CN1978680A - Method for preparing metal magnesium from magnesium mineral - Google Patents
Method for preparing metal magnesium from magnesium mineral Download PDFInfo
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- CN1978680A CN1978680A CNA2005101263170A CN200510126317A CN1978680A CN 1978680 A CN1978680 A CN 1978680A CN A2005101263170 A CNA2005101263170 A CN A2005101263170A CN 200510126317 A CN200510126317 A CN 200510126317A CN 1978680 A CN1978680 A CN 1978680A
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Abstract
The invention relates to the method used magnesium bearing mineral to make magnesium metal. It includes the following steps: fluidizing and activating roasting for the magnesium bearing mineral to make active magnesium oxide; processing chlorination reaction distilling dehydrating for the active magnesium oxide to gain high concentration anhydrous magnesium chloride organic medium solution; using anhydrous organic medium to match to make anhydrous magnesium chloride organic solution, cool and filter; reaction crystallization under ammonia saturated conditions for the filtrate to gain magnesium chloride hex-ammoniate organic slime; filtrating to separate the magnesium chloride hex-ammoniate crystal from the organic medium filtrate back to use repeatedly; washing by ammonia saturated micro-molecule anhydrous alcohol and rapid fluidizing dryi ng to gain anhydrous magnesium chloride hex-ammoniate; setting in de-ammoniation electrolysis coupled reactor to do de-ammoniation and electrolysis to gain magnesium metal.
Description
Technical field
The invention relates to the technology method of production MAGNESIUM METAL, relate to the production of magnesium chloride hex-ammoniate preparation and MAGNESIUM METAL thereof, Magnesium Chloride Anhydrous and activated magnesia simultaneously.
Background technology
At present, both at home and abroad MAGNESIUM METAL industrialized producing technology method has three kinds: (1) is raw material with containing magnesium halogen stone (as bischofite, potassium carnallitite, ammonium carnallitite), they after dewatering, electrolysis production MAGNESIUM METAL in the magnesium chloride fused salt; (2) adopting rhombspar is raw material, and reductive agents such as its calcining back and ferrosilicon carry out thermal reduction reaction production MAGNESIUM METAL (hot reducing method) under high temperature, high vacuum; (3) adopting magnesium-containing mineral is raw material, carries out chlorination reaction with chlorine and carbon and generates Magnesium Chloride Anhydrous, fused salt electrolysis production MAGNESIUM METAL then.
Hot reducing method production MAGNESIUM METAL method, though can commercial move, but resource, energy consumption are big, resource, energy utilization rate are low, and production efficiency is low, the serious (S.Ramakrishnan of environmental pollution, P.Koltun, " Resources, Conservation and Recycling ", 42 (2004) 49-64)
The crucial workshop section of electrolytic chlorination magnesium production MAGNESIUM METAL is the preparation of Magnesium Chloride Anhydrous, and commercial used method has:
The a kind of of Norsk Hydro development produces Magnesium Chloride Anhydrous particulate method from concentrating magnesium chloride bittern; this method is described in US 3742199 patents: after the magnesium chloride bittern evaporation is concentrated; under 200 ℃, carry out the fluidization dehydration and produce the magnesium chloride dihydrate powder with air; then under 300 ℃; carry out three grades of fluidised bed dehydrations with anhydrous hydrogen chloride gas; make anhydrous magnesium chloride; this method can commercial be moved; but need the hydrogen chloride gas circulation of a great deal of, for example dehydration needs 50 times theoretical amount, therefore; the recycling use process is numerous and diverse; equipment corrosion is serious; the environment protection condition is poor, and capital investment is very big.
Magnesium-containing mineral production MAGNESIUM METAL method has:
Patent CN 1049381A report adopts the magnesite caustic-calcined magnesite to make raw material, with addition of the ferrosilicon powder of 90-110% reduction reaction theoretical amount or industrial silicon multi-element compounds as reductive agent and a small amount of Ca, Mg, F, after mixing, the group of pressure, put into the heat-resisting retort of sealing, thermal reduction production MAGNESIUM METAL under condition of high vacuum degree 0.1-30Pa, temperature 1150-1250 ℃ of constant temperature 5-12 hour condition, this method belongs to hot reducing method, still exist this method inherent resource, energy utilization rate is low, production efficiency is low, the environmental pollution important disadvantages.
Magnesite electrolysis production MAGNESIUM METAL, be IG Farben method at first, this method is that magnesite is prepared into magnesium oxide, and the agglomerate of magnesium oxide and coke is produced molten magnesium chloride with chlorine reaction (about 800 ℃) in vertical shaft type electrical heater, and electrolysis generates MAGNESIUM METAL then.The main drawback of this method is that productivity is low, and needs regularly to stop work to remove furnace bottom because react the bits that produce, and chlorine consumption is big, and has hydrogenchloride in the exhaust.
The US4269816 patent report a kind of shaft type stove chlorination process, make reductive agent directly from block magnesite production fusion Magnesium Chloride Anhydrous with CO, the advantage of this method is to have got rid of the briquetting piece step of magnesite to magnesian calcining and magnesium oxide/coke, but preparation high-test metal magnesium needs very pure magnesium-containing mineral, and, it does not still solve IG Farben chlorinator institute inherent shortcoming, and promptly productivity is low, reaction efficiency is low, chlorine consumption big, distribute hydrogenchloride.
Norway adopts magnesite (" MAGNESIUM METAL process technology ", press of Central South University, Changsha, 2003, p4), with obtaining magnesium chloride brine after the salt acidleach, through two sections saturated dehydrations of hydrogen chloride gas after the electrolysis production MAGNESIUM METAL, be characterized in thorough through two sections saturated dehydrations of hydrogen chloride gas, the Magnesium Chloride Anhydrous electrolysis energy consumption of generation is low, but still has the saturated dehydration inherent of hydrogen chloride gas shortcoming, be that the recycling use process is numerous and diverse, equipment corrosion is serious, the running cost height, and capital investment is very big.
Australia magnesium industry company's (" MAGNESIUM METAL process technology ", press of Central South University, Changsha, 2003, p5-6), adopt the acidleach of magnesite salt to get magnesium chloride brine, carry out network and dehydration with organic solvent, in ammonia, spray again magnesium chloride hex-ammoniate, make Magnesium Chloride Anhydrous through 400-450 ℃ of deamination of secondary low temperature, get MAGNESIUM METAL in the electrolyzer electrolysis then.Compare the characteristics of this technology with above-mentioned technology: low temperature dewatering, Environmental Protection Level height; But have following deficiency at present: (1) makes with the magnesium-containing mineral hydrochloric acid leaching is MgCl
2(6-8) H
2The many hydrated magnesium chlorides of O, many aqueous magnesium chlorides dehydrating amount ambassador energy consumption increases, and secondly, utilizes economic angle from atom, the water molecules of in this reaction process the hydrogen atom in the hydrogenchloride being sloughed for the need power consumption, cost up; (2) the magnesium chloride hex-ammoniate deamination makes Magnesium Chloride Anhydrous and Magnesium Chloride Anhydrous electrolysis production MAGNESIUM METAL is divided two workshop sections, the as easy as rolling off a log suction of Magnesium Chloride Anhydrous becomes hydrated magnesium chloride, send at Magnesium Chloride Anhydrous to be difficult to guarantee that the electrolysis raw material does not absorb water in the fortune process, processing line increases complicated.
Patent CN1229400A and patent US6042794 have reported and have adopted the chloride leach solution of the magnesia calcined of magnesium-containing mineral at organic solvent, then the organic chloride magnesium solution is without dehydration, enter crystallizer, feed excess of ammonia and be settled out magnesium chloride six ammoniates, thermolysis magnesium chloride six ammoniates make Magnesium Chloride Anhydrous then.The characteristics of this technology: low temperature generates magnesium chloride, Environmental Protection Level height in organic liquid; But in this technological process, the output capacity that the unit organic solvent prepares magnesium chloride lower (/ 1000 milliliters of organic solvents of about 118 grams) makes the unit product hear rate increase, and production efficiency reduces, and the unit product investment increases the product cost height.
The industrialized producing technology for preparing MAGNESIUM METAL from magnesium-containing mineral has key issue to be solved: (1) improves the production efficiency of intermediate electrolysis material, cuts down the consumption of energy, reduces cost, and reduces investment; (2) reduce electrolysis energy consumption, improve electrolytic efficiency.
Summary of the invention
The objective of the invention is:
(1) improves the production efficiency for preparing the intermediate electrolysis material of MAGNESIUM METAL process from magnesium-containing mineral, cut down the consumption of energy, for this reason, the intensifying technology of fluidization calcination for activation technology and the organic dehydration of chlorinated distillation is provided, by magnesium-containing mineral prepared in reaction high density Magnesium Chloride Anhydrous organic medium solution, improve unit organic solvent magnesium chloride output capacity, cut down the consumption of energy, adopt the intensifying technology of fluidization reactive crystallization to prepare the intermediate (MgCl26 NH3) of electrolytic magnesium simultaneously, heat transfer, mass transfer that these have strengthened reaction process have improved reaction efficiency and production efficiency;
(2) reduce electrolysis energy consumption, improve electrolytic efficiency, for this reason, provide deamination electrolysis coupling technique to produce electrolytic magnesium, it makes full use of the Magnesium Chloride Anhydrous sensible heat, has reduced the energy consumption of the electrolysis of magnesium chloride, shortens the flow process that electrolytic magnesium is produced, avoided Magnesium Chloride Anhydrous to transport suction in the process, the purity of Magnesium Chloride Anhydrous when having guaranteed electrolysis.
For achieving the above object, technical solution of the present invention provides and a kind ofly prepares the method for MAGNESIUM METAL by magnesium-containing mineral, comprising: the chlorination reaction distillation dehydration technology of the fast fluidization calcination for activation technology of activated magnesia preparation, the preparation of high density Magnesium Chloride Anhydrous organic solution, the fluidization reactive crystallization technology and the deamination electrolysis coupling reaction technology of magnesium chloride hex-ammoniate preparation.This processing method is: 1. magnesium-containing mineral adopts fast fluidization calcination for activation technology to prepare the activated carbon oxide powder; 2. by chlorination reaction distillation dehydration technology, with activated magnesia powder and chlorination reaction agent in no aqueous organic media, carry out chlorination reaction and slough the water that reaction generates simultaneously, prepared in reaction high density Magnesium Chloride Anhydrous organic medium solution, the ammonia reclaiming clean of by-product is a product; 3. the no aqueous organic media of the employing of the high density Magnesium Chloride Anhydrous organic medium solution under temperature of reaction is mixed with Magnesium Chloride Anhydrous organic solution and the cooling that is used for reactive crystallization, then removes by filter unreacted impurity; 4. filtrate magnesium chloride organic solution is carried out the fluidization reactive crystallization under the ammonia saturation conditions in the fluidization reaction crystalizer, obtains magnesium chloride hex-ammoniate organic medium slip; 5. this slurry filtration separate magnesium chloride hex-ammoniate crystal and organic medium filtrate, a part of organic medium filtrate is returned above-mentioned operation and is 2. reused, residue is returned operation and is 3. reused; 6. magnesium chloride hex-ammoniate is after the saturated small molecules absolute alcohol of ammonia washs, and the fast fluidization drying makes anhydrous magnesium chloride hex-ammoniate; 7. anhydrous magnesium chloride hex-ammoniate adopts deamination electrolysis coupling reaction technology, carries out deamination, electrolysis makes MAGNESIUM METAL, and the chlorine reclaiming clean is a product, and ammonia recycles and reuses.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, it comprises the following steps:
1) magnesium-containing mineral fragmentation, grinding add fast fluidization calcination for activation device and carry out calcination for activation to the powder of certain particle size, 400 ℃ of-850 ℃ of temperature, make activated magnesia.
2) with 1) preparation activated magnesia powder, ammonium chloride and do not have aqueous organic media, place chlorination reaction distillation dehydration reactor, under 100 ℃-190 ℃ of temperature, carry out chlorination reaction and distill the water of sloughing the reaction generation simultaneously, make high density Magnesium Chloride Anhydrous organic medium solution.
3) with 2) high density Magnesium Chloride Anhydrous organic medium solution under the temperature of reaction, adopt no aqueous organic media that it is mixed with Magnesium Chloride Anhydrous organic solution and the cooling that is used for reactive crystallization, then remove by filter unreacted impurity, make the Magnesium Chloride Anhydrous organic solution of reactive crystallization.
4) with 3) the Magnesium Chloride Anhydrous organic solution that is used for reactive crystallization that makes, add gas-liquid-solid fluidization reaction crystalizer, fluidizing medium is an ammonia, under 10 ℃ of-30 ℃ of temperature, under the ammonia saturation conditions, carry out the fluidization reactive crystallization, obtain magnesium chloride hex-ammoniate organic medium slip.
5) with 4) magnesium chloride hex-ammoniate organic medium slurry filtration separate magnesium chloride hex-ammoniate crystal and organic medium filtrate, a part of organic medium filtrate is returned above-mentioned operation 2) reuse, residue is returned above-mentioned operation 3) reuse.
6) with 5) magnesium chloride hex-ammoniate that makes, after the saturated small molecules absolute alcohol washing of ammonia, make anhydrous magnesium chloride hex-ammoniate 100-120 ℃ of fast fluidization drying.
7) with 6) anhydrous magnesium chloride hex-ammoniate places deamination electrolysis coupling reaction device, this reaction unit divides deamination reaction section and electrolytic reaction section, the Magnesium Chloride Anhydrous that generates behind 150 ℃ of-500 ℃ of following magnesium chloride hex-ammoniate deaminations directly enters the electrolytic reaction section, under 700-720 ℃, fused salt electrolysis makes MAGNESIUM METAL, the chlorine reclaiming clean is a product, and ammonia recycles and reuses.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, it is described 1 years old) step activated magnesia preparation employing fast fluidization calcination for activation technology, it has heat transfer, mass transfer is fast, energy consumption is low, the calcination reaction temperature is even, the magnesium oxide that roasting obtains is active high, helps its chlorination reaction generation magnesium chloride and carries out.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 2 years old) the high density Magnesium Chloride Anhydrous organic solution preparation in step is characterised in that: adopt chlorination reaction distillation dehydration technology, magnesium chloride generates with dehydration carries out simultaneously, prepares high density Magnesium Chloride Anhydrous organic solution.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 2 years old) concentration of high density Magnesium Chloride Anhydrous organic solution in the step determines by temperature of reaction, along with temperature of reaction increases and increases.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 2 years old) and 3) step in no aqueous organic media be: high boiling alcohol or high boiling point alcohol mixture, as the alcohol mixture of ethylene glycol, glycerol or ethylene glycol and methyl alcohol, ethylene glycol and ethanol, ethylene glycol and propyl alcohol, ethylene glycol and butanols.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 4 years old) step magnesium chloride hex-ammoniate preparation adopts gas-liquid-solid fluidization reactive crystallization technology, mass transfer, rapid heat dissipation, reaction efficiency height.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 3 years old) with 5) step solid-liquid filtering separation adopts press filtration to separate or centrifugation.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 6 years old) the dry fast fluidization dry technology that adopts of step magnesium chloride hex-ammoniate, can well reclaim pure washings.
Describedly prepare MAGNESIUM METAL technology by magnesium-containing mineral, they are described 7 years old) preparation of single metal magnesium adopts deamination electrolysis coupling reaction technology.
Of the present inventionly prepare MAGNESIUM METAL technology by magnesium-containing mineral and have following principal feature:
(1) the reaction output capacity (400-500g/L) of the unit's of increasing substantially organic solvent magnesium chloride reduces the energy consumption (750-850kcal/kg-MgCl2) that magnesium chloride is produced.
(2) magnesium elements is converted into the transformation efficiency height (95-99%) of magnesium chloride in the magnesium-containing mineral.
(3) avoid the suction of electrolysis material, improved electrolytic efficiency.
(4) effective recycling organic medium and reaction by-product Chemicals.
(5) energy consumption is low, efficient is high, is convenient to industrial operation, is convenient to reach the environmental requirement level.
MAGNESIUM METAL preparation technology of the present invention is applicable to magnesium-containing mineral production MAGNESIUM METAL such as magnesite, rhombspar, activated magnesia, comprises the technology that is applicable to that magnesium chloride hex-ammoniate preparation and production MAGNESIUM METAL, Magnesium Chloride Anhydrous production and activated magnesia are produced simultaneously.
Description of drawings
Fig. 1. prepare the MAGNESIUM METAL process flow sheet for of the present invention by magnesium-containing mineral;
Fig. 2. be sample magnesite and the X-ray collection of illustrative plates after 750 ℃ of calcinings thereof;
Fig. 3. be MgCl
2Reaction generating rate and temperature of reaction concern synoptic diagram;
Fig. 4. be MgCl
2Solubleness and temperature variation in no water glycol organic medium concern synoptic diagram;
Fig. 5. be the X-ray collection of illustrative plates of sample magnesium chloride hex-ammoniate.
Embodiment
As shown in Figure 1, prepare the MAGNESIUM METAL process flow sheet by magnesium-containing mineral, wherein have: fast fluidization calcination for activation device 1 for of the present invention; Chlorination reaction distillation dehydration reactor 2; Filter plant 3; Fluidization reaction crystalizer 4; Filter plant 5; Washing plant 6; Fast fluidization drying plant 7; Deamination electrolysis coupling reaction device 8; Cooling recovery tower 9; Refining plant 10; Dewatering purifying equipment 11.Each operation is sealed interconnecting of separating by flow process with the external world.
Magnesium-containing mineral is an example with magnesite, further describes explanation preparation MAGNESIUM METAL Technology of the present invention.It is one as follows that the chemical analysis of magnesite sees Table:
Table one. the chemical analysis of magnesite
| Form | MgO | SiO2 | CaO | ?Fe2O3+A12O3 |
| Content (%) | 46.0 | 0.8 | 1.2 | ?0.6 |
First workshop section: behind the powder with magnesite fragmentation, grinding to 200 order mean particle size, add fast fluidization calcination for activation device and (be the patent of invention of inventor's application, application number is 200510004574.7), carry out calcination for activation at 750 ℃, make activated magnesia.The X-ray diffraction analysis is carried out in sampling, the results are shown in Figure 2 and table two, and magnesite is converted into activated magnesia.
Table two. sample magnesite and the 750 ℃ of magnesian X-ray data analysis of product results thereof
| The magnesite sample | 750 ℃ of calcinate magnesium oxide | ||||||
| °2Th | d/ | Int/％ | The thing phase | °2Th | d/ | Int/％ | The thing phase |
| 25.197 1 | 3.53449 | 0.06 | MgCO 3 | 36.9722 | 2.4314 | 7.66 | ?M ?g ?O |
| 29.474 8 | 3.03054 | 0.34 | ?(Mg 03Ca 97)CO 3？ | 42.9446 | 2.10609 | 100.00 | ?M ?g ?O |
| 31.055 7 | 2.87979 | 0.63 | CaMg(CO 3) 2？ | 62.3246 | 1.48984 | 44.39 | ?M ?g ?O |
| 31.642 5 | 2.82770 | 0.28 | MgCO 3 | 74.6866 | 1.27094 | 4.31 | ?M ?g ?O |
| 32.722 6 | 2.73680 | 100.00 | MgCO 3 | 78.6198 | 1.21591 | 9.19 | ?M ?g ?O |
| 35.930 9 | 2.4994 | 3.35 | MgCO 3 | ||||
| 38.919 9 | 2.3141 | 0.45 | MgCO 3 | ||||
| 43.056 8 | 2.10086 | 5.79 | MgCO 3 | ||||
| 46.912 0 | 1.93681 | 0.91 | MgCO 3 | ||||
| 51.675 0 | 1.76893 | 0.28 | MgCO 3 | ||||
| 53.942 2 | 1.69982 | 5.91 | MgCO 3 | ||||
| 61.430 2 | 1.50936 | 0.44 | MgCO 3 | ||||
| 62.450 5 | 1.48714 | 0.39 | MgCO 3 | ||||
| 66.457 9 | 1.40682 | 0.54 | MgCO 3 | ||||
| 68.433 7 | 1.36984 | 1.24 | MgCO 3 | ||||
| 68.677 7 | 1.36896 | 0.60 | MgCO 3 | ||||
| 69.391 2 | 1.35326 | 1.04 | MgCO 3 | ||||
| 70.364 6 | 1.33691 | 0.70 | MgCO 3 | ||||
| 76.034 9 | 1.25069 | 1.07 | MgCO 3 | ||||
| 76.974 0 | 1.23775 | 0.24 | MgCO 3 | ||||
| 79.736 2 | 1.20167 | 0.14 | MgCO 3 | ||||
| 81.569 6 | 1.17923 | 0.24 | MgCO 3 | ||||
| 83.418 9 | 1.15773 | 0.05 | MgCO 3 | ||||
| 88.870 3 | 1.10027 | 0.21 | MgCO 3 |
Second workshop section: activated magnesia powder 45.0 grams of first workshop section preparation are restrained and 250 milliliters of no water glycols with ammonium chloride 122.8, place chlorination reaction distillation dehydration reactor, 160 ± 5 ℃ of temperature, under 2.5 hours time, carry out chlorination reaction, vacuum distillation is sloughed water and the ammonia that reaction generates under the 10mmHg post simultaneously, under this temperature, make the translucent solution of 408 gram/L ethylene glycol high density Magnesium Chloride Anhydrous organic mediums, this solution records moisture 800ppm through the karl Fischer analytical method, no water glycol with room temperature adds this reactor for 750 milliliters subsequently, be mixed with 102 gram/L magnesium chloride ethylene glycol transparent and stable solution and be cooled to room temperature simultaneously, this solution removes by filter unreacted impurity then, uses for next workshop section.This operation is to be based upon to experimental studies have found that on the basis, the contriver experimental studies have found that:
(1) MgO+2NH in ethylene glycol medium
4C1=MgCl
2+ 2NH
3+ H
2O generates MgCl
2Speed of reaction has a sudden change with the temperature of reaction variation, about 140 ℃ of beginning MgCl
2The reaction generating rate increases (see figure 3) fast with temperature of reaction, when temperature of reaction when 140 ℃ are increased to 160 ℃, generate MgCl
2Speed of reaction increases to 188.1g/h by 47.5g/h, MgCl when temperature of reaction is 180 ℃
2Speed of reaction 303.7g/h, this discovers it is the important foundation of prepared in reaction high density Magnesium Chloride Anhydrous organic medium solution, to improve from magnesium-containing mineral prepare the production efficiency of the intermediate electrolysis material of MAGNESIUM METAL process, the direct reality that cut down the consumption of energy mainly acts on.
(2) MgCl
2Solubility with temperature in no water glycol organic medium changes and has sudden change section (as a Fig. 4), when temperature when 130 ℃ are increased to 160 ℃, MgCl
2Solubleness in no water glycol increases to 408g/L by 148g/L, MgCl when temperature is 180 ℃
2Solubleness 458g/L in no water glycol, this discovers it is to be mixed with the important foundation that the Magnesium Chloride Anhydrous that is used for reactive crystallization is stablized organic solution.
The 3rd workshop section: the Magnesium Chloride Anhydrous ethylene glycol organic solution that is used for reactive crystallization that second workshop section is made, add gas-liquid-solid fluidization reaction crystalizer, fluidizing medium is an ammonia, gas speed 0.1m/s, at 17 ± 1 ℃, 2 hours, under the ammonia saturation conditions, carry out the fluidization reactive crystallization, obtain magnesium chloride hex-ammoniate organic medium slip.
The 4th workshop section: with the magnesium chloride hex-ammoniate organic medium slip press filtration of the 3rd workshop section filter magnesium chloride hex-ammoniate crystal and the organic filtrate of ethylene glycol, containing magnesium chloride in its filtrate ethylene glycol is 0.91g/L, the organic filtrate of this ethylene glycol is returned above-mentioned second workshop section and is reused; Behind the anhydrous methanol washing and filter pressing that magnesium chloride hex-ammoniate filter cake usefulness ammonia is saturated, filter cake makes anhydrous magnesium chloride hex-ammoniate 100 ℃ of fast fluidization dryings, and the methyl alcohol cooling that simultaneously drying is gone out is reclaimed and returned washing.The magnesium chloride hex-ammoniate that drying obtains is through carrying out the X-ray diffraction analysis, the results are shown in Figure 5 and table three; This sample is 2.67% by the determination of elemental analysis methanol content, and icp analysis is measured iron content 0.00652%, calcium element content 0.026%, aluminium element content 0.0084%, magnesium element content 11.44%.
Table three. sample magnesium chloride hex-ammoniate X-ray diffraction analytical results
| The sample magnesium chloride hex-ammoniate | |||||||
| °2Th | d/ | Int/％ | The thing phase | °2Th | d/ | Int/％ | The thing phase |
| 15.1464 | 5.84960 | 50.66 | MgCl 2·6NH 3 | 53.1835 | 1.72226 | 1.15 | NH 4Cl |
| 17.4401 | 5.08510 | 0.47 | MgCl 2·6NH 3 | 57.1541 | 1.61036 | 1.89 | MgCl 2·6N H 3 |
| 23.0124 | 3.86485 | 2.67 | NH 4Cl | 58.3130 | 1.58108 | 1.87 | NH 4Cl |
| 24.7659 | 3.59504 | 15.12 | MgCl 2·6NH 3 | 60.2167 | 1.53557 | 1.04 | MgCl 2·6N H 3 |
| 29.1228 | 3.06636 | 1.83 | MgCl 2·6NH 3 | 63.2212 | 1.46963 | 3.12 | MgCl 2·6N H 3 |
| 30.4602 | 2.93471 | 100.00 | MgCl 2·6NH 3 | 65.3795 | 1.42742 | 0.57 | MgCl 2·6N H 3 |
| 32.7316 | 2.73606 | 10.67 | NH 4Cl | 68.9290 | 1.3612 | 1.14 | MgCl 2·6N H 3 |
| 35.2649 | 2.54510 | 15.71 | MgCl 2·6NH 3 | 78.0256 | 1.22469 | 0.31 | NH 4Cl |
| 39.3899 | 2.27647 | 0.45 | MgCl 2·6NH 3 | 79.8106 | 1.20173 | 0.35 | MgCl 2·6N H 3 |
| 40.3240 | 2.23670 | 0.52 | NH 4Cl | ||||
| 43.5343 | 2.07891 | 5.44 | MgCl 2·6NH 3 | ||||
| 46.3074 | 1.96089 | 1.98 | MgCl 2·6NH 3 | ||||
| 46.9048 | 1.93709 | 1.21 | NH 4Cl | ||||
| 50.6919 | 1.80090 | 4.59 | MgCl 2·6NH 3 | ||||
The 5th workshop section: the anhydrous magnesium chloride hex-ammoniate of the 4th workshop section is placed deamination electrolysis coupling reaction device, this reaction unit divides deamination reaction section and electrolytic reaction section, at 150 ℃-480 ℃, 2 hours following magnesium chloride hex-ammoniate deaminations, the ammonia of sloughing reclaimed and returns the repeated use of the 3rd workshop section; The Magnesium Chloride Anhydrous that generates behind the magnesium chloride hex-ammoniate deamination directly enters the electrolytic reaction section, and under 700-720 ℃, fused salt electrolysis makes MAGNESIUM METAL, and the chlorine reclaiming clean is a product.
Claims (8)
1. one kind prepares the method for MAGNESIUM METAL by magnesium-containing mineral, it is characterized in that: comprise step: 1. adopt fast fluidization calcination for activation technology to prepare the activated carbon oxide compound to magnesium-containing mineral; 2. by chlorination reaction distillation dehydration technology, with activated magnesia powder and chlorination reaction agent in no aqueous organic media, carry out chlorination reaction and slough the water that reaction generates simultaneously, prepared in reaction high density Magnesium Chloride Anhydrous organic medium solution, the ammonia reclaiming clean of by-product is a product; 3. the high density Magnesium Chloride Anhydrous organic medium solution under temperature of reaction, Magnesium Chloride Anhydrous organic solution and the cooling adopting no aqueous organic media to be mixed with to be used for reactive crystallization refilter and remove unreacted impurity; 4. filtrate magnesium chloride organic solution is carried out the fluidization reactive crystallization under the ammonia saturation conditions in the fluidization reaction crystalizer, obtains magnesium chloride hex-ammoniate organic medium slip; 5. this slip separate after filtration magnesium chloride hex-ammoniate crystal and organic medium filtrate, a part of organic medium filtrate is returned operation and is 2. reused, residue is returned operation and is 3. reused; 6. magnesium chloride hex-ammoniate is after the saturated small molecules absolute alcohol of ammonia washs, and the fast fluidization drying makes anhydrous magnesium chloride hex-ammoniate; 7. anhydrous magnesium chloride hex-ammoniate adopts deamination electrolysis coupling reaction technology, carries out deamination, electrolysis makes MAGNESIUM METAL, and the chlorine reclaiming clean is a product, and ammonia recycles and reuses.
2. the method for claim 1, it is characterized in that: the described 1. preparation of the activated magnesia in step, be to adopt fast fluidization calcination for activation technology, magnesium-containing mineral makes the active powder of magnesium oxide under 400 ℃ of-850 ℃ of temperature of fast fluidization, it has heat transfer, mass transfer is fast, energy consumption is low, the calcination reaction temperature is even, and the magnesium oxide that roasting obtains is active high, helps its chlorination reaction and generates magnesium chloride.
3. the method for claim 1, it is characterized in that: the described 2. preparation of the high density Magnesium Chloride Anhydrous organic solution in step, be to adopt chlorination reaction distillation dehydration technology, under 100 ℃-190 ℃ of temperature, activated magnesia and ammonium chloride react in no aqueous organic media and generate magnesium chloride, and the water that reacting phase should generate is sloughed in distillation from organic medium simultaneously; The concentration of high density Magnesium Chloride Anhydrous organic solution is determined by temperature of reaction, along with temperature of reaction increases and increases.
4. the method for claim 1, it is characterized in that: the described 4. preparation of the magnesium chloride hex-ammoniate in step, the Magnesium Chloride Anhydrous organic solution that will be used for reactive crystallization, by gas-liquid-solid fluidization reactive crystallization technology, fluidizing medium is an ammonia, under 10 ℃ of-30 ℃ of temperature, under the ammonia saturation conditions, carry out the fluidization reactive crystallization, obtain magnesium chloride hex-ammoniate, its mass transfer, rapid heat dissipation, reaction efficiency height.
5. the method for claim 1 is characterized in that: the described 6. magnesium chloride hex-ammoniate drying in step, and adopt fast fluidization simultaneously dry, can well reclaim pure washings.
6. the method for claim 1, it is characterized in that: the described 7. preparation of the MAGNESIUM METAL in step, be to adopt deamination electrolysis coupling reaction technology, magnesium chloride hex-ammoniate places deamination electrolysis coupling reaction device, and this reaction unit divides deamination reaction section and electrolytic reaction section, and the Magnesium Chloride Anhydrous that generates behind 150 ℃ of-500 ℃ of following magnesium chloride hex-ammoniate deaminations directly enters the electrolytic reaction section, under 700-720 ℃, fused salt electrolysis makes MAGNESIUM METAL, and the chlorine reclaiming clean is a product, and ammonia recycles and reuses; Be characterized in having made full use of the Magnesium Chloride Anhydrous sensible heat, reduced the energy consumption of the electrolysis of magnesium chloride, shorten the flow process that electrolytic magnesium is produced, avoided Magnesium Chloride Anhydrous to transport suction in the process.
7. the method for claim 1, it is characterized in that: described organic medium is high boiling alcohol or high boiling point alcohol mixture.
8. method as claimed in claim 7 is characterized in that: described high boiling alcohol or high boiling point alcohol mixture are the alcohol mixture of ethylene glycol, glycerol or ethylene glycol and methyl alcohol, ethylene glycol and ethanol, ethylene glycol and propyl alcohol, ethylene glycol and butanols.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336422A (en) * | 2010-07-14 | 2012-02-01 | 中国科学院过程工程研究所 | Method for circulating fluidized bed pyrolysis and deamination of magnesium chloride hexammoniate and equipment thereof |
| WO2012065338A1 (en) * | 2010-11-16 | 2012-05-24 | 华东理工大学 | Method for preparing anhydrous magnesium chloride by calcining and deaminating magnesium chloride hexammoniate |
| 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 |
| WO2015003657A1 (en) * | 2013-07-12 | 2015-01-15 | 中国科学院过程工程研究所 | K3namgcl6, preparation method therefor and use thereof |
| CN113620324A (en) * | 2021-08-03 | 2021-11-09 | 安徽亚格盛电子新材料有限公司 | Process for deamination of magnesium chloride hexammoniate using water vapour |
| CN115747516A (en) * | 2022-11-21 | 2023-03-07 | 昆明理工大学 | Method for recovering nickel, cobalt, magnesium and iron from high-magnesium-silicon laterite-nickel ore |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056599A (en) * | 1975-10-20 | 1977-11-01 | Bechtel International Corporation | Process for the recovery of magnesium chloride hydrate and potassium chloride from carnallite and bischofite |
| JPS54112396A (en) * | 1978-02-22 | 1979-09-03 | Ube Ind Ltd | Production of high purity anhydrous magnesium chloride |
| IL109189A (en) * | 1993-04-06 | 1997-11-20 | Alcan Int Ltd | Process for making anhydrous magnesium chloride |
| NO308352B1 (en) * | 1997-06-20 | 2000-09-04 | Norsk Hydro As | Process for producing anhydrous MgCl2 |
| CN1326773C (en) * | 2004-04-29 | 2007-07-18 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
| CN1632436A (en) * | 2005-01-18 | 2005-06-29 | 中国科学院过程工程研究所 | Fast fluidized calcining process |
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2005
- 2005-12-07 CN CNB2005101263170A patent/CN100494425C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN102336422A (en) * | 2010-07-14 | 2012-02-01 | 中国科学院过程工程研究所 | Method for circulating fluidized bed pyrolysis and deamination of magnesium chloride hexammoniate and equipment thereof |
| CN102336422B (en) * | 2010-07-14 | 2013-08-21 | 中国科学院过程工程研究所 | Method for circulating fluidized bed pyrolysis and deamination of magnesium chloride hexammoniate and equipment thereof |
| WO2012065338A1 (en) * | 2010-11-16 | 2012-05-24 | 华东理工大学 | Method for preparing anhydrous magnesium chloride by calcining and deaminating magnesium chloride hexammoniate |
| WO2015003657A1 (en) * | 2013-07-12 | 2015-01-15 | 中国科学院过程工程研究所 | K3namgcl6, preparation method therefor and use thereof |
| CN113620324A (en) * | 2021-08-03 | 2021-11-09 | 安徽亚格盛电子新材料有限公司 | Process for deamination of magnesium chloride hexammoniate using water vapour |
| CN115747516A (en) * | 2022-11-21 | 2023-03-07 | 昆明理工大学 | Method for recovering nickel, cobalt, magnesium and iron from high-magnesium-silicon laterite-nickel ore |
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| CN100494425C (en) | 2009-06-03 |
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