohol salt, and its hydrolysis, drying and calcining are obtained iron level less than the high-purity oxidation powder of 6ppm.
Claims (3)
1. a complexing-crystallization process removes the purification process of trace iron in the aluminium-alcohol salt, and organic solvent, complexing agent kind selected when it is characterized in that the aluminium-alcohol salt crystallization purifying are as follows:
Organic alcohol is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol in the prescription; Organic solvent is chosen in ethanol, propyl alcohol, Virahol, butyl alcohol, aromatic hydrocarbons and naphthenic hydrocarbon; Complexing agent is chosen in organic molecule that contains N, S, P, O functional group or compound.Formula rate between solvent, complexing agent and the aluminium-alcohol salt (weight ratio) is as follows:
The strength of solution that aluminium-alcohol salt and organic solvent are made in the prescription changes in 30%～90%wt scope, and the concentration of complexing agent in aluminium-alcohol salt is 0.001%～5%wt.
The technical process of purification process is as follows:
(1) the synthetic and preliminary purification of aluminium-alcohol salt: with the Industrial Metal aluminium ingot is raw material, is cut into behind the fragment under normal pressure to return with organic alcohol to heat up in a steamer reaction generation aluminium-alcohol salt; It is distilled and is collected in the container with distillation under vacuum.
(2) complexing of iron and aluminium-alcohol salt crystallization: the aluminium-alcohol salt that will just distill out is dissolved in selected organic solvent, and adds complexing agent.After it is mixed, stir and control cooling rate in confined conditions at a slow speed.Stirring velocity is controlled to be 10-1000 rev/min, and churning time is 2-12 hour; Cooling rate is controlled to be 3-15 ℃/hour; Temperature is reduced to room temperature from about 70 ℃, makes crystallization complete, and at this moment, the above aluminium-alcohol salt of 95-98% is crystallized out, and most of iron contamination form the bigger complex compound of solubleness stay solution mutually in.
(3) crystallization phases and mother liquor separating mutually: after solution stirring 2-12 hour, static depositing 2-12 hour, make crystal and mother liquor layering, then with method of pumping filtration with mother liquor and Crystallization Separation, use a small amount of clean solvent with crystallizing and washing again, and suction filtration is clean fast, and its iron level of the aluminium-alcohol salt that stays is less than 6ppm (Al
2O
3Meter).
(4) recovery of mother liquor: the mother liquor behind the suction filtration carries out air distillation, reclaims solvent, stays in the container and contain aluminium-alcohol salt saturated in iron complex and the mother liquor, can be prepared into other purposes aluminum oxide or some catalysis aluminium-alcohol salt.
2. a kind of complexing-crystallization process according to claim 1 removes the purification process of trace iron in the aluminium-alcohol salt, it is characterized in that the formula rate (weight ratio) between described organic solvent, complexing agent and the aluminium-alcohol salt is as follows:
The strength of solution that aluminium-alcohol salt and organic solvent are made in the prescription changes in 50%～85%wt scope, and the concentration of complexing agent in aluminium-alcohol salt is 0.005%～0.5%wt.
3. a kind of complexing-crystallization process according to claim 1 removes the purification process of trace iron in the aluminium-alcohol salt, it is characterized in that can containing sense atom more than 2 kinds simultaneously in the described complexing agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031337007A CN1513762A (en) | 2003-08-12 | 2003-08-12 | Purification technology of removing trace iron in alfol salt using complexation-crystallization method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031337007A CN1513762A (en) | 2003-08-12 | 2003-08-12 | Purification technology of removing trace iron in alfol salt using complexation-crystallization method |
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| Publication Number | Publication Date |
|---|---|
| CN1513762A true CN1513762A (en) | 2004-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031337007A Pending CN1513762A (en) | 2003-08-12 | 2003-08-12 | Purification technology of removing trace iron in alfol salt using complexation-crystallization method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673038A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Aluminum alkoxide preparation method |
| CN110759371A (en) * | 2019-12-04 | 2020-02-07 | 新疆国峰嘉和环保科技有限公司 | Method for preparing calcium oxide by purifying and recycling carbide slag |
| CN111116315A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
| CN111116314A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
-
2003
- 2003-08-12 CN CNA031337007A patent/CN1513762A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111116315A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
| CN111116314A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
| CN111116315B (en) * | 2018-10-31 | 2023-03-31 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
| CN111116314B (en) * | 2018-10-31 | 2023-04-07 | 中国石油化工股份有限公司 | Method for removing iron impurities in alkoxy aluminum |
| CN110759371A (en) * | 2019-12-04 | 2020-02-07 | 新疆国峰嘉和环保科技有限公司 | Method for preparing calcium oxide by purifying and recycling carbide slag |
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