CN101983922B - Method for preparing anhydrous magnesium chloride by calcinating deamination of magnesium chloride hexammouiate - Google Patents
Method for preparing anhydrous magnesium chloride by calcinating deamination of magnesium chloride hexammouiate Download PDFInfo
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- CN101983922B CN101983922B CN2010105458728A CN201010545872A CN101983922B CN 101983922 B CN101983922 B CN 101983922B CN 2010105458728 A CN2010105458728 A CN 2010105458728A CN 201010545872 A CN201010545872 A CN 201010545872A CN 101983922 B CN101983922 B CN 101983922B
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- magnesium chloride
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- ammoniate
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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
- C01F5/305—Dehydrating ammonium or alkali magnesium chlorides, e.g. carnalite
Abstract
The invention relates to a method for preparing anhydrous magnesium chloride by calcinating deamination of magnesium chloride hexammouiate, comprising the following specific steps: (1) drying and decontaminating magnesium chloride under the protection of ammonia; (2) calcining the magnesium chloride at high temperature, transporting the dried magnesium chloride under the protection of ammonia to high-temperature calcination equipment via a sealed pipeline for calcinating deamination, calcining and deaminizing material under the motion state, wherein the beginning temperature for calcination is 200-300 DEG C, calcination temperature gradually rises along with the calcination process, and finally, calcination temperature is 380-450 DEG C, calcination time is 2-4 hours, electricity is adopted for heating, or gas is adopted to directly heat outside the equipment; and (3) cooling and packaging in a sealed mode to obtain a qualified anhydrous magnesium chloride product. The invention has the advantages that ammonia used in the drying step adopts ammonia generated by subsequent calcination, and meanwhile heat energy is used for simply drying energy consumption, thus realizing the effective utilization of energy. The invention has the advantages of simple process flow, simple operation and low cost.
Description
[technical field]
The present invention relates to the Magnesium Chloride Anhydrous technical field, specifically, is the method that a kind of magnesium chloride hex-ammoniate calcining deamination prepares Magnesium Chloride Anhydrous.
[background technology]
Magnesium Chloride Anhydrous is the important source material that electrolytic process prepares MAGNESIUM METAL 99, also is that a kind of important chemical petrochemical complex is used raw material with Catalyst Production.The preparation technology of Magnesium Chloride Anhydrous adds by using magnesite granule mainly that the charcoal chlorination makes, and also has to contain bischofite and make through thermal dehydration technology, and in addition, in producing the Titanium Sponge 40-60 mesh process, Magnesium Chloride Anhydrous is a kind of main by product.The process method of producing Magnesium Chloride Anhydrous is separately confirmed according to the difference of its other resources situation and technology level in different areas.
In numerous routes of preparation Magnesium Chloride Anhydrous, it is through preparation magnesium chloride hex-ammoniate intermediate product that a technological line is arranged, and then deamination prepares this route of Magnesium Chloride Anhydrous and enjoys people to pay close attention to.About preparing Magnesium Chloride Anhydrous from hydrated magnesium chloride, existing both at home and abroad number of patents relates to and adopts hydrated magnesium chloride to prepare magnesium chloride hex-ammoniate and then preparation Magnesium Chloride Anhydrous; Wherein mainly be how hydrated magnesium chloride to be prepared qualified magnesium chloride hex-ammoniate carried out detailed elaboration; Like US5514359, ZL94194221.X, ZL01126495.0; ZL200510028286.5, CN101734693A etc.See from the patent of having announced, the calcining of magnesium chloride hex-ammoniate for being expressed as in cryodrying, high-temperature calcination, is not related to control condition.Chinese patent ZL94194221.X has provided operating parameters in embodiment, in its drying and calcination process, all feed argon gas or gases such as nitrogen or carbonic acid gas.Remove part ammonia because magnesium chloride hex-ammoniate can take place to decompose at a lower temperature, form five ammonia magnesium chlorides and four ammonia magnesium chlorides, it very easily forms the magnesium chloride complex compound with organic solvent, as forming MgCl with methyl alcohol
25NH
3CH
3OH and MgCl
24NH
32CH
3OH etc., organism is difficult to remove in the magnesium chloride complex compound, and at high temperature cracking forms materials such as carbon, water easily, and magnesium chloride and water form Natural manganese dioxide and basic magnesium chloride, form product gas purity and color and luster.The drying and calcining process all has rare gas element to add simultaneously, must separate back ammonia and could use.
[summary of the invention]
It is low to the objective of the invention is to overcome in the prior art magnesium chloride hex-ammoniate deamination process Magnesium Chloride Anhydrous product purity, and the defective that impurity is many provides a kind of magnesium chloride hex-ammoniate calcining deamination to prepare the method for Magnesium Chloride Anhydrous.
Of the present invention being contemplated that: under coldcondition, magnesium chloride hex-ammoniate is carried out drying under the ammonia protective atmosphere, remove organic impuritys such as reaction medium; Because the ammonia atmosphere protection, under low-temperature condition, magnesium chloride hex-ammoniate does not decompose; Organic cpds can not form magnesium chloride compound with magnesium chloride and be able to effectively deviate from; When actual production, the ammonia that adopts the comparatively high temps that follow-up calcining produces provides dry necessary energy simultaneously as shielding gas.Magnesium chloride hex-ammoniate after effectively deviating from organic medium is under the micro-vacuum condition, and high temperature removal ammonia obtains Magnesium Chloride Anhydrous, and its ammonia can other industry use and self recycle through the gas booster compressor compression.The ammonia that ammonia protection drying-micro-vacuum calcining process, the employed ammonia of its drying stage can adopt follow-up calcining to produce utilizes heat energy simultaneously, and simple energy consumption for drying does not have other generation of waste materials in whole process of production, realized effective utilization of energy.
The objective of the invention is to realize through following technical scheme:
A kind of magnesium chloride hex-ammoniate calcining deamination prepares the method for Magnesium Chloride Anhydrous, and its concrete steps do,
(1) the magnesium chloride hex-ammoniate cryodrying removal of impurities under the ammonia protection
No matter be the magnesium chloride hex-ammoniate magnesium chloride that adopts the reaction-crystallization method preparation, still wait the magnesium chloride hex-ammoniate of by-product in other processes in silicon production, the magnesium chloride hex-ammoniate that it obtains through solid-liquid separation, inevitable entrainment mother liquor, its mother liquor mainly is an organic cpds; In the drying plant of sealing, material is kept in motion down all the time, carries out dry removal of impurities through drying under the ammonia protection, and drying temperature is 60～120 ℃; Also can adopt follow-up calcine 300～450 ℃ ammonia of workshop section's generation and the pending abundant contact drying removal of impurities of magnesium chloride hex-ammoniate; Both made full use of the heat energy of calcining the high temperature ammonia that is produced; Reduced the demand of drying process to heat, reduced the ammonia temperature simultaneously and helped follow-up use, this drying removal of impurities process can be that continuous production also can intermittent process production; The employing successive processes is produced, and keeping the residence time is 0.5～2 hour; Adopt interrupter method production to finish the back insulation in charging got final product in 1 hour;
(2) the magnesium chloride hex-ammoniate high-temperature calcination is handled
The dry good magnesium chloride hex-ammoniate of ammonia protection is calcined deamination through the pipe-line transportation entering high-temperature calcination equipment of sealing, and high-temperature calcination equipment is Sealing Arrangement, and material is kept in motion down and calcines the deamination process all the time; Calcining beginning temperature is controlled at 200～300 ℃, and calcining temperature progressively raises with the carrying out of calcination process, and last calcining temperature is 380～450 ℃, and high-temperature calcination equipment internal pressure is the micro-vacuum pressure condition; Calcination time is 2～4 hours, adds the thermal recovery electrically heated, perhaps adopts combustion gas direct heating outside equipment;
(3) airtight cooling packing obtains qualified anhydrous chlorides of rase magnesium products, and ammonia directly supplies segment process use down through compression, need not isolation of purified.
Compared with prior art, positively effect of the present invention is:
(1) the high temperature ammonia of adopting process of the present invention self generation is protection gas; Provide the magnesium chloride hex-ammoniate drying process needed heat simultaneously; Avoid magnesium chloride hex-ammoniate to decompose and stay the complexing room, stopped organism and formed muriate, thereby avoid organism decomposition generation water when high-temperature calcination at drying stage and magnesium chloride in the cryodrying stage; And then form basic magnesium chloride and Natural manganese dioxide with magnesium chloride, influence Magnesium Chloride Anhydrous purity and use value;
(2) calcination process of the present invention does not add other gases, for the follow-up use of ammonia provides good condition, avoids follow-up gas delivery;
(3) technical process of the present invention is simple, easy to operate, and cost is low.
[description of drawings]
Fig. 1 process flow sheet of the present invention.
[embodiment]
Below provide a kind of magnesium chloride hex-ammoniate calcining of the present invention deamination to prepare the method embodiment of Magnesium Chloride Anhydrous.
Embodiment 1
Adopt the method for Chinese patent ZL01126495.0; Preparation magnesium chloride hex-ammoniate sample, wherein, Chinese patent 01126495.0 relates to a kind of method of producing Magnesium Chloride Anhydrous; Be the patent of applicant in first to file, its key step is the preparation of organic hydrated magnesium chloride solution; The complex compound of reactive crystallization coupling preparation Magnesium Chloride Anhydrous; Solid-liquid separation and washing; Crystalline mother solution and precipitation agent recycle; Thermal treatment complex compound intermediate preparation Magnesium Chloride Anhydrous.Analyzing its water-content is 0.21%, gets magnesium chloride hex-ammoniate 200g, and in the 500ml round-bottomed flask, this flask is furnished with the glass impeller and stirs; The outside electrically heated cover temperature control that adopts heats, and feeds protection of ammonia, and ammonia flow is 50ml/min, stirs dry removal of impurities 1.5 hours under 100 ℃ of conditions of temperature control; Stop protection of ammonia, further be warmed up to 400 ℃ and carry out the magnesium chloride hex-ammoniate calcining, taking out the ammonia that discharges through vacuum pump; Keep little negative pressure, calcined 4 hours, get the anhydrous chlorides of rase magnesium products.Through analyzing the finished product is Magnesium Chloride Anhydrous, and wherein the major impurity water-content 0.2%, content of magnesia 0.18%.
Embodiment 2
Adopt the method for Chinese patent ZL01126495.0, preparation magnesium chloride hex-ammoniate sample, analyzing its water-content is 0.21%, gets magnesium chloride hex-ammoniate 200g; In the 500ml round-bottomed flask, this flask is furnished with the glass impeller and stirs, and the outside electrically heated cover temperature control that adopts heats; Feed protection of ammonia, ammonia flow is 50ml/min, stirs dry removal of impurities 1 hour under 90 ℃ of conditions of temperature control; Stop protection of ammonia, further be warmed up to 450 ℃ and carry out the magnesium chloride hex-ammoniate calcining, taking out the ammonia that discharges through vacuum pump; Keep little negative pressure, calcined 3 hours, get the anhydrous chlorides of rase magnesium products.Through analyzing the finished product is Magnesium Chloride Anhydrous, and wherein the major impurity water-content 0.18%, content of magnesia 0.19%.
Embodiment 3
Adopt the method for Chinese patent ZL01126495.0, preparation magnesium chloride hex-ammoniate sample, analyzing its water-content is 0.21%, gets magnesium chloride hex-ammoniate 200g; In the 500ml round-bottomed flask, this flask is furnished with the glass impeller and stirs, and the outside electrically heated cover temperature control that adopts heats; Feed protection of ammonia, ammonia flow is 50ml/min, stirs dry removal of impurities 1 hour under 90 ℃ of conditions of temperature control; Stop protection of ammonia, further be warmed up to 450 ℃ and carry out the magnesium chloride hex-ammoniate calcining, taking out the ammonia that discharges through vacuum pump; Keep little negative pressure, calcined 3 hours, get the anhydrous chlorides of rase magnesium products.Through analyzing the finished product is Magnesium Chloride Anhydrous, and wherein the major impurity water-content 0.18%, content of magnesia 0.19%.
Embodiment 4
Adopt the method for Chinese patent ZL01126495.0, preparation magnesium chloride hex-ammoniate sample, analyzing its water-content is 0.21%; Adopt two continuous fluidized beds to carry out dry removal of impurities and the operation of calcining deamination, magnesium chloride hex-ammoniate gets into first fluidized-bed and carries out dry removal of impurities, the ammonia that its protection discharges from second fluidized bed calcination with ammonia; Under 120 ℃ of conditions of temperature control, 1 hour residence time is through the magnesium chloride hex-ammoniate entering secondary calcining deamination fluidized-bed of too dry removal of impurities; 380 ℃ of calcining temperatures; Residence time of material 4 hours is kept little negative pressure, is taking out the ammonia that discharges through gas blower and is delivering into dry removal of impurities fluidized-bed.Get the anhydrous chlorides of rase magnesium products.Through analyzing the finished product is Magnesium Chloride Anhydrous, and wherein the major impurity water-content 0.16%, content of magnesia 0.18%.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (2)
1. magnesium chloride hex-ammoniate calcining deamination prepares the method for Magnesium Chloride Anhydrous, it is characterized in that, concrete steps do,
(1) the magnesium chloride hex-ammoniate cryodrying removal of impurities under the ammonia protection
In the drying plant of sealing, material is kept in motion down all the time, carries out dry removal of impurities through drying under the ammonia protection, and drying temperature is 60～120 ℃;
(2) the magnesium chloride hex-ammoniate high-temperature calcination is handled
The dry good magnesium chloride hex-ammoniate of ammonia protection is calcined deamination through the pipe-line transportation entering high-temperature calcination equipment of sealing, and material is kept in motion down and calcines the deamination process all the time; Calcining beginning temperature is 200～300 ℃, and calcining temperature progressively raises with the carrying out of calcination process, and last calcining temperature is 380～450 ℃; Calcination time is 2～4 hours, adds the thermal recovery electrically heated, perhaps adopts combustion gas direct heating outside equipment;
Described high-temperature calcination equipment is Sealing Arrangement;
Described high-temperature calcination equipment internal pressure is a micro-vacuum pressure;
(3) airtight cooling packing obtains the anhydrous chlorides of rase magnesium products.
2. a kind of magnesium chloride hex-ammoniate calcining deamination as claimed in claim 1 prepares the method for Magnesium Chloride Anhydrous; It is characterized in that; Described dry removal of impurities process is continuous production or intermittent process production, adopts successive processes production, and keeping the residence time is 0.5～2 hour; Adopt interrupter method production to finish back insulation 1 hour in charging.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105458728A CN101983922B (en) | 2010-11-16 | 2010-11-16 | Method for preparing anhydrous magnesium chloride by calcinating deamination of magnesium chloride hexammouiate |
| PCT/CN2010/080210 WO2012065338A1 (en) | 2010-11-16 | 2010-12-24 | Method for preparing anhydrous magnesium chloride by calcining and deaminating magnesium chloride hexammoniate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105458728A CN101983922B (en) | 2010-11-16 | 2010-11-16 | Method for preparing anhydrous magnesium chloride by calcinating deamination of magnesium chloride hexammouiate |
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| CN101983922A CN101983922A (en) | 2011-03-09 |
| CN101983922B true CN101983922B (en) | 2012-05-09 |
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| WO (1) | WO2012065338A1 (en) |
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| RU2754213C1 (en) * | 2020-10-07 | 2021-08-30 | Публичное Акционерное Общество "Корпорация Всмпо-Ависма" | Method for obtaining anhydrous carnallite and processing line for implementation thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514359A (en) * | 1993-04-06 | 1996-05-07 | Alcan International Limited | Process for making anhydrous magnesium chloride |
| CN1689973A (en) * | 2004-04-29 | 2005-11-02 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CZ293993B6 (en) * | 1993-10-28 | 2004-09-15 | Commonwealth Scientific And Industrial Research Organisation | Process for preparing substantially 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 |
| CN100494425C (en) * | 2005-12-07 | 2009-06-03 | 中国科学院过程工程研究所 | Method for preparing metal magnesium from magnesium mineral |
| 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 |
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- 2010-12-24 WO PCT/CN2010/080210 patent/WO2012065338A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514359A (en) * | 1993-04-06 | 1996-05-07 | Alcan International Limited | Process for making anhydrous magnesium chloride |
| CN1689973A (en) * | 2004-04-29 | 2005-11-02 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
Non-Patent Citations (1)
| Title |
|---|
| 宋兴福 等.六氨氯化镁热解过程及其非等温动力学.《化工学报》.2008,第59卷(第9期),第2255-2259页. * |
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| CN101983922A (en) | 2011-03-09 |
| WO2012065338A1 (en) | 2012-05-24 |
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