CN1270983C - Recovering process for Gram-waste water - Google Patents
Recovering process for Gram-waste water Download PDFInfo
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- CN1270983C CN1270983C CN 200410073583 CN200410073583A CN1270983C CN 1270983 C CN1270983 C CN 1270983C CN 200410073583 CN200410073583 CN 200410073583 CN 200410073583 A CN200410073583 A CN 200410073583A CN 1270983 C CN1270983 C CN 1270983C
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- Prior art keywords
- gram
- reaction
- waste water
- recovery
- technology
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- 239000002351 wastewater Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 16
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000003747 Grignard reaction Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 abstract 1
- 229940006460 bromide ion Drugs 0.000 abstract 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract 1
- 235000019341 magnesium sulphate Nutrition 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 6
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 6
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 6
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 6
- 235000019155 vitamin A Nutrition 0.000 description 6
- 239000011719 vitamin A Substances 0.000 description 6
- 229940045997 vitamin a Drugs 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229930003427 Vitamin E Natural products 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019165 vitamin E Nutrition 0.000 description 3
- 229940046009 vitamin E Drugs 0.000 description 3
- 239000011709 vitamin E Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- -1 β-Hu Luobusu Chemical compound 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a recovering process for Gram-waste water. A headstream process is reformed, an ammonium bromide water solution is used for hydrolysis reaction, bromide ion is recovered by a bromoethane preparation method, magnesium ions are recovered by a magnesium sulfate preparation method, and therefore, the process can recover ions in Gram-waste water. The method is a new technique for the recovery of the Gram-waste water and has the advantages of simple operation, high yield and low cost.
Description
Technical field
The present invention relates to Wastewater Recovery novel process in the grignard reaction.
Background technology
Grignard reaction is the important reaction of a class of the various alcohol compounds of preparation.In the production of products such as vitamin A, β-Hu Luobusu, vitamin-E, usually to adopt grignard reaction to synthesize.For example in vitamin A synthetic, Roche company takes the technological line of C14+C6, and promptly C14 aldehyde and C6 alcohol carry out the key intermediate that grignard reaction obtains vitamin A, obtain vitamin A through partial hydrogenation, acetylize, bromination, hydrolysis etc. then.This method technical maturity, yield is more stable, is the main production method of vitamin A in the world.The key of this reaction is a grignard reaction, in traditional method, usually with C6 alcohol, magnesium and monobromethane reaction, forms Grignard reagent, and with the C14 aldehyde reaction, reaction solution is hydrolyzed with aqueous ammonium chloride solution then.Because the aqueous phase of grignard reaction contains a large amount of chlorine, bromine, magnesium ion, so be difficult to carry out Separation and Recovery, forms a large amount of Gram-waste waters, contaminate environment.In the similar grignard reaction of other synthetic β-Hu Luobusu, vitamin-E etc., also can produce this chloride, bromine, the isoionic Gram-waste water of magnesium.
Summary of the invention
The purpose of this invention is to provide the novel process that a kind of Gram-waste water simple to operate, that yield is high, cost is low reclaims.
The technology that Gram-waste water provided by the invention reclaims is characterized in that: with the reaction that is hydrolyzed of brometo de amonio solution, and by prepare the method recovery bromide anion of monobromethane, preparing the method recovery magnesium ion of sal epsom, thus the recovery of realization Gram-waste water intermediate ion.
The invention is characterized in and utilize source technology to reform that with the bromize ammonium solution reaction that is hydrolyzed, the concentration of bromize ammonium solution normally 5%～50% is good with 10%～30% especially.
The recovery of bromide anion can be reclaimed with hydrobromic form, also can reclaim with the form of monobromethane, and preferable methods is the form of monobromethane.
It is catalyzer that the recovery of monobromethane is adopted usually with the vitriol oil, and the method that drips dehydrated alcohol is carried out.Temperature of reaction is generally 50 ℃～150 ℃, is good with 70 ℃～100 ℃ especially.Reaction pressure is generally more than the normal pressure, below 20 normal atmosphere, is good with 1～5 normal atmosphere especially.
Magnesium ion reclaims in the mode that is prepared into sal epsom, reclaims main sulfur acid magnesium in the mother liquor behind the monobromethane, and the mode by crystallisation by cooling can obtain the sal epsom solid.The crystalline temperature normally-20 ℃～60 ℃, be good especially with 0～20 ℃.
The present invention is directed to as if common grignard reaction in the general considerations that produced, problem as the Gram-waste water in the products productions such as vitamin A, vitamin-E, be to contain chlorine, bromine, magnesium ion in the Gram-waste water, because chlorine is difficult to separate difficult recovery problem with bromide anion.
Advantage of the present invention is: 1) reform from source technology, replace the aqueous ammonium chloride solution reaction that is hydrolyzed with bromize ammonium solution, reduced the kind of effects of ion, reduced the generation of " three wastes ".2) reclaim ion in the Gram-waste water in the mode of monobromethane and sal epsom, the yield height, simple to operate, realize industrialization easily.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.The present invention is not limited to following example.
Embodiment 1
In 1000 milliliters three-necked bottle, add, 200 milliliters of anhydrous diethyl ethers, 22 gram magnesium and 110 gram monobromethanes, stirred then 0.5 hour, slowly add 100 milliliters of diethyl ether solutions that contain 39.6 gram methyl heptene alkynols then, stirred 3 hours, and dripped 100 milliliters of diethyl ether solutions that contain 72 gram C14 aldehyde then, restir 2.5 hours, 60 ℃ of controlled temperature add the 500 ml water solution that contain 120 gram brometo de amonios then and are hydrolyzed.Layering, organic phase reclaims solvent, obtains product 94 grams, yield 91%.Water concentrates earlier, adds the vitriol oil of 220 grams then, drips 100 gram dehydrated alcohols at 100 ℃ then, can obtain 210 gram monobromethanes, yield 96%.Reactant is cooled to 20 ℃ then, suction filtration, drying obtains 93 gram sal epsom, yield 98%.
Embodiment 2
Comparative examples 1
In 1000 milliliters three-necked bottle, add, 200 milliliters of anhydrous diethyl ethers, 22 gram magnesium and 110 gram monobromethanes, stirred then 0.5 hour, slowly add 100 milliliters of diethyl ether solutions that contain 39.6 gram methyl heptene alkynols then, stirred 3 hours, and dripped 100 milliliters of diethyl ether solutions that contain 72 gram C14 aldehyde then, restir 2.5 hours, 60 ℃ of controlled temperature add the 500 ml water solution that contain 70 gram ammonium chlorides then and are hydrolyzed.Layering, organic phase reclaims solvent, obtains product 93 grams, yield 90%.
Embodiment 3
In 1000 milliliters three-necked bottle, add, 200 milliliters of anhydrous diethyl ethers, 22 gram magnesium and 110 gram monobromethanes, stirred then 0.5 hour, slowly add 100 milliliters of diethyl ether solutions that contain 39.6 gram methyl heptene alkynols then, stirred 3 hours, and dripped 100 milliliters of diethyl ether solutions that contain 72 gram C14 aldehyde then, restir 2.5 hours, 60 ℃ of controlled temperature add the 400 ml water solution that contain 120 gram brometo de amonios then and are hydrolyzed.Layering, organic phase reclaims solvent, obtains product 94 grams, yield 91%.Water concentrates earlier, adds the vitriol oil of 200 grams then, drips 100 gram dehydrated alcohols at 90 ℃ then, can obtain 205 gram monobromethanes, yield 93%.Reactant is cooled to 30 ℃ then, suction filtration, drying obtains 90 gram sal epsom, yield 95%.
Claims (4)
1. technology that reclaims Gram-waste water, it is characterized in that reclaiming bromide anion with the method for preparing monobromethane, behind grignard reaction, add the bromize ammonium solution reaction that is hydrolyzed, add the catalyzer vitriol oil, drip the dehydrated alcohol method and carry out, bromize ammonium solution concentration is 5%～50%, 50 ℃～150 ℃ of temperature of reaction, reaction pressure is more than the normal pressure, under the condition below 20 normal atmosphere, generates monobromethane; The mode that is prepared into sal epsom with crystallisation by cooling reclaims magnesium ion, and main sulfur acid magnesium is cooled to mother liquor-20 ℃～60 ℃ in the mother liquor, and crystallization obtains the sal epsom solid.
2. the technology of recovery Gram-waste water according to claim 1 is characterized in that the described bromize ammonium solution that is hydrolyzed reaction is 10%～30%.
3. the technology of recovery Gram-waste water according to claim 1 is characterized in that the recovery of described bromide anion, and temperature of reaction is 70 ℃～100 ℃, and reaction pressure is 1～5 normal atmosphere.
4. the technology of recovery Gram-waste water according to claim 1 is characterized in that described magnesium ion reclaims, and Tc is 0～20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410073583 CN1270983C (en) | 2004-12-23 | 2004-12-23 | Recovering process for Gram-waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410073583 CN1270983C (en) | 2004-12-23 | 2004-12-23 | Recovering process for Gram-waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1648065A CN1648065A (en) | 2005-08-03 |
| CN1270983C true CN1270983C (en) | 2006-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410073583 Expired - Fee Related CN1270983C (en) | 2004-12-23 | 2004-12-23 | Recovering process for Gram-waste water |
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| Country | Link |
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| CN (1) | CN1270983C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130487A (en) * | 2011-11-26 | 2013-06-05 | 费雄略 | Recovery processing method of Grignard reaction wastewater |
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- 2004-12-23 CN CN 200410073583 patent/CN1270983C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1648065A (en) | 2005-08-03 |
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