CN106745112B - The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard - Google Patents
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard Download PDFInfo
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- CN106745112B CN106745112B CN201611163030.XA CN201611163030A CN106745112B CN 106745112 B CN106745112 B CN 106745112B CN 201611163030 A CN201611163030 A CN 201611163030A CN 106745112 B CN106745112 B CN 106745112B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The present invention relates to the preparation method that Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard, under normal temperature condition, according to certain volume ratio sodium carbonate liquor is added into grignard waste residue hydrolyzate, magnesium carbonate solid is obtained, the pH of grignard waste residue hydrolyzate is adjusted with obtained magnesium carbonate, then adds appropriate magnesium powder removal of impurities, add activated carbon decolorizing, filtrate add salt acid for adjusting pH, be concentrated under reduced pressure, the crystallization that cool, centrifuge, obtain the Magnesium dichloride hexahydrate of white high-purity.The present invention reclaims magnesium chloride from waste liquid, improves production environment, reduces three waste discharge, reduces environmental pollution, by-product magnesium chloride is reclaimed, technological operation is simple, process stabilizing, and recovery Magnesium dichloride hexahydrate cost is low, operation is safe, good product quality, beneficial to industrialization.
Description
Technical field
The invention belongs to the synthetically prepared field of medicine intermediate, and in particular to one kind reclaims from grignard waste residue hydrolyzate
The preparation method of Magnesium dichloride hexahydrate.
Background technology
Magnesium chloride hexahydrate also known as water chlorine stone, sterling is colourless monoclinic crystal under normal temperature, and industrial goods are generally in yellowish-brown, Yi Chao
Solution, has bitter saline taste, is dissolved in water and ethanol.It is widely used, in metallurgical industry, the binder as refractory material and block furnace wall,
The raw material of smelting magnesium；Hard magnesia cement is made with magnesium chloride and magnesia in building industry, can artificial stone processed；
It is the raw material for manufacturing various magnesium salts in chemical industry；Agriculturally, cotton defoliant is manufactured；Bean curd solidification is done in food industry
Agent；It also is used as analytical reagent；Also serve as fireproof agent；For medical industry, medical dialysis solution etc..Structural formula such as following formula：
The composite signal of Magnesium dichloride hexahydrate is less, and domestic and foreign literature is also few, patent 93109924《The standby white of making from brine
The production new technique of Magnesium dichloride hexahydrate》By sea bittern it is aquatic production white magnesium chloride process of preparing, after being evaporated brine with seawater
It is that raw brine be raw material that bittern, which extracts the mother liquor after potassium chloride and bromine, through adding alkali to neutralize, add calcium sulphur removal, slagging-off, bleaching,
The processing step such as vacuum evaporation and film-making, white magnesium chloride is can obtain, this method cost is high, and environmental pollution is serious, expends work
Shi Duo, post-processing operation are cumbersome, it is difficult to form large-scale production；There is document introduction to be added to the water magnesite.After mixing slowly
Add hydrochloric acid.After reaction completely, sulfuric acid and saturated hydrog en sulphide solution are added in the solution.Stand, filtering, by filtrate 80~
Heated at 90 DEG C, filtrate is concentrated into relative density 1.33~1.35.Refilter, cool down, filtering and to obtain magnesium chloride, the method raw material
It is not easy to obtain, industrially should not largely uses, obtains that product purity is not high, and yield is low；
These are unfavorable for industrialized production and raising product quality is easy to get, it is necessary to develop a kind of raw material, and cost is low, rear place
Manage simple to operate, environmental pollution is small, and operation is safe, and reaction yield is high, good product quality, beneficial to industrialized six water
Close the preparation method of magnesium chloride.
Contain a large amount of magnesium chlorides and impurity in grignard waste residue hydrolyzate（Such as Cu2+, HCl, THF etc.）, directly work as wastewater treatment
Increase processing cost.Accessory substance magnesium chloride hexahydrate can be extracted therefrom, reduce wastewater discharge.
The content of the invention
It is an object of the invention to provide the preparation method that Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard.
Based on above-mentioned purpose, this invention takes following technical scheme：
The present invention relates to the preparation method that Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard, normal temperature condition
Under, using grignard waste residue hydrolyzate as raw material, certain density carbonic acid is added into grignard waste residue hydrolyzate according to certain volume ratio
Sodium solution, stir, centrifugation, rinsing first obtains magnesium carbonate solid, and the pH of grignard waste residue hydrolyzate is adjusted with obtained magnesium carbonate, is added
Enter appropriate magnesium powder, stand 1~2h；Centrifugation, appropriate activated carbon is added into filtrate, and temperature rising reflux is after 1 hour, while hot mistake
Filter, filtrate are concentrated under reduced pressure, the crystallization that cool, centrifuged, obtained white high-purity with salt acid for adjusting pH（The ﹪ of content of magnesium chloride >=46.0）
Magnesium dichloride hexahydrate.The present invention reclaims magnesium chloride from waste liquid, improves production environment, reduces three waste discharge, reduces ring
Border is polluted, and reclaims by-product magnesium chloride, and technological operation is simple, process stabilizing, and recovery Magnesium dichloride hexahydrate cost is low, operation
It is safe, good product quality, beneficial to industrialization.
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of above-mentioned waste residue hydrolyzate from grignard, it is characterised in that normal temperature
Under the conditions of, using grignard waste residue hydrolyzate as raw material, sodium carbonate liquor is added, the concentration of sodium carbonate liquor is 15 ~ 20 ﹪, and grignard is given up
The volume ratio of slag hydrolyzate and sodium carbonate liquor is 4:1；
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of above-mentioned waste residue hydrolyzate from grignard, it is characterised in that use carbon
The mass ratio 0.006 of the pH to 6~7 of sour magnesium solid regulation grignard waste residue hydrolyzate, magnesium carbonate solid and grignard waste residue water solution liquid ~
0.008：1；
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of above-mentioned waste residue hydrolyzate from grignard, it is characterised in that regulation
After the pH of grignard waste residue hydrolyzate, magnesium powder is added, removes the Cu2+ in grignard waste residue hydrolyzate, magnesium powder and grignard waste residue water solution liquid
Mass ratio be 0.001 ~ 0.003:1；
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of above-mentioned waste residue hydrolyzate from grignard, it is characterised in that use salt
Acid for adjusting pH is concentrated under reduced pressure into the 1/2 of former form waste residue hydrolyzed liquid product, is cooled to 10~15 DEG C, insulated and stirred analysis to 3~4
It is brilliant 2 hours.
The present invention does reaction raw materials with grignard waste residue hydrolyzate, and post-processing operation is simple, and environmental pollution is small, operation peace
Quan Xinggao, reaction yield is high, and good product quality, cost is low, beneficial to industrialization.
Embodiment
Technical scheme is described in further detail below by way of specific embodiment, but the protection model of the present invention
Enclose and be not limited thereto.
Embodiment 1
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard
Comprise the following steps that：
1. prepare the sodium carbonate liquor 200mL of 20 ﹪ concentration；
2. to stirring, thermometer, reflux condenser（Band calcium oxide drying tube）Four-hole bottle in add 800mL grignard
Waste residue hydrolyzate, 200mL sodium carbonate liquors are added dropwise, stir, centrifuge, filter cake is rinsed 2-3 times with proper amount of clear water, obtains white
Magnesium carbonate solid；
3. to stirring, thermometer, addition funnel, reflux condenser（Band calcium oxide drying tube）Four-hole bottle in successively
Add 200mL（260g）Grignard waste residue hydrolyzate（PH is about 3）, 1.6g magnesium carbonate solids obtained above are added, stirring is equal
It is even, pH to 6.5 is adjusted, 0.44g magnesium powders is then added while stirring into reaction solution, makes and the Cu in grignard waste residue water solution liquid2+
Fully reaction, stand 1~2h, centrifugation；Appropriate activated carbon is added into filtrate, temperature rising reflux filters while hot after 1 hour, drop
Temperature, hydrochloric acid is added, adjust pH=4, be warming up to 60~70 DEG C, be concentrated under reduced pressure into the 1/2 of former grignard waste residue hydrolyzed liquid product, cooling
To 10~15 DEG C, insulated and stirred crystallization 2 hours；Centrifugation, filter cake are rinsed 2-3 times with proper amount of clear water, obtain white six chloride hydrates
Magnesium solid, dry the 136.5g that weighs, sampling detection, the ﹪ of content of magnesium chloride 46.5
Embodiment 2
The preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard
Comprise the following steps that：
1. prepare the sodium carbonate liquor 200mL of 15 ﹪ concentration；
2. to stirring, thermometer, reflux condenser（Band calcium oxide drying tube）Four-hole bottle in add 800mL forms
Waste residue, 200mL sodium carbonate liquors are added dropwise, stir, centrifuge, filter cake is rinsed 2-3 times with proper amount of clear water, obtains white magnesium carbonate
Solid；
3. to stirring, thermometer, addition funnel, reflux condenser（Band calcium oxide drying tube）Four-hole bottle according to
Secondary addition 200mL（260g）Form waste residue（PH is 3.5）, 1.5g magnesium carbonate solids are added, are stirred, adjust pH to 6,
Then 0.40g magnesium powders are added while stirring into waste residue, are made and the Cu in form waste residue2+Fully reaction, stand 1~2h；Centrifugation,
Appropriate activated carbon is added into filtrate, temperature rising reflux filters while hot after 1 hour, cooling, adds hydrochloric acid, adjusts pH to 3, rises
Temperature is concentrated under reduced pressure into the 1/2 of former form waste residue volume, is cooled to 10~15 DEG C, insulated and stirred crystallization 2 hours to 60~70 DEG C；
Centrifugation, filter cake are rinsed 2-3 times with proper amount of clear water, obtain white Magnesium dichloride hexahydrate solid, dry the 142.5g that weighs, sampling inspection
Survey, the ﹪ of content 46.7.
Claims (5)
1. reclaiming the preparation method of Magnesium dichloride hexahydrate in a kind of waste residue hydrolyzate from grignard, it is characterized in that under normal temperature condition, press
Certain volume ratio adds certain density sodium carbonate liquor into grignard waste residue hydrolyzate, obtains magnesium carbonate solid, with what is obtained
Magnesium carbonate adjusts the pH to 6~7 of new grignard waste residue hydrolyzate, then adds appropriate magnesium powder and activated carbon copper removal ionic impurity
And decolouring, filtrate add salt acid for adjusting pH, be concentrated under reduced pressure, the crystallization that cool, centrifuge, obtain six chloride hydrates of white high-purity
Magnesium.
2. the preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard according to claim 1, its
It is characterised by under normal temperature condition, using grignard waste residue hydrolyzate as raw material, adds sodium carbonate liquor, the concentration of sodium carbonate liquor is 15
The volume ratio of ~ 20 ﹪, grignard waste residue hydrolyzate and sodium carbonate liquor is 4:1.
3. the preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard according to claim 1, its
It is characterised by the mass ratio 0.006 ~ 0.008 of magnesium carbonate solid and grignard waste residue water solution liquid：1.
4. the preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard according to claim 1, its
After being characterised by the pH of regulation grignard waste residue hydrolyzate, magnesium powder is added, removes the Cu in grignard waste residue hydrolyzate2+, magnesium powder dative
The mass ratio of family name's waste residue hydrolyzate is 0.001 ~ 0.003:1.
5. the preparation method of Magnesium dichloride hexahydrate is reclaimed in a kind of waste residue hydrolyzate from grignard according to claim 1, its
It is characterised by using salt acid for adjusting pH to be concentrated under reduced pressure into the 1/2 of former form waste residue hydrolyzed liquid product to 3~4, be cooled to 10~15
DEG C, insulated and stirred crystallization 2 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108069448B (en) * | 2017-12-27 | 2020-11-10 | 安徽金善化工科技有限公司 | Preparation method of magnesium chloride solution |
| CN109399674B (en) * | 2018-10-24 | 2021-03-19 | 国家海洋局天津海水淡化与综合利用研究所 | Method for extracting bromine magnesium compound from Grignard reaction wastewater and mother liquor |
| RU2737659C1 (en) * | 2020-02-23 | 2020-12-01 | Общество с ограниченной ответственностью "Научно-исследовательский институт технологий органической, неорганической химии и биотехнологий" | Method of producing magnesium chloride of hexavalent |
| CN111689506B (en) * | 2020-07-21 | 2022-09-16 | 河南华龙香料有限公司 | Method for recovering magnesium chloride and tetrahydrofuran from Grignard reaction wastewater |
| CN114315888B (en) * | 2021-12-16 | 2023-12-26 | 袁有学 | Environment-friendly method for synthesizing organic compound based on Grignard method |
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| US3565579A (en) * | 1968-11-18 | 1971-02-23 | Nalco Chemical Co | Recovery of magnesium chloride dihydrate |
| US20030143152A1 (en) * | 2002-01-31 | 2003-07-31 | Vohra Rajinder Nath | Process for recovery of low sodium salt from bittern |
| US20070172433A1 (en) * | 2004-02-27 | 2007-07-26 | Norberto Roveri | Biometic compounds containing hydroxyapatites substituted with magnesium and carbonate, and the processes used to obtain them |
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| CN102344154A (en) * | 2010-08-04 | 2012-02-08 | 张英才 | Method for preparing high-purity magnesium chloride hexahydrate from waste brine |
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| US3565579A (en) * | 1968-11-18 | 1971-02-23 | Nalco Chemical Co | Recovery of magnesium chloride dihydrate |
| US20030143152A1 (en) * | 2002-01-31 | 2003-07-31 | Vohra Rajinder Nath | Process for recovery of low sodium salt from bittern |
| US20070172433A1 (en) * | 2004-02-27 | 2007-07-26 | Norberto Roveri | Biometic compounds containing hydroxyapatites substituted with magnesium and carbonate, and the processes used to obtain them |
| CN101638400A (en) * | 2009-08-26 | 2010-02-03 | 上海益民化工有限公司 | Method for recovering tetrahydrofuran from Grignard reaction waste residue of magnesium chloride |
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