CN1648065A - Recovering process for Gram-waste water - Google Patents
Recovering process for Gram-waste water Download PDFInfo
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- CN1648065A CN1648065A CN 200410073583 CN200410073583A CN1648065A CN 1648065 A CN1648065 A CN 1648065A CN 200410073583 CN200410073583 CN 200410073583 CN 200410073583 A CN200410073583 A CN 200410073583A CN 1648065 A CN1648065 A CN 1648065A
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Abstract
The present invention discloses Grignard process of recovering waste water as one radically improved technological process. The Grignard process includes hydrolysis with ammonium bromide aqua to recover bromine ion via preparing bromoethane and recovering magnesium ion via preparing magnesium sulfate, so as to recover ions from Grignard waste water. The said process is simple, high in yield and low in 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 reforming,, reclaim bromide anion by the method for preparing monobromethane with the bromize ammonium solution reaction that is hydrolyzed from source technology, the method for preparing sal epsom reclaims magnesium ion, thereby realizes the recovery of Gram-waste water intermediate ion.
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, reclaims with the form of monobromethane, employing is catalyzer with the vitriol oil, the method that drips dehydrated alcohol is carried out 70 ℃～100 ℃ of temperature of reaction, reaction pressure 1～5 normal atmosphere.
4. the technology of recovery Gram-waste water according to claim 1 is characterized in that described magnesium ion reclaims in the mode that crystallisation by cooling is prepared into sal epsom, 0～20 ℃ of crystalline temperature.
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 |
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| Publication Number | Publication Date |
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| CN1648065A true CN1648065A (en) | 2005-08-03 |
| CN1270983C CN1270983C (en) | 2006-08-23 |
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| CN 200410073583 Expired - Fee Related CN1270983C (en) | 2004-12-23 | 2004-12-23 | Recovering process for Gram-waste water |
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Cited By (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
Cited By (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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| CN1270983C (en) | 2006-08-23 |
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