CN103991846A - Method for recovering iodine and gallium from raffinate produced in preparation of trimethyl gallium from iodomethane - Google Patents
Method for recovering iodine and gallium from raffinate produced in preparation of trimethyl gallium from iodomethane Download PDFInfo
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- CN103991846A CN103991846A CN201410170301.9A CN201410170301A CN103991846A CN 103991846 A CN103991846 A CN 103991846A CN 201410170301 A CN201410170301 A CN 201410170301A CN 103991846 A CN103991846 A CN 103991846A
- Authority
- CN
- China
- Prior art keywords
- gallium
- iodine
- raffinate
- trimethyl
- methyl iodide
- Prior art date
- 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.)
- Granted
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 37
- 239000011630 iodine Substances 0.000 title claims abstract description 37
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 36
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 7
- 229940006461 iodide ion Drugs 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 3
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 238000004871 chemical beam epitaxy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LRPWSMQGXLANTG-UHFFFAOYSA-M iodogallium Chemical compound I[Ga] LRPWSMQGXLANTG-UHFFFAOYSA-M 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering iodine and gallium from raffinate produced in preparation of trimethyl gallium from iodomethane. The method is characterized by comprising the following six steps for recovery: alcoholysis; acidolysis; reduction and sublimation for recovery of iodine; neutralization and sedimentation of raffinate; filtering; and collection of mixed liquor of washing water and filtrate and precipitation of gallium. The method provided by the invention has the advantages of easiness, practicality, high recovery rates of iodine and gallium, small investment, low cost, easy operation and friendliness to the environment.
Description
Technical field
The present invention relates to the reacted raffinate of organometallic complex and reclaim, especially relate to a kind of methyl iodide and prepare the method that reclaims iodine and gallium in trimethyl-gallium raffinate.
Background technology
The organometallicss such as high-purity trimethyl-gallium, be grow light electronic material in metal organic chemical vapor deposition technology (MO CVD), chemical beam epitaxy (CBE) process most important, be also the raw material of current consumption maximum, the compound semiconductor film materials such as the indium gallium arsenic nitrogen (InGaAsN) that is widely used in growing, indium gallium arsenic (InGaAs), indium gallium phosphorus (InGaP).The preparation method of trimethyl-gallium is more, and common method is aluminum alkyls method and alloyage.Alloyage generally adopts gallium-magnesium alloy and iodomethane reaction, methyl iodide is due to more expensive, in its raffinate after having reacted, reclaim iodine and gallium for reducing costs and comprehensive harmless treatment has great significance, but do not have patent report methyl iodide to prepare the method that reclaims iodine and gallium in trimethyl-gallium raffinate at present.
Summary of the invention
Object of the present invention, is to provide a kind of and can overcomes the deficiencies in the prior art, proposes a kind of simple and practical, the iodine gallium rate of recovery is high, less investment cost is low, easy handling, and the environment amenable methyl iodide that can comprehensively reclaim is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate.
To achieve these goals, methyl iodide of the present invention is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate, and removal process adopts following steps:
(1) alcoholysis, prepares and in trimethyl-gallium raffinate, adds volume ratio V raffinate to methyl iodide: the ethanol of V ethanol=1:0.5～1, stirring reaction;
(2) acidolysis adds appropriate hydrochloric acid in above-mentioned solution, regulates PH < 1;
(3) iodine is reclaimed in reduction distillation, to dripping oxygenant in the solution of acidifying, iodide ion is reduced into iodine, and is heated to 200～280 ℃ of distillations and reclaims iodine;
(4) raffinate neutralization precipitation, adds sodium hydrate regulator solution PH > 13 in the raffinate after distilling to above-mentioned iodine;
(5) filter, wash filter residue with water to neutral, wash water and filtrate are mixed;
(6) wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds sulfuric acid to regulate PH=3～5 deposition gallium.
In described step (1), stirring reaction is to liquid, without paste.
In described step (3), oxygenant is ferric sulfate, sulfuric acid or hydrogen peroxide.
In described step (3), oxygenant is mixture between two or three's mixture of ferric sulfate, sulfuric acid and hydrogen peroxide.
The invention has the beneficial effects as follows:
1. simple and practical, do not need special equipment and complicated chemical reagent, easy handling
2. the iodine gallium rate of recovery is high, and the rate of recovery of iodine can reach more than 85%, and the rate of recovery of gallium can reach more than 90%
3. less investment, cost is low
3. environmentally friendly.
Embodiment
Describe methyl iodide of the present invention below in detail and prepare the method that reclaims iodine and gallium in trimethyl-gallium raffinate.
According to the present invention, methyl iodide is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate, comprise step: alcoholysis, to methyl iodide, prepare and in trimethyl-gallium raffinate, add volume ratio V raffinate: the ethanol of V ethanol=1:0.5～1, stirring reaction, until become liquid completely without paste; Acidolysis adds appropriate hydrochloric acid in above-mentioned solution, regulates PH < 1, during need ceaselessly to stir; Iodine is reclaimed in reduction distillation, in the solution of acidifying, drip suitable oxygenant, add-on for completely reduce the required oxidant content of iodide ion n doubly, iodide ion is reduced into iodine, and be heated to 200～280 ℃ of distillation recovery iodine, until solution is without obvious red-purple; Raffinate neutralization precipitation, adds sodium hydrate regulator solution PH > 13 in the raffinate after distilling to above-mentioned iodine; Filter, obtain filtrate and filter residue (filter residue is the mixing slag of magnesium hydroxide or magnesium hydroxide and ironic hydroxide), wash filter residue with water to neutral, wash water and filtrate are mixed; Wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds appropriate sulfuric acid to regulate PH=3～5 deposition gallium.
Embodiment mono-
To methyl iodide, prepare the ethanol that adds 160ml in trimethyl-gallium raffinate 200ml, stirring reaction, until become liquid completely without paste; In above-mentioned solution, add 8ml hydrochloric acid, regulate PH < 1, during need ceaselessly to stir, obtain 360ml solution, iodine content is 95.6g/L after testing, gallium is 189PPM; Iodine is reclaimed in reduction distillation, in the solution of acidifying, drips 50% ferrum sulfuricum oxydatum solutum 60ml, and iodide ion is reduced into iodine, and is heated to 200～280 ℃ of distillation recovery iodine, until solution, without obvious red-purple, obtains iodine 30.28g, the iodine rate of recovery is 88%; In raffinate after distilling to above-mentioned iodine, add sodium hydrate regulator solution PH > 13; Filter, obtain the mixing slag of filtrate and magnesium hydroxide and ironic hydroxide, wash filter residue with water to neutral, wash water and filtrate are mixed; Wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds appropriate sulfuric acid to regulate PH=3.5 deposition gallium, obtains gallium hydroxide 0.11g, and the gallium rate of recovery is 93.4%.
Embodiment bis-
To methyl iodide, prepare the ethanol that adds 500ml in trimethyl-gallium raffinate 500ml, stirring reaction, until become liquid completely without paste; In above-mentioned solution, add 20ml hydrochloric acid, regulate PH < 1, during need ceaselessly to stir, obtain 990ml solution, iodine content is 87.2g/L after testing, gallium is 220PPM; Iodine is reclaimed in reduction distillation, in the solution of acidifying, drips 50% ferrum sulfuricum oxydatum solutum 80ml and vitriol oil 20ml, and iodide ion is reduced into iodine, and be heated to 200～280 ℃ of distillations and reclaim iodine, until solution, without obvious red-purple, obtains iodine 78.56g, the iodine rate of recovery is 91%; In raffinate after distilling to above-mentioned iodine, add sodium hydrate regulator solution PH > 13; Filter, obtain the mixing slag of filtrate and magnesium hydroxide and ironic hydroxide, wash filter residue with water to neutral, wash water and filtrate are mixed; Wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds appropriate sulfuric acid to regulate PH=4 deposition gallium, obtains gallium hydroxide 0.34g, and the gallium rate of recovery is 90%.
Embodiment tri-
To methyl iodide, prepare the ethanol that adds 270ml in trimethyl-gallium raffinate 300ml, stirring reaction, until become liquid completely without paste; In above-mentioned solution, add 13ml hydrochloric acid, regulate PH < 1, during need ceaselessly to stir, obtain 560ml solution, iodine content is 90.5g/L after testing, gallium is 337PPM; Iodine is reclaimed in reduction distillation, in the solution of acidifying, drips 50% ferrum sulfuricum oxydatum solutum 45ml and vitriol oil 12ml and hydrogen peroxide 10ml, and iodide ion is reduced into iodine, and be heated to 200～280 ℃ of distillations and reclaim iodine, until solution, without obvious red-purple, obtains iodine 43.1g, the iodine rate of recovery is 85%; In raffinate after distilling to above-mentioned iodine, add sodium hydrate regulator solution PH > 13; Filter, obtain the mixing slag of filtrate and magnesium hydroxide and ironic hydroxide, wash filter residue with water to neutral, wash water and filtrate are mixed; Wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds appropriate sulfuric acid to regulate PH=3.5 deposition gallium, obtains gallium hydroxide 0.3g, and the gallium rate of recovery is 91.8%.
Claims (4)
1. methyl iodide is prepared a method that reclaims iodine and gallium in trimethyl-gallium raffinate, it is characterized in that removal process adopts following steps:
(1) alcoholysis, prepares and in trimethyl-gallium raffinate, adds volume ratio V raffinate to methyl iodide: the ethanol of V ethanol=1:0.5～1, stirring reaction;
(2) acidolysis adds appropriate hydrochloric acid in above-mentioned solution, regulates PH < 1;
(3) iodine is reclaimed in reduction distillation, to dripping oxygenant in the solution of acidifying, iodide ion is reduced into iodine, and is heated to 200～280 ℃ of distillations and reclaims iodine;
(4) raffinate neutralization precipitation, adds sodium hydrate regulator solution PH > 13 in the raffinate after distilling to above-mentioned iodine;
(5) filter, wash filter residue with water to neutral, wash water and filtrate are mixed;
(6) wash water filtrate mixed solution is collected heavy gallium, by wash water and filtrate collection, adds sulfuric acid to regulate PH=3～5 deposition gallium.
2. methyl iodide according to claim 1 is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate, it is characterized in that: in described step (1), stirring reaction is to liquid, without paste.
3. methyl iodide according to claim 1 is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate, is characterised in that: in described step (3), oxygenant is ferric sulfate, sulfuric acid or hydrogen peroxide.
4. methyl iodide according to claim 1 is prepared the method that reclaims iodine and gallium in trimethyl-gallium raffinate, is characterised in that: in described step (3), oxygenant is mixture between two or three's mixture of ferric sulfate, sulfuric acid and hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410170301.9A CN103991846B (en) | 2014-04-25 | 2014-04-25 | Iodomethane prepares iodine and the method for gallium of reclaiming in trimethyl gallium residual liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410170301.9A CN103991846B (en) | 2014-04-25 | 2014-04-25 | Iodomethane prepares iodine and the method for gallium of reclaiming in trimethyl gallium residual liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103991846A true CN103991846A (en) | 2014-08-20 |
| CN103991846B CN103991846B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410170301.9A Expired - Fee Related CN103991846B (en) | 2014-04-25 | 2014-04-25 | Iodomethane prepares iodine and the method for gallium of reclaiming in trimethyl gallium residual liquid |
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| Country | Link |
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| CN (1) | CN103991846B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175438A (en) * | 2015-09-30 | 2015-12-23 | 江西佳因光电材料有限公司 | Preparation method of trimethylgallium |
| CN108862199A (en) * | 2018-06-28 | 2018-11-23 | 广东先导稀材股份有限公司 | The method of iodine is recycled in the waste liquid of trimethyl gallium containing iodine |
| CN111875472A (en) * | 2020-07-23 | 2020-11-03 | 江苏南大光电材料股份有限公司 | Method for recovering methyl iodide from iodine-containing residual liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554994A (en) * | 2009-05-20 | 2009-10-14 | 山西新天源医药化工有限公司 | Method for recovering iodine in production waste liquid of X-CT series contrast media |
| CN103103339A (en) * | 2012-12-19 | 2013-05-15 | 紫金矿业集团股份有限公司 | Method for selectively recovering alum and gallium from alunite concentrate |
-
2014
- 2014-04-25 CN CN201410170301.9A patent/CN103991846B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554994A (en) * | 2009-05-20 | 2009-10-14 | 山西新天源医药化工有限公司 | Method for recovering iodine in production waste liquid of X-CT series contrast media |
| CN103103339A (en) * | 2012-12-19 | 2013-05-15 | 紫金矿业集团股份有限公司 | Method for selectively recovering alum and gallium from alunite concentrate |
Non-Patent Citations (1)
| Title |
|---|
| 刘淑坤: "废旧高分子材料的综合利用", 《辽宁化工》, no. 5, 31 May 1996 (1996-05-31), pages 53 - 56 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175438A (en) * | 2015-09-30 | 2015-12-23 | 江西佳因光电材料有限公司 | Preparation method of trimethylgallium |
| CN108862199A (en) * | 2018-06-28 | 2018-11-23 | 广东先导稀材股份有限公司 | The method of iodine is recycled in the waste liquid of trimethyl gallium containing iodine |
| CN111875472A (en) * | 2020-07-23 | 2020-11-03 | 江苏南大光电材料股份有限公司 | Method for recovering methyl iodide from iodine-containing residual liquid |
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| Publication number | Publication date |
|---|---|
| CN103991846B (en) | 2016-08-17 |
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