CN1333183A - Methodf or preparing anhydrous magnesium chloride - Google Patents
Methodf or preparing anhydrous magnesium chloride Download PDFInfo
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- CN1333183A CN1333183A CN 01126495 CN01126495A CN1333183A CN 1333183 A CN1333183 A CN 1333183A CN 01126495 CN01126495 CN 01126495 CN 01126495 A CN01126495 A CN 01126495A CN 1333183 A CN1333183 A CN 1333183A
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- magnesium chloride
- organic solvent
- anhydrous
- ammonia
- solution
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Abstract
The method for preparing anhydrous magnesium chloride includes the following steps: 1. preparation of organic hydrated magnesium chloride; 2. reaction, crystallization and coupling reaction to prepare anhydrous magnesium chloride complex; 3. solid-liquid separation and washing; 4. crystallizing mother liquor and circular utilization of precipitant; and 5. heat treatment of complex intermediate product to obtain the anhydrous magnesium chloride. Said invention adopts mixed organic solvent to prepare hydrated magnesium chloride solution, can reduce production of alkoxide in the course of crystallization, and can return the washing liquor containing saturated hexamine magnesium chloride into crystallization reaction procedure, and can raise rate of deposition of magnesium chloride and utilization rate of ammonia, and can reduce the running load of recovery tower. Said invention also adopts the reaction cold-crystallization process, and is favorable for implementing industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of Magnesium Chloride Anhydrous, particularly a kind of method that adopts bischofite to prepare Magnesium Chloride Anhydrous adopts the directly electrolysis magnesium chloride system MAGNESIUM METAL use of Magnesium Chloride Anhydrous of present method preparation.
Background technology
MAGNESIUM METAL is of many uses in modern industry.Traditional industry system magnesium technology is that the double salt (potassium carnallitite or ammonium carnallitite) with magnesite, rhombspar or magnesium chloride is that raw material dewaters to obtain Magnesium Chloride Anhydrous.
By product---bischofite in the Repone K production process of salt lake, super quality and competitive price are desirable feedstock of electrolytic magnesium.Bischofite can be deviate from wherein 4 parts of water by traditional heater means, forms MgCl
22H
2O, and magnesium chloride dihydrate can't continue to deviate from wherein water with hot method, because of under the situation of being heated, MgCl
22H
2Serious hydrolysis reaction also takes place in O except that dewatering, generate magnesium oxide and emit hydrogen chloride gas, can't satisfy the requirement of electrolytic magnesium production to content of magnesia in the Magnesium Chloride Anhydrous.So, adopt conventional heating means can't obtain to satisfy the Magnesium Chloride Anhydrous of electrolytic magnesium requirement.
Another kind of method of producing Magnesium Chloride Anhydrous is a thermal dehydration under hydrogenchloride atmosphere, obtains being used for the Magnesium Chloride Anhydrous that electrolytic process generates MAGNESIUM METAL thereby this method is based on the hydrolysis that can suppress the hydrated form magnesium chloride under the hydrogenchloride atmosphere.The basic procedure of this method is that the magnesium chloride mother liquor after purifying is concentrated into MgCl
2＞45% solution carries out mist projection granulating, takes off into MgCl under 100-200 ℃ of hot gas flow
22H
2O dewaters to containing MgCl under 620-650 ℃ of HCl atmosphere again
2＞95%, the Magnesium Chloride Anhydrous of MgO＜0.5%.Because MgCl
2Facile hydrolysis often contains some impurity such as MgO in the resultant, MgOHCl etc. are so dehydrate is handled through the fusion carburizing chlorination again.Rare HCl recycles in the recovery tail gas.This method corrosion is more serious, and section H Cl G﹠W vapour condenses in MgCl
2In the product, all there are many problems in the storage of simultaneously a large amount of hydrogen chloride gas and use.
Another kind of method of producing Magnesium Chloride Anhydrous is the double salt method, adopts ammonium chloride and bischofite to form the ammonium carnallitite, and the ammonium carnallitite is through dewatering, taking off ammonium and obtain Magnesium Chloride Anhydrous.This method is performed such: with NH
4In the water-soluble chloromagnesite aqueous solution of Cl, utilize NH
4Cl-MgCl
2-H
2O ternary system solubleness is synthesized ammonium carnallitite NH
4ClMgCl
26H
2O dewaters, takes off ammonium to the ammonium carnallitite again.This method can suppress the magnesium chloride hydrolysis, produces to be bordering on anhydrous magnesium chloride.But at NH
4The capture of Cl dust, equipment corrosion, free " NH
3" recovery, improve NH
4It is perfect that aspects such as Cl yield have a large amount of problems to need.
The another kind of method that is prepared Magnesium Chloride Anhydrous by hydrated magnesium chloride is an ammoniation process, and its basic thought is that hydrated magnesium chloride is changed into magnesium chloride hex-ammoniate, and magnesium chloride hex-ammoniate pyrolysis deamination is produced Magnesium Chloride Anhydrous.
Prepare in the research of Magnesium Chloride Anhydrous at ammonia process, mainly divide two kinds:
(1) be reaction medium with water, patent US.3092450 and US.4228144 are described in detail this method: in containing the aqueous solution of ammonia, add the hydration solution of magnesium chloride and ammonium chloride, react generation MgCl down at low temperature (as-50～0 ℃)
26NH
3Precipitation, deamination makes Magnesium Chloride Anhydrous after methanol wash.The main drawback of this method has: (1) reaction conversion ratio is low, and (2) temperature is low, the energy consumption height, and (3) ammonia consumption is big.
(2) be reaction medium with the organic solvent, the basic step of this method comprises: (1) hydrated magnesium chloride and organic solvent form magnesium chloride organic solution; (2) magnesium chloride organic solution dehydration, the organic solution of formation Magnesium Chloride Anhydrous; (3) form the magnesium chloride complex precipitate by anhydrous organic solution and precipitation agent reaction; (4) complex-precipitation of heating magnesium chloride prepares Magnesium Chloride Anhydrous, and the recovery of organic solvent and precipitation agent is used.
After proposing this method from nineteen forty-two US2381995, constantly there is patent documentation to make improvements.Improved technology mainly concentrates on choosing of organic solvent.
U.S. Patent No. 2,381,995 with ethylene glycol and the MgCl that contains 30-35%
2Mix with other halide solution, vacuum distilling is removed portion water and is just obtained anhydrous MgCl
2Ethylene glycol solution forms hexammine MgCl through ammonification
26NH
3Precipitation.With methanol wash precipitation, slough methyl alcohol and 400 ℃ 70-80 ℃ of heating and take off NH
3, product MgCl
2: 99.5%.In addition, U.S. Patent No. 3,352,634 adopt the magnesium chloride of partial dehydration to be decomposed in the alcohol of a kind of 4-10 of containing carbon atom, and solution produces the magnesium chloride solution that parches through azeotropic drying in alcohol, produce MgCl through ammonia treatment then
26NH
3Precipitation.This method need be washed the amide precipitation by the low-boiling point alcohol as methyl alcohol, decomposes generation impurity to reduce high-boiling point alcohol.And the high-dissolvability of ammino compound causes MgCl in high-boiling point alcohol
26NH
3Low deposition rate.
About adopting ethylene glycol is that the patent of solvent is more, and patent CN 1135743A has detailed narration to this.
Patent US5514359 improves aforesaid method, provides a kind of and has directly generated MgCl from organic hydrated magnesium chloride solution ammonification
26NH
3Sedimentary method, select for use with methyl alcohol is the low-boiling point alcohol of representative, be reflected under 10～60 ℃ and carry out, this invention was increasing aspect the utilization ratio of precipitation, solvent and the ammonia of magnesium chloride more in the past, but defective such as the technology that this patent provides still exists that deposition rate has much room for improvement, ammonia and organic solvent demand are still bigger.
Summary of the invention
Defectives such as the technical issues that need to address of the present invention provide a kind ofly produces electrolysis with the method for Magnesium Chloride Anhydrous from magnesium chloride hexahydrate (bischofite), and the deposition rate that prior art exists is not high enough to remedy, ammonia and organic solvent demand are still bigger.
Method of the present invention comprises the steps:
1) preparation of organic hydrated magnesium chloride solution; 2) complex compound of reactive crystallization coupling preparation Magnesium Chloride Anhydrous: 3) solid-liquid separation and washing; 4) crystalline mother solution and ammonia recycling use; 5) thermal treatment anhydrous chlorides of rase magnesium complex deamination prepares Magnesium Chloride Anhydrous.
The present invention has adopted blended organic solvent preparation hydrated magnesium chloride solution, therefore adopts the mixing solutions of methyl alcohol and ethanol, propyl alcohol or butanols, can reduce the generation of alkoxide in the crystallisation process.Simultaneously, the washings that the present invention will contain the organic solvent of saturated magnesium chloride hex-ammoniate, ammonia is sent the crystallization reaction operation back to, has changed prior art and has directly imported the flow process that rectifying tower reclaims.The improvement of this technology, to improving the deposition rate of magnesium chloride, improve the utilization ratio of ammonia, the operating load that alleviates recovery tower all has a significant effect, the productive rate of magnesium chloride is brought up to more than 95% from 90% of prior art, the ammonia consumption of producing 1 mole of magnesium chloride drops to 9～10 moles from 15～30 moles, and the consumption of producing the organic solvent of 1 mole of magnesium chloride also drops to 24～30 moles from 32～40 moles.Simultaneously, contain the small-crystalline of magnesium chloride hex-ammoniate in the washings of reuse, play the effect of crystal seed in crystallizer, therefore, this technology crystalline magnesium chloride hex-ammoniate has certain particle, is easy to filter.
Method of the present invention has very significant advantage, and (1) the present invention adopts reaction cold crystallization technology, and the reaction dehydration does not have the hydrolysis phenomenon and takes place, and magnesian content is low in the product; (2) production technique of the present invention is a friendly process, and production process does not almost have corrosion, does not have " three waste discharge "; (3) operational condition gentleness of the present invention does not need poisonous and hazardous dangerous gases such as hydrogenchloride, chlorine.(4) organic solvent of the present invention's employing does not need anhydrous state: the deposition rate height of (5) magnesium chloride, and productive rate reaches more than 95%, and the consumption of ammonia and organic solvent is low, promptly adopts this technology, and the internal circulating load of generation will reduce by 20～45%; (6) the reactive crystallization granularity is big, helps filtering, washing, and helps the industrialization of this technology.
Description of drawings
Fig. 1 is a schema of the present invention.
The specific embodiment
As seen from Figure 1, method of the present invention comprises the steps:
1) preparation of organic hydration magnesium chloride solution:
Physicochemical property according to bischofite, bischofite and ammonium chloride are dissolved in the organic solvent in dissolving tank 1, the weight percentage of Chlorine in Solution magnesium is 8～20%, and the content of ammonium chloride is 1～3%, and the organic solvent of employing is C1～C
4Low-carbon alcohols, its percentage by weight ratio of components scope is:
1 carbon: 10-90%; 2 carbon: 5-80%; 3 carbon: 0-20%; 4 carbon: 0-10%;
A kind of and composition thereof in methyl alcohol, ethanol, propyl alcohol, butanols or the ethylene glycol preferably;
2) complex compound of reactive crystallization coupling preparation anhydrous magnesium chloride
In crystallizer 2, add the cleaning solution from the magnesium chloride hexammoniate crystal in the washer 5, stirring bar Under the part, add step 1) organic hydration magnesium chloride solution, in adition process, can replenish precipitating reagent, Guaranteeing that precipitating reagent is in saturated or excessive state all the time, the simultaneous reactions temperature is controlled at-5-40 ℃, with 10～30 ℃ be best, crystal, obtains through aging, secondary recrystallization 0.5～2 hour 0～20 ℃ temperature after the crystallization Certain granules size and the crystal that distributes are the anhydrous chlorides of rase magnesium complex; The precipitating reagent that adopts comprises liquefied ammonia or ammonia Gas etc.; Used organic solvent is and step 1) a kind of and composition thereof in the identical low-carbon alcohols, its group Becoming and step 1) middle organic solvent is identical; Temperature remains unchanged substantially in reaction crystallization process.
Because the present invention has adopted the cleaning solution of the washing magnesium chloride hexammoniate crystal in washer 5, this washing Liquid contains crystal seed and the saturated organic solvent of ammonia of magnesium chloride hexammoniate, and therefore, the solid granularity that crystallization goes out is big, Be easy to Separation of Solid and Liquid, simultaneously, reduced widely the consumption of organic solvent and precipitating reagent, improved magnesium chloride Rate of deposition and the utilization rate of organic solvent and ammonia, thereby reduced energy consumption.
3) Separation of Solid and Liquid and washing
Mixture in the crystallizer 2 is filtered in separator 3, and filter cake is sent into washer 5, uses through precipitating reagent Saturated organic solvent washs, and obtains the anhydrous chlorides of rase magnesium complex;
The cleaning solution that contains the saturated organic solvent of magnesium chloride hexammoniate crystal seed and ammonia is sent crystallizer 2 back to and is recycled; Crystalline mother solution is sent to recovery tower 4, crystalline mother solution is carried out rectifying separate, and ammonia and organic solvent direct circulation make With, tower reactor magnesium chloride organic solution then can be sent crystallizer 2 back to and be recycled;
4) the standby anhydrous magnesium chloride of heat treatment anhydrous chlorides of rase magnesium complex Study of Deamination
In revolving burner 6 the anhydrous chlorides of rase magnesium complex is heat-treated, heat treatment temperature is at 120～140 ℃ Lower dry 0.5～2 hour, remove remaining organic solvent, the roasting that heats up again removes the ammonia of complexing, roasting Temperature is 400～800 ℃, and roasting time is 1～3 hour, but can obtain the anhydrous magnesium chloride of use in electrolysis, The water content of anhydrous magnesium chloride is lower than 0.1%, and content of magnesia is lower than 0.1%. Be removed the organic molten of remnants Agent and ammonia enter recovery tower 4 and reclaim.
The raw material magnesium chloride hexahydrate that this invention requires not necessarily, the crystallization water of its magnesium chloride be lower than at 6 o'clock with Sample is suitable for, and magnesium chloride containing is suitable for too at the magnesium chloride solution more than 40%.
Embodiment 1
In 1 liter reactor, add 250 gram methyl alcohol and 50 gram ethanol and 3 gram ammonium chlorides, reach at normal temperature Under the stirring condition, pass into ammonia and make it saturated in solvent, the magnesium chloride solution that simultaneously slow adding has prepared 300 grams, wherein magnesium chloride containing 9.3%, water 10.7%, ammonium chloride 1.2%, organic solvent 78.8%: reaction 1.5 after hour, the paste-like feed liquid is filtered, restrains the mixed liquor of ethanol with the saturated 100 gram methyl alcohol and 20 of ammonia Washing, solid product 550 ℃ of calcinings 1.2 hours, can get anhydrous magnesium chloride, wherein moisture content through secluding air Content is less than 0.1%, and content of magnesia is less than 0.1%, and the productive rate of magnesium chloride is 89.3%, produces 1 in the production The ammonia demand of mole of magnesium chloride is 15 moles.
In 1 liter reactor, add embodiment 1 cleaning solution 300 grams, the other the same as in Example 1 is through knot The anhydrous magnesium chloride of crystalline substance, deamination, its water content is 0.1%, content of magnesia is 0.1%, magnesium chloride Productive rate is 98.6%. The consumption of ammonia and organic solvent reduces 40.4% and 35.8% than embodiment 1 respectively. Embodiment 3
In 1 liter reactor, add 300 gram low-boiling point alcohol, wherein methyl alcohol 87%, ethanol 10% and fourths Alcohol 3% and 3 gram ammonium chlorides under normal temperature and stirring condition, pass into ammonia and make it saturated in solvent, and are simultaneously slow Slowly add magnesium chloride solution 300 grams that prepared, wherein magnesium chloride containing 9.6%, water 14.6%, ammonium chloride 1.5%, low-boiling point alcohol 74.3%, wherein methyl alcohol 87%, ethanol 10% and butanols 3%; React after 1.5 hours, The paste-like feed liquid is filtered, with the saturated low-boiling point alcohol washing of 100 gram ammonia, wherein methyl alcohol 87%, ethanol 10% With butanols 3%, solid product 450 ℃ of calcinings 1.5 hours, can get anhydrous magnesium chloride through secluding air, its Middle water content is less than 0.3%, and content of magnesia is less than 0.2%, and the productive rate of magnesium chloride is 90.2%, produces 1 The ammonia demand of mole of magnesium chloride is 18 moles. Embodiment 4
In 1 liter reactor, add embodiment 3 cleaning solutions 300 grams, the other the same as in Example 3 is through knot The anhydrous magnesium chloride of crystalline substance, deamination, its water content is 0.3%, magnesia is 0.2%, the productive rate of magnesium chloride Be 97.5%. The consumption of ammonia and organic solvent reduces 37.4% and 32.4% than embodiment 3 respectively.
Claims (6)
1. a method of producing Magnesium Chloride Anhydrous comprises the steps: 1) preparation of organic hydrated magnesium chloride solution; 2) complex compound of reactive crystallization coupling preparation Magnesium Chloride Anhydrous; 3) solid-liquid separation and washing; 4) crystalline mother solution and ammonia recycling use; 5) thermal treatment anhydrous chlorides of rase magnesium complex deamination prepares Magnesium Chloride Anhydrous, it is characterized in that:
1. said organic solvent is C
1～C
4The mixture of low-carbon alcohol; 2. the washings that will contain the organic solvent of saturated magnesium chloride hex-ammoniate, ammonia is sent step 2 back to) the crystallization reaction operation.
2. the method for claim 1 is characterized in that, said organic solvent is C
1～C
4The mixture of low-carbon alcohol, its weight percent ratio of components scope is:
1 carbon: 10-90%; 2 carbon: 5-80%:3 carbon: 0-20%; 4 carbon: 0-10%.
3. method as claimed in claim 1 or 2 is characterized in that said organic solvent comprises methyl alcohol, ethanol, propyl alcohol, butanols or ethylene glycol.
4. the method for claim 1 is characterized in that, bischofite and ammonium chloride are dissolved in the above-mentioned organic solvent in dissolving tank (1), and the weight percentage of magnesium chloride is 8～20% in the solution, and the content of ammonium chloride is 1～3%.
5. the method for claim 1, it is characterized in that, in crystallizer (2), add organic hydrated magnesium chloride solution from magnesium chloride hex-ammoniate crystalline washings in the washer (5) and claim 1, and additional precipitation agent, temperature of reaction is-5-40 ℃, after the crystallization crystal 0～20 ℃ temperature through aging, secondary recrystallization 0.5～2 hour, mixture in the crystallizer (2) is filtered in separator (3), filter cake is sent into washer (5), with washing, obtain the anhydrous chlorides of rase magnesium complex through the saturated organic solvent of precipitation agent; The washings that contains the saturated organic solvent of magnesium chloride hex-ammoniate crystal seed and ammonia is sent crystallizer (2) back to and is recycled; Crystalline mother solution is sent to recovery tower (4), and crystalline mother solution is carried out rectifying separation, and ammonia and organic solvent directly recycle, and tower still magnesium chloride organic solution then can be sent crystallizer (2) back to and be recycled; In rotary oven (6), the anhydrous chlorides of rase magnesium complex is heat-treated, 120～140 ℃ dry 0.5～2 hour down, and then be 400～800 ℃ of following roastings 1～3 hour, but can obtain the Magnesium Chloride Anhydrous of use in electrolysis in temperature.
6. method as claimed in claim 5 is characterized in that, temperature of reaction is 10～30 ℃.
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|---|---|---|---|
| CNB011264950A CN1156398C (en) | 2001-08-17 | 2001-08-17 | Methodf or preparing anhydrous magnesium chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011264950A CN1156398C (en) | 2001-08-17 | 2001-08-17 | Methodf or preparing anhydrous magnesium chloride |
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|---|---|
| CN1333183A true CN1333183A (en) | 2002-01-30 |
| CN1156398C CN1156398C (en) | 2004-07-07 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295151C (en) * | 2004-07-24 | 2007-01-17 | 陈瑜 | Process for producing anhydrous magnesium chloride by microwave energy |
| CN1302994C (en) * | 2005-07-29 | 2007-03-07 | 华东理工大学 | Bischofite dehydration-electrolysis method for refining magnesian |
| CN1326773C (en) * | 2004-04-29 | 2007-07-18 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
| CN100379682C (en) * | 2004-11-01 | 2008-04-09 | 中信国安盟固利新能源科技有限公司 | Method for preparing anhydrous magnesium chloride |
| CN101462746B (en) * | 2007-12-19 | 2012-06-27 | 中国科学院过程工程研究所 | Method for preparing anhydrous magnesium chloride from bischofite |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
-
2001
- 2001-08-17 CN CNB011264950A patent/CN1156398C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326773C (en) * | 2004-04-29 | 2007-07-18 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
| CN1295151C (en) * | 2004-07-24 | 2007-01-17 | 陈瑜 | Process for producing anhydrous magnesium chloride by microwave energy |
| CN100379682C (en) * | 2004-11-01 | 2008-04-09 | 中信国安盟固利新能源科技有限公司 | Method for preparing anhydrous magnesium chloride |
| CN1302994C (en) * | 2005-07-29 | 2007-03-07 | 华东理工大学 | Bischofite dehydration-electrolysis method for refining magnesian |
| CN101462746B (en) * | 2007-12-19 | 2012-06-27 | 中国科学院过程工程研究所 | Method for preparing anhydrous magnesium chloride from bischofite |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
| CN106745163B (en) * | 2015-11-24 | 2018-10-19 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1156398C (en) | 2004-07-07 |
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Owner name: QINGHAI SALT LAKE MAGNESIUM CO., LTD. Free format text: FORMER OWNER: EAST CHINA UNIVERSITY OF SCIENCE Effective date: 20101025 |
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Effective date of registration: 20101025 Address after: 816000 No. 28, the Yellow River Road, Qinghai, Golmud Patentee after: Qinghai Saline Lake magnesium Co., Ltd. Address before: 200237 Meilong Road, Shanghai, No. 130, No. Patentee before: East China University of Science and Technology |
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