CN104418370A - Method and device for preparing anhydrous magnesium chloride - Google Patents

Method and device for preparing anhydrous magnesium chloride Download PDF

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Publication number
CN104418370A
CN104418370A CN201310395723.1A CN201310395723A CN104418370A CN 104418370 A CN104418370 A CN 104418370A CN 201310395723 A CN201310395723 A CN 201310395723A CN 104418370 A CN104418370 A CN 104418370A
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magnesium chloride
anhydrous
ammonium
magnesium
dehydration furnace
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CN104418370B (en
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卢旭晨
张志敏
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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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
    • C01F5/34—Dehydrating magnesium chloride containing water of crystallisation
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention relates to a device for preparing anhydrous magnesium chloride and a preparation method which uses the device. The device is a chlorination dehydration furnace and comprises a storage cabin, wherein the upper part of the storage cabin is a preheating zone; the middle part of the storage cabin is a double salt forming zone; the bottom of the storage cabin is an ammonium removing zone; the storage cabin is connected with an outlet and has certain sealing property. The preparation method comprises the following steps: uniformly mixing magnesium oxide and/or hydrated magnesium chloride and ammonium chloride, adding the mixture into the chlorination dehydration furnace, and heating, thereby preparing anhydrous magnesium chloride; and repeating the above operation steps when the anhydrous magnesium chloride is discharged out, thereby achieving continuous production. A method for preparing anhydrous magnesium chloride by using the rich magnesite and magnesium chloride hexahydrate resources in China is provided by the invention, continuous production of anhydrous magnesium chloride is achieved, the production efficiency is improved, the production cost is lowered, and the cost of environment protection is lowered; the prepared anhydrous magnesium chloride is high in purity, the content of the main impurity magnesium oxide in the anhydrous magnesium chloride can be controlled to be 0.5% or even less than 0.1%, and the anhydrous magnesium chloride can be used for preparing magnesium metal in an electrolysis manner and has very good industrial and commercial prospect.

Description

A kind of preparation method of Magnesium Chloride Anhydrous and device
Technical field
The present invention relates to preparation method and the device of Magnesium Chloride Anhydrous, specifically, relate to a kind of magnesium oxide or hydrated magnesium chloride of utilizing and prepare method and the device of Magnesium Chloride Anhydrous for raw material, adopt technique of the present invention and device can realize the continuous prodution of Magnesium Chloride Anhydrous, prepare MAGNESIUM METAL for electrolytic process and supply raw materials.
Background technology
Magnesium belongs to IIA(second main group on the periodic table of elements) race's alkali earth metal, MAGNESIUM METAL is argenteous metal, and matter is hard, and slightly ductility, the density of magnesium is little, and ionization tendency is large.Compared with plastics, magnesium alloy have lightweight, specific tenacity is high, damping good, thermal fatigue property is good, not easily aging, there is again strong, the extraordinary extrusion process performance of good thermal conductivity, electromagnetic shielding capability, especially being easy to the advantages such as recovery, is the high performance structures material of new generation of alternative iron and steel, aluminium alloy and engineering plastics.For adapting to the development trend of electronics, communication device Highgrade integration and frivolous miniaturization, magnesium alloy is the ideal material of the product casings such as traffic, electronic information, communication, computer, acoustic image equipment, hand-held tool, motor, forestry, weaving, nuclear power plant.
The preparation method of magnesium has two classes usually: electrolytic process and hot reducing method.The raw material that wherein electrolytic process uses is generally magnesium chloride, thus adopts the key link of generating metal magnesium by electrolyzing magnesium chloride to be prepare Magnesium Chloride Anhydrous.At present, the preparation method of Magnesium Chloride Anhydrous has following several:
(1) low water ammonium carnallite ammonia process prepares Magnesium Chloride Anhydrous
Yuichi Suzukaw is described the specific operation process of the method and principle in patent US3798314: first by low water ammonium carnallite (MgCl 2nH 4clnH 2o, n=0.5 ~ 4) carry out preliminary hydro-extraction at 110 DEG C-160 DEG C, the product of preliminary hydro-extraction generates ammino ammonium carnallite MgCl at 200 ~ 400 DEG C with ammonia contact reacts 2nH 4clnNH 3(n=0.2 ~ 3).Ammino ammonium carnallite is carried out calcining for some time at 712 ~ 900 DEG C and just obtains Magnesium Chloride Anhydrous.The large usage quantity of the method ammonia in the process implemented, energy consumption is higher, causes implementation cost too high.
(2) gas-solid reaction legal system is for Magnesium Chloride Anhydrous
One method adopts ammonium carnallite (MgCl 2nH 4cl6H 2o) be the gas-solid reaction method (as " ammonium carnallite prepares Magnesium Chloride Anhydrous novel process and fundamental research ", Zhou Ningbo, Central South University, Ph D dissertation in 2005) of raw material: by low for raw material water ammonium carnallite (MgCl 2nH 4clnH 2o, n=0.5 ~ 1.0) mix according to mass ratio 1:4 with ammonium chloride after at 410 DEG C of thermal dehydrations, generate product ammino ammonium carnallite.Ammino ammonium carnallite is obtained Magnesium Chloride Anhydrous 700 DEG C of calcinings, and wherein magnesian massfraction is less than 0.1%.
Another kind method adopts bischofite (MgCl 26H 2o) be the gas-solid reaction method of raw material; as Zhou Ningbo etc. describes the method (Zhou Ningbo etc. in detail in " bischofite gas-solid reaction prepares Magnesium Chloride Anhydrous "; [J]. chemical research and application; 2010,22(10): 1290-1294): make low water of hydration chloromagnesite (MgCl in 135 DEG C of dehydration 2h under nitrogen protection by Bischofite in Salt lake 2nH 2o, n=1.6).Low water of hydration chloromagnesite mixes according to mass ratio 1:6.5 with solid ammonium chloride, makes the dividing potential drop of ammonia in reaction system reach more than 49.6KPa under high temperature, within 12 minutes, makes Magnesium Chloride Anhydrous in 440 DEG C of dehydrations 18 minutes and 710 DEG C of calcinings.In obtained Magnesium Chloride Anhydrous, magnesian massfraction is less than 0.15%.The consumption of the method ammonium chloride in the process implemented is excessive, and it is excessive that ammonium chloride decomposes power consumption, causes the running cost of the method very high, and ammonium chloride a large amount of in addition reclaims difficulty and easy blocking pipe in process of production.
(3) magnesium oxide chlorination process prepares Magnesium Chloride Anhydrous
One method adopts chlorine as chlorizating agent (IG Farben method), it be by the agglomerate of magnesium oxide and reductive agent charcoal in electrically heated shaft furnace with chlorine reaction (about 800 DEG C) to prepare melting Magnesium Chloride Anhydrous, its shortcoming is that production efficiency is low, chlorine utilization is low and vent gas treatment has high input, and has chlorinated hydrocarbons in exhaust.
Another kind method adopts ammonium chloride as chlorizating agent, as described the method in detail in CN102491383A: are added solid covers aluminum oxide or quartz sand above the mixture that magnesium oxide and ammonium chloride Homogeneous phase mixing are obtained, heat, reaction prepares the Magnesium Chloride Anhydrous of content of magnesia within 0.5wt%.There is following problem in the method: a) coverture is in heat-processed, due to the mobile change of the bed of material, is easy to be mixed in product Magnesium Chloride Anhydrous, had a strong impact on the purity of Magnesium Chloride Anhydrous; B) reactant needs coverture quartz sand or aluminum oxide to continue to protect, and causes the method to realize batch production, cannot meet the requirement of continuous automatic production.
(4) melting chlorination evaporation prepares anhydrous chlorides of rase Serum Magnesium
One method adopts chlorine to be chlorizating agent, and as US3953574 discloses a kind of method of producing melting Magnesium Chloride Anhydrous, it utilizes containing MgO and H 2o is the spraying dry MgCl of 5% 2powder and solid carbon reductive agent and chlorine react at 800 DEG C.Realizing this process is complete in the square furnace of two series connection, the MgCl finally obtained 2fused solution is containing the MgO lower than 0.5wt%.US4981674 is by spray-dired MgCl 2powder, magnesite or magnesium oxide add the MgCl of 750-850 DEG C 2in fused solution, gaseous reactant chlorine and carbon monoxide are by melting MgCl 2the magnesium oxide that gas distributor in pond enters in fused solution formation tiny bubble and pond reacts, and content of magnesia can be made to be reduced to below 0.1wt%.
Another kind method adopts hydrogen chloride gas to be chlorizating agent, as Japanese Patent 32-9052 describes the method in detail: hydrated magnesium chloride is added the electrolytic solution of magnesium chloride containing (containing the MgCl of 25wt% 2) in, at 750 DEG C, inject anhydrous hydrogen chloride gas, obtained anhydrous chlorides of rase Serum Magnesium simultaneously, but obtained electrolysis of magnesium chloride liquid electrolysis is by graphite more for consumption rate, produce MAGNESIUM METAL per ton and will consume 13-15kg graphite, graphite consumption is large, represents that the content of MgO is high.CN1146757A discloses a kind of method directly containing Magnesium Chloride Anhydrous fused solution or electrolytic solution from the production of hydrated magnesium chloride feed, it be by hydrated magnesium chloride from magnesium eletrolysis pond feed containing molten electrolyte stove in produce fused solution, furnace temperature remains on 450-650 DEG C, anhydrous hydrogen chloride gas is injected fused solution simultaneously, and stir fused solution to disperse injecting gas, magnesium oxide in fused solution is kept to be suspended state, magnesium chloride is made to dewater and react with magnesium oxide, obtain the fused solution of enrichment Magnesium Chloride Anhydrous, content of magnesia in fused solution is not more than 0.2wt% (magnesium chloride in 100%).Utilize gas chlorination agent (HCl or Cl 2) in fused solution preparation mainly there is following point containing anhydrous chlorides of rase Serum Magnesium: a) gas chlorination agent utilization ratio is not high, because gas not easily realizes dispersed in fused solution, and need to keep enough chloridating gas concentration that magnesium oxide just can be made to be converted into magnesium chloride in whole fused solution, when especially in fused solution, content of magnesia is low, gas chlorination agent utilization ratio is very low; B) the moisture hydrogen chloride gas obtained during dehydration recycle the complicated dehumidification system of needs one, and this system cost and running cost are all very high.
The key link reducing electrolytic magnesium production cost is exactly with relatively simple process economics, prepares the very low Magnesium Chloride Anhydrous of content of MgO efficiently.At present, the key issue that restriction Magnesium Chloride Anhydrous is produced has: the use of (1) a large amount of chlorine and hydrogen chloride gas requires very high to the stopping property of equipment and solidity to corrosion, and steam-laden tail gas purification difficulty comparatively large (purity need reach more than 99.5%), adds the cost of operation; (2) Magnesium Chloride Anhydrous is difficult to realize continuous prodution, and production efficiency is low; (3) product Magnesium Chloride Anhydrous purity is low, seriously reduces the current efficiency of follow-up electrolytic process, adds power consumption.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of device preparing Magnesium Chloride Anhydrous, and an object of the present invention is also to provide the method utilizing described device to prepare Magnesium Chloride Anhydrous.The continuous prodution of Magnesium Chloride Anhydrous can be realized by described device and preparation method under relatively simple processing condition, the Magnesium Chloride Anhydrous that content of MgO is less than 0.1% can be prepared in certain preferred circumstances.。
The preparation facilities of Magnesium Chloride Anhydrous provided by the invention is chlorination dehydration furnace, and described chlorination dehydration furnace comprises preheating zone, top 11, middle part double salt forms band 12 and bottom and takes off the storage bin 8 with certain stopping property that ammonium band 13 is connected with by discharge port 4.Wherein, the storage bin with certain stopping property refers to ensure that Magnesium Chloride Anhydrous does not contact with water vapour with the oxygen in air, and ensures the inert atmosphere in storehouse, and storage bin, on the basis ensureing rare gas element circulate, has certain stopping property.
Preferably, the Heating temperature of described preheating zone 11 is 50-200 DEG C, be such as 53 DEG C, 58 DEG C, 66 DEG C, 78 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 166 DEG C, 174 DEG C, 180 DEG C, 189 DEG C, 197 DEG C etc., preferred 80-150 DEG C; The Heating temperature that described middle part double salt forms band 12 is 250-400 DEG C, be such as 256 DEG C, 267 DEG C, 276 DEG C, 285 DEG C, 290 DEG C, 296 DEG C, 305 DEG C, 315 DEG C, 325 DEG C, 335 DEG C, 345 DEG C, 355 DEG C, 365 DEG C, 375 DEG C, 385 DEG C, 395 DEG C etc., preferred 300-400 DEG C; The Heating temperature that described bottom takes off ammonium band 13 is 420-750 DEG C, be such as 423 DEG C, 431 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 540 DEG C, 560 DEG C, 580 DEG C, 600 DEG C, 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C etc., preferred 450-700 DEG C.
Preferably, the length-to-diameter ratio >=2:1 of described chlorination dehydration furnace is such as 2.2:1,2.8:1,3.1:1,3.6:1,4.1:1,4.6:1,5.1:1,5.6:1,6.1:1,6.6:1,7.1:1,7.6:1,8.1:1,8.6:1 etc., is preferably >=3.5:1.
Preferably, described storage bin 8 has inert atmosphere.Pass in storehouse by rare gas element by inert gas entrance 9, in storehouse, gas from gas outlet 10 is discharged, and ensure that the inert atmosphere in storehouse.
Preferably, described chlorination dehydration furnace also comprises gas overflowing mouth 2 and discharge port 4.
Preferably, described chlorination dehydration furnace also comprises whipping appts 3.
An object of the present invention is also to provide the method utilizing described device to prepare Magnesium Chloride Anhydrous, comprises the steps:
A magnesium oxide and ammonium chloride mix by ();
B step (a) gained mixture adds in chlorination dehydration furnace and heats by (), obtained Magnesium Chloride Anhydrous;
C () Magnesium Chloride Anhydrous is discharged while, repeating step (a) and (b), realize continuous prodution.
Preferably, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 2.6-25.00 weight part, be such as 2.8 parts, 4.8 parts, 6.8 parts, 8.8 parts, 10.8 parts, 12.8 parts, 14.8 parts, 16.8 parts, 18.8 parts, 20.0 parts, 22.0 parts, 24.0 parts, be preferably 2.70-20.10 weight part.
The method two utilizing described device to prepare Magnesium Chloride Anhydrous provided by the invention, comprises the steps:
A molecular formula is MgCl by () 2mH 2the hydrated magnesium chloride of O and ammonium chloride mix; Or be MgCl by magnesium oxide and molecular formula 2mH 2the hydrated magnesium chloride of O and ammonium chloride mix;
Wherein, m > 0, preferably 6 >=m > 0; M represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule;
B step (a) gained mixture adds in chlorination dehydration furnace and heats by (), obtained Magnesium Chloride Anhydrous;
C () Magnesium Chloride Anhydrous is discharged while, repeating step (a) and (b), realize continuous prodution.
Preferably, with the magnesium chloride not containing crystal water, or magnesium oxide and be not 1.00 parts by weight containing the feeding quantity of magnesium chloride of crystal water, namely the feeding quantity of hydrated magnesium chloride is 1+0.19m weight part, the feeding quantity of ammonium chloride is 0.28-60.00 weight part, be such as 0.30 part, 5.30 parts, 10.30 parts, 15.30 parts, 20.30 parts, 25.30 parts, 30.30 parts, 35.30 parts, 40.30 parts, 45.30 parts, 50.30 parts, 55.30 parts, 58.00 parts, be preferably 0.28-56.00 weight part.
Two kinds of described methods, preferably, in chlorination dehydration furnace in step (b), the Heating temperature of preheating zone 11 is 50-200 DEG C, be such as 53 DEG C, 58 DEG C, 66 DEG C, 78 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 166 DEG C, 174 DEG C, 180 DEG C, 189 DEG C, 197 DEG C etc., preferred 80-150 DEG C; The Heating temperature that middle part double salt forms band 12 is 250-400 DEG C, be such as 256 DEG C, 267 DEG C, 276 DEG C, 285 DEG C, 290 DEG C, 296 DEG C, 305 DEG C, 315 DEG C, 325 DEG C, 335 DEG C, 345 DEG C, 355 DEG C, 365 DEG C, 375 DEG C, 385 DEG C, 395 DEG C etc., preferred 300-400 DEG C; The Heating temperature of the de-ammonium band 13 in bottom is 420-750 DEG C, be such as 423 DEG C, 431 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 540 DEG C, 560 DEG C, 580 DEG C, 600 DEG C, 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C etc., preferred 450-700 DEG C;
Preferably, the length-to-diameter ratio >=2:1 of described chlorination dehydration furnace is such as 2.2:1,2.8:1,3.1:1,3.6:1,4.1:1,4.6:1,5.1:1,5.6:1,6.1:1,6.6:1,7.1:1,7.6:1,8.1:1,8.6:1 etc., is preferably >=3.5:1;
Preferably, described storage bin 8 has inert atmosphere; Pass in storehouse by rare gas element by inert gas entrance 9, in storehouse, gas from gas outlet 10 is discharged, and ensure that the inert atmosphere in storehouse.
Preferably, described chlorination dehydration furnace also comprises gas overflowing mouth 2 and discharge port 4.The ammonia that step (b) can be made to produce and ammonium chloride are discharged through gas overflowing mouth, and carry out reclaiming with recycle.The obtained discharge port 4 of Magnesium Chloride Anhydrous bottom superchlorination dehydration furnace is discharged, and the process inert atmosphere of discharge is protected, and while discharge, a new batch materials is added by the charging opening on stove top.
Preferably, described chlorination dehydration furnace also comprises whipping appts 3.Installing whipping appts in chlorination dehydration furnace is to ensure burden direct motion.
Preferably, described mixture is 0.2-5.0h in the heat-up time of preheating zone, such as, be 0.3h, 0.6h, 0.9h, 1.2h, 1.5h, 1.8h, 2.1h, 2.4h, 2.7h, 3.0h, 3.3h, 3.7h, 4.1h, 4.4h, 4.8h etc., is preferably 0.2-3.5h; The heat-up time forming band at double salt is 0.2-5.0h, be such as 0.3h, 0.5h, 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h, 3.0h, 3.3h, 3.7h, 4.1h, 4.4h, 4.8h etc., be preferably 0.2-2.5h; Being 0.5-5.0h in the heat-up time of de-ammonium band, such as, is 0.6h, 0.8h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, 2.7h, 3.0h, 3.3h, 3.7h, 4.1h, 4.4h, 4.8h etc., is preferably 0.5-2.5h.
Preferably, the thickness of mixture described in step (b) in chlorination dehydration furnace is not less than 10cm, be such as 12cm, 16cm, 21cm, 26cm, 31cm, 36cm, 41cm, 46cm, 51cm, 56cm, 61cm, 66cm, 71cm, 76cm, 81cm etc., be preferably not less than 15cm.
Preferably, the ammonia produced in step (b), hydrogenchloride and ammonium chloride are discharged through gas overflowing mouth (2), and carry out reclaiming with recycle.Because ammonium chloride has partial sublimation decomposed to be ammonia and hydrogenchloride, so the gas that place overflows comprises ammonia, hydrogenchloride and ammonium chloride.
Fig. 1 is the process flow sheet of Magnesium Chloride Anhydrous prepared according to the methods of the invention.Concrete preparation process is: magnesium oxide or hydrated magnesium chloride and ammonium chloride mix by (a), obtain the mixture of magnesium oxide or hydrated magnesium chloride and ammonium chloride; B said mixture adds in chlorination dehydration furnace by (), first at 50-200 DEG C of heating 0.2-5.0h, then at 250-400 DEG C of heating 0.2-5.0h, finally at 420-750 DEG C of heating 0.5-5.0h.In heat-processed, in order to ensure that material can direct motion, material is constantly stirred, and the ammonium chloride of discharging from gas overflowing mouth in heat-processed and ammonia are recycled; C Magnesium Chloride Anhydrous is discharged from discharge port by (), the operation of repeating step (a) and (b), realizes continuous prodution.
Contriver is found by large quantity research, and the mechanism of above-mentioned reaction is as follows: magnesium oxide and ammonium chloride carry out preheating at 50-200 DEG C, can remove the moisture in material, prevent the generation of hydrolysis reaction in heat-processed; Hydrated magnesium chloride and ammonium chloride carry out preheating at 50-200 DEG C, and hydrated magnesium chloride can be made to carry out preliminary hydro-extraction, weaken the hydrolysis degree in follow-up intensification heat-processed.About 300 DEG C, magnesium oxide or hydrated magnesium chloride all can react with ammonium chloride and form double salt NH 4clMgCl 2nH 2o (0≤n < 6) (refers to document: Zhang ZM, Lu XC etal, Preparation of anhydrous magnesium chloride from magnesia, Industrial & Engineering Chemistry Research, 2012,51 (29): 9713-9718; Zhang ZM, Lu XC etal, Preparation of Anhydrous Magnesium Chloride from Magnesium ChlorideHexahydrate.Metallurgical and Materials Transactions B, 2013,44 (2): 354-358), the structure of double salt reduces the combination of crystal water and magnesium chloride, is conducive to the carrying out dewatered, and reduces the hydrolysis of dehydration.Even if there occurs hydrolysis, ammonium chloride can also react with hydrolysate (hydroxy chloride magnesium and magnesium oxide) at a certain temperature, generates Magnesium Chloride Anhydrous, thus ensure that the purity of product Magnesium Chloride Anhydrous.When temperature continues to raise, above-mentioned double salt sloughs crystal water gradually, and when temperature rises to more than 420 DEG C, ammonium chloride sloughed by double salt.Ammonium chloride is decomposed into ammonia and hydrogen chloride gas in the process removed, these gases not only can the dividing potential drop of water vapour and oxygen in diluting reactor effectively, and hydrogen chloride gas can also the generation of hydrolysis reaction in inhibited reaction device effectively, obtains highly purified Magnesium Chloride Anhydrous.
Contriver is also found by large quantity research, and ammonium chloride has following effect in the preparation of above-mentioned Magnesium Chloride Anhydrous: under (1) low temperature can with magnesium oxide or chloride hydrate reactive magnesium, generate the double salt NH of easily dehydration 4clMgCl 2nH 2o (0≤n < 6), this double salt effectively can suppress the generation of hydrolysis reaction in heat-processed; (2) ammonium chloride can react with the hydrolysate in double salt heat-processed, is translated into Magnesium Chloride Anhydrous; (3) in ammonium chloride thermal degradation process, the aerial spread coefficient of hydrogen chloride gas is about the half of ammonia spread coefficient, ammonia overflows (ammonia and hydrogen chloride gas in atmosphere spread coefficient are similar) with water vapour prior to hydrogen chloride gas, hydrogen chloride gas be stranded in for a long time material bed in, effectively inhibit the generation of hydrolysis reaction; (4) ammonium chloride decompose the hydrogenchloride of release and ammonia can the dividing potential drop of water vapour and oxygen in diluting reactor, hydrogen chloride gas can the generation of inhibited reaction thing hydrolysis reaction effectively.
Contriver is also found by large quantity research, the effect of chlorination dehydration furnace preheating zone is as follows: (1) mixture to magnesium oxide or hydrated magnesium chloride and ammonium chloride carries out preheating, thoroughly remove the moisture in material or predrainage is carried out to material, preventing or weaken the generation of hydrolysis reaction in heat-processed; (2) double salt effectively can be suppressed to form the volatilization Sum decomposition of ammonium chloride in band and de-ammonium band as tectum, improve the utilization ratio of ammonium chloride; (3) effectively can completely cut off contacting of de-ammonium band product Magnesium Chloride Anhydrous and oxygen in air and water vapour as tectum, under guarantee Magnesium Chloride Anhydrous high temperature, hydrolysis reaction not occur.From gas overflowing mouth discharge ammonium chloride and ammonia can reclaim, the ammonium chloride of recovery turns back to recycle in step (a), thus reduce production cost, enhance productivity.
Fig. 2 shows the schematic diagram of the main device-chlorination dehydration furnace realizing this technique.Material is added by charging opening 1, chlorination dehydration furnace adopts zone heating, preheating zone, stove top 11, the temperature that middle part double salt forms band 12, bottom takes off ammonium band 13 are formed by preheating zone heating unit 5, double salt respectively and are with heating unit 6 and de-ammonium band heating unit 7 to control, and from top to bottom form preheating zone respectively, double salt forms band and de-ammonium band in the burner hearth of chlorination dehydration furnace.In order to ensure that material in a furnace can direct motion, stirring with whipping appts 3 pairs of materials in heat-processed, making material loosening, easily direct motion.The Magnesium Chloride Anhydrous be obtained by reacting enters in storage bin 8 via discharge port 4, react to prevent the water vapour in discharging process in Magnesium Chloride Anhydrous and air and oxygen, storage bin is sealed, and rare gas element is passed in storehouse by inert gas entrance 9, in storehouse, gas from gas outlet 10 is discharged, ensure that the inert atmosphere in storehouse, the ammonia produced in heat-processed, hydrogenchloride and ammonium chloride are overflowed by the gas overflowing mouth 2 of upper of furnace body.
All be not specifically limited the raw material adopted in the inventive method (such as, magnesium oxide, magnesium chloride hexahydrate, ammonium chloride etc.), they all can adopt common commercial products.Described raw material is preferably in powder type, is not particularly limited the particle diameter of described powder.
Compared with the existing method preparing Magnesium Chloride Anhydrous, the invention has the advantages that: (1) technical process is short, and can realize continuous prodution, production efficiency is high; (2) technique is simple, does not need special equipment and atmosphere protection, easy operation control; (3) purity of Magnesium Chloride Anhydrous is high, can reach content of MgO and be less than 0.1 % by weight, can meet the requirement of most advanced electrolyzer to raw material; (4) utilize magnesium oxide or hydrated magnesium chloride and ammonium chloride to prepare Magnesium Chloride Anhydrous for raw material, these cheaper starting materials, to be easy to get; (5) ammonium chloride easily reclaims and realizes recycle, and the corrodibility of ammonium chloride to equipment is little, also lower to the sealing requirements of equipment.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention prepares Magnesium Chloride Anhydrous;
Fig. 2 is the present invention's chlorination dehydration furnace schematic diagram;
In figure: 1-charging opening; 2-gas overflowing mouth; 3-whipping appts; 4-discharge port; 5-preheating zone heating unit; 6-double salt forms band heating unit; 7-takes off ammonium band heating unit; 8-storage bin; 9-inert gas entrance; 10-pneumatic outlet; 11-preheating zone; 12-double salt forms band; 13-takes off ammonium band;
Fig. 3 is the XRD figure spectrum of the Magnesium Chloride Anhydrous utilizing magnesium oxide magnesium to prepare in the embodiment of the present invention 1;
Fig. 4 is the XRD figure spectrum of the Magnesium Chloride Anhydrous utilizing magnesium chloride hexahydrate to prepare in the embodiment of the present invention 12.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
In the present invention, based on the Magnesium Chloride Anhydrous meter of 100%, (namely magnesian content be less than 0.5wt%, the upper limit of contained magnesian content in acceptable Magnesium Chloride Anhydrous for the technique of general electrolytic method production MAGNESIUM METAL), preferably be less than 0.1wt% (that is, in current electrolysis method production MAGNESIUM METAL in state-of-the-art multipolarity electrolyzer acceptable Magnesium Chloride Anhydrous the upper limit of contained magnesian content).Therefore, Magnesium Chloride Anhydrous prepared according to the methods of the invention solution production MAGNESIUM METAL of not only can directly powering uses, and directly can prepare MAGNESIUM METAL for multipolarity electrolytic tank electrolysis.
In addition, in the present invention, unless otherwise noted, the described content containing the magnesium oxide (MgO) in Magnesium Chloride Anhydrous refers to the magnesian weight percentage in the Magnesium Chloride Anhydrous of 100%.
In the present invention, unless otherwise noted, term " hydrated magnesium chloride " refers to the magnesium chloride (MgCl containing crystal water 2mH 2o, wherein m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule, m>0).
According to following method, Magnesium Chloride Anhydrous prepared by the present invention is tested.
1. titration measuring sample aqueous solution throw out is to determine the content of magnesium oxide in Magnesium Chloride Anhydrous
By soluble in water for the Magnesium Chloride Anhydrous sample obtained, with the quantitative paper (Hangzhou Special Paper Industry Co., Ltd.) of four Φ 90mm, at least three times are filtered repeatedly till filtrate is clarified especially to the aqueous solution.Filter paper deionized water is rinsed repeatedly wash away the magnesium ion adhered to above, putting into beaker by washing the rear filter paper containing magnesium oxide particle, adding sulfuric acid (analytical pure, the purity 95.98% of the 1:100 of excessive preparation; Producer: Beijing North fine chemicals limited liability company), beaker heated and boiled also leaves standstill by electric furnace and within five minutes, makes to react completely.Solution in beaker is carried out EDTA titration to determine the content of magnesium ion, thus obtain magnesian content in Magnesium Chloride Anhydrous.
The precondition calculating magnesian content in Magnesium Chloride Anhydrous according to above method can not there is MgOHCl in Magnesium Chloride Anhydrous.The time that MgOHCl is converted into MgO completely 500 DEG C time is 30 minutes, and the time transformed when temperature is higher can shorten.Judge thus, under the condition of the embodiment of the present invention, MgOHCl all can be converted into MgO, and namely sedimentary composition only has magnesium oxide to exist.Data Source is shown in document: Kashani-Nejad, S., K.Ng, et al. (2005) .MgOHCl kinetics of thermal decomposition (MgOHCl thermaldecomposition kinetics.), metallurgical and material publication (Metallurgical and Materials TransactionsB) 2005.
2. the mensuration of moisture content in sample
The sample obtained with present invention process process is because be incubated the long period at relatively high temperatures, free water or crystal water should not be contained in sample, even if there is water also to generate magnesium oxide with anhydrous chlorides of rase reactive magnesium at such high temperatures, test the moisture that the moisture measured is all absorption of sample in mensuration process and in normal temperature preservation process.The mensuration of moisture adopts karl Fischer titration measuring moisture, and instrument adopts the KF-1B type moisture content tester of instrucment and meter plant of Shanghai Chemical Research Inst.Concrete grammar is see " preparation of basic magnesium chloride and the research of physicochemical property thereof ", salt lake S&T resource allocation (1980).
3. use X-ray diffractometer (model: X'Pert PRO MPD; Producer: Philips), the existence of Magnesium Chloride Anhydrous is determined by X-ray diffraction (XRD).
Raw material used in the present invention is commercially available product, comprising:
Magnesium oxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.5%;
Magnesium chloride hexahydrate: magnesium chloride hexahydrate: Xilong Chemical Co., Ltd, purity >=98.0%.
Ammonium chloride: Xilong Chemical Co., Ltd, purity >=99.5%.
Hydrated magnesium chloride: by above-mentioned magnesium chloride hexahydrate 80-160 DEG C of heating, reduced gravity situations judges final product per sample.
Typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
945g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 15cm, mixture heats in different heating zones: first 150 DEG C of heating 0.2 hour, then 300 DEG C of heating 2.5 hours, finally 700 DEG C of heating 0.5 hour, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this embodiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 2.7 weight parts.Fig. 3 is the XRD figure spectrum of Magnesium Chloride Anhydrous prepared by the present embodiment.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2, as shown in Figure 3; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.31%; Measure moisture content in sample, recording moisture content in sample is 0.24%.
Embodiment 2
1404g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 23cm, mixture heats in different heating zones: first 80 DEG C of heating 3.5 hours, then 400 DEG C of heating 0.2 hour, finally 450 DEG C of heating 2.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 4.0 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2show; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.11%; Measure moisture content in sample, recording moisture content in sample is 0.09%.
Embodiment 3
1404g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 15:1, the thickness of mixture in stove is 95cm, mixture heats in different heating zones: first 100 DEG C of heating 1.0 hours, then 380 DEG C of heating 1.8 hours, finally 700 DEG C of heating 1.0 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 4.0 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.05%; Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 4
2340g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 15:1, the thickness of mixture in stove is 134cm, mixture heats in different heating zones: first 120 DEG C of heating 0.5 hour, then 350 DEG C of heating 2.0 hours, finally 680 DEG C of heating 1.2 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 6.7 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.03%; Measure moisture content in sample, recording moisture content in sample is 0.06%.
Embodiment 5
7035g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 126cm, mixture heats in different heating zones: first 120 DEG C of heating 0.5 hour, then 400 DEG C of heating 2.0 hours, finally 650 DEG C of heating 1.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 20.1 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.02%; Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 6
7035g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 2:1, the thickness of mixture in stove is 56cm, mixture heats in different heating zones: first 50 DEG C of heating 5.0 hours, then 250 DEG C of heating 5.0 hours, finally 420 DEG C of heating 5.0 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 20.1 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.08%; Measure moisture content in sample, recording moisture content in sample is 0.09%.
Embodiment 7
1404g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 23cm, mixture heats in different heating zones: first 200 DEG C of heating 0.2 hour, then 400 DEG C of heating 0.2 hour, finally 750 DEG C of heating 0.5 hour, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 4.0 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.06%; Measure moisture content in sample, recording moisture content in sample is 0.06%.
Embodiment 8
910g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 2:1, the thickness of mixture in stove is 10cm, mixture heats in different heating zones: first 150 DEG C of heating 0.5 hour, then 350 DEG C of heating 1.0 hours, finally 650 DEG C of heating 3.0 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 2.6 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.09%; Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 9
8750g ammonium chloride adds length-to-diameter ratio after mixing with 350g magnesium oxide be in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 72cm, mixture heats in different heating zones: first 150 DEG C of heating 0.5 hour, then 350 DEG C of heating 1.0 hours, finally 750 DEG C of heating 4.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with magnesian feeding quantity, the feeding quantity of ammonium chloride is 25 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.03%; Measure moisture content in sample, recording moisture content in sample is 0.02%.
Embodiment 10
535g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl 26H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 38cm, mixture heats in different heating zones: first 150 DEG C of heating 0.2 hour, then 400 DEG C of heating 2.5 hours, finally 700 DEG C of heating 0.5 hour, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 0.56 weight part.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.07%; Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 11
267.5g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl 26H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 21cm, mixture heats in different heating zones: first 50 DEG C of heating 5 hours, then 250 DEG C of heating 5 hours, finally 750 DEG C of heating 0.5 hour, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 0.28 weight part.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.09%; Measure moisture content in sample, recording moisture content in sample is 0.04%.
Embodiment 12
535g ammonium chloride and 2030g magnesium chloride hexahydrate (MgCl 26H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 38cm, mixture heats in different heating zones: first 200 DEG C of heating 0.2 hour, then 250 DEG C of heating 0.2 hour, finally 450 DEG C of heating 5.0 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 0.56 weight part.Fig. 4 is the XRD figure spectrum of Magnesium Chloride Anhydrous prepared by the present embodiment.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.06%; Measure moisture content in sample, recording moisture content in sample is 0.08%.
Embodiment 13
1070g ammonium chloride and 1436g hydrated magnesium chloride (MgCl 22.7H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 3.5:1, the thickness of mixture in stove is 43cm, mixture heats in different heating zones: first 80 DEG C of heating 3.5 hours, then 300 DEG C of heating 0.2 hour, finally 450 DEG C of heating 2.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 1.13 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.04%; Measure moisture content in sample, recording moisture content in sample is 0.06%.
Embodiment 14
2140g ammonium chloride and 1238g hydrated magnesium chloride (MgCl 21.6H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 15:1, the thickness of mixture in stove is 126cm, mixture heats in different heating zones: first 120 DEG C of heating 2.0 hours, then 350 DEG C of heating 2.0 hours, finally 650 DEG C of heating 1.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 2.25 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.03%; Measure moisture content in sample, recording moisture content in sample is 0.07%.
Embodiment 15
5320g ammonium chloride and 123.8g hydrated magnesium chloride (MgCl 21.6H 2o) adding length-to-diameter ratio after mixing is in the chlorination dehydration furnace of 15:1, the thickness of mixture in stove is 126cm, mixture heats in different heating zones: first 150 DEG C of heating 3.5 hours, then 400 DEG C of heating 2.5 hours, finally 700 DEG C of heating 2.5 hours, obtain Magnesium Chloride Anhydrous.Magnesium Chloride Anhydrous is discharged from furnace bottom discharge port, and new a collection of mixture material is added by the charging opening on stove top.In this experiment, be 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 56 weight parts.
According to above-mentioned measuring method, the Magnesium Chloride Anhydrous obtained is characterized.Its result is as follows:
Carry out XRD material phase analysis to sample composition, composition is anhydrous MgCl 2; Throw out after water-soluble to sample carries out titration, and record that magnesian weight is Magnesium Chloride Anhydrous 0.02%; Measure moisture content in sample, recording moisture content in sample is 0.04%.
Can be seen by the result of above embodiment, in the Magnesium Chloride Anhydrous prepared by the technique utilizing magnesium oxide to prepare Magnesium Chloride Anhydrous according to of the present invention and device, objectionable impurities magnesium oxide can be controlled to the upper limit that is 0.5% as industrial application relative to the content of Magnesium Chloride Anhydrous.In addition, after optimizing, objectionable impurities magnesium oxide can be controlled to less than 0.1% relative to the content of Magnesium Chloride Anhydrous, reach the advanced electrolytic magnesium technique in the world to the requirement of raw material.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. the preparation facilities of a Magnesium Chloride Anhydrous, for chlorination dehydration furnace, it is characterized in that, described chlorination dehydration furnace comprises preheating zone, top (11), middle part double salt forms band (12), bottom and take off the storage bin (8) with certain stopping property that ammonium band (13) is connected with by discharge port (4).
2. device as claimed in claim 1, it is characterized in that, the Heating temperature of described preheating zone (11) is 50-200 DEG C, preferred 80-150 DEG C; The Heating temperature that described middle part double salt forms band (12) is 250-400 DEG C, preferred 300-400 DEG C; The Heating temperature that described bottom takes off ammonium band (13) is 420-750 DEG C, preferred 450-700 DEG C.
3. device as claimed in claim 1 or 2, is characterized in that, the length-to-diameter ratio >=2:1 of described chlorination dehydration furnace, is preferably >=3.5:1;
Preferably, described storage bin (8) has inert atmosphere;
Preferably, described chlorination dehydration furnace also comprises gas overflowing mouth (2) and discharge port (4);
Preferably, described chlorination dehydration furnace also comprises whipping appts (3).
4. utilize device described in any one of claim 1-3 to prepare a method for Magnesium Chloride Anhydrous, comprise the steps:
A magnesium oxide and ammonium chloride mix by ();
B step (a) gained mixture adds in chlorination dehydration furnace and heats by (), obtained Magnesium Chloride Anhydrous;
C () Magnesium Chloride Anhydrous is discharged while, repeating step (a) and (b), realize continuous prodution.
5. utilize device described in any one of claim 1-3 to prepare a method for Magnesium Chloride Anhydrous, comprise the steps:
A molecular formula is MgCl by () 2mH 2the hydrated magnesium chloride of O and ammonium chloride mix; Or be MgCl by magnesium oxide and molecular formula 2mH 2the hydrated magnesium chloride of O and ammonium chloride mix;
Wherein, m > 0, preferably 6 >=m > 0;
B step (a) gained mixture adds in chlorination dehydration furnace and heats by (), obtained Magnesium Chloride Anhydrous;
C () Magnesium Chloride Anhydrous is discharged while, repeating step (a) and (b), realize continuous prodution.
6. method as claimed in claim 4, it is characterized in that, be 1.00 parts by weight with magnesian feeding quantity, and the feeding quantity of ammonium chloride is 2.60-25.00 weight part, is preferably 2.70-20.10 weight part.
7. method as claimed in claim 5, it is characterized in that, with not containing the magnesium chloride of crystal water, or magnesium oxide is 1.00 parts by weight with the feeding quantity of the magnesium chloride not containing crystal water, the feeding quantity of ammonium chloride is 0.28-60.00 weight part, is preferably 0.28-56.00 weight part.
8. the method as described in any one of claim 4-7, is characterized in that, in the chlorination dehydration furnace in step (b), the Heating temperature of preheating zone (11) is 50-200 DEG C, preferred 80-150 DEG C; The Heating temperature that middle part double salt forms band (12) is 250-400 DEG C, preferred 300-400 DEG C; The Heating temperature of the de-ammonium band (13) in bottom is 420-750 DEG C, preferred 450-700 DEG C;
Preferably, the length-to-diameter ratio >=2:1 of described chlorination dehydration furnace, is preferably >=3.5:1;
Preferably, described storage bin (8) has inert atmosphere;
Preferably, described chlorination dehydration furnace also comprises gas overflowing mouth (2) and discharge port (4);
Preferably, described chlorination dehydration furnace also comprises whipping appts (3).
9. method as claimed in claim 8, it is characterized in that, described mixture is 0.2-5.0h in the heat-up time of preheating zone, is preferably 0.2-3.5h; The heat-up time forming band at double salt is 0.2-5.0h, is preferably 0.2-2.5h; Be 0.5-5.0h in the heat-up time of de-ammonium band, be preferably 0.5-2.5h.
10. the method as described in any one of claim 4-9, is characterized in that, the thickness of mixture described in step (b) in chlorination dehydration furnace is not less than 10cm, is preferably not less than 15cm;
Preferably, the ammonia produced in step (b), hydrogenchloride and ammonium chloride are discharged through gas overflowing mouth (2), and carry out reclaiming with recycle.
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CN109607581A (en) * 2019-02-19 2019-04-12 河北工业大学 A kind of device and method for producing anhydrous magnesium chloride using ammonium chloride and magnesium carbonate
CN109607581B (en) * 2019-02-19 2023-08-29 河北工业大学 Device and method for preparing anhydrous magnesium chloride by using ammonium chloride and magnesium carbonate
CN112899728A (en) * 2021-04-09 2021-06-04 河北大有镁业有限责任公司 Ammonium carnallite dehydration material and method for preparing magnesium electrolyte melt by using same
CN113106497A (en) * 2021-04-09 2021-07-13 河北大有镁业有限责任公司 Method for continuously producing raw materials for electrolytic rare earth magnesium alloy by utilizing hydrolysis-chlorination coupling reaction
CN113106497B (en) * 2021-04-09 2022-04-01 河北大有镁业有限责任公司 Method for continuously producing raw materials for electrolytic rare earth magnesium alloy by utilizing hydrolysis-chlorination coupling reaction
CN113479917A (en) * 2021-08-02 2021-10-08 青海盐湖工业股份有限公司 Method and system for preparing anhydrous magnesium chloride

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