CN103184352A - Technique method for manufacturing magnesium metal by dolomite - Google Patents
Technique method for manufacturing magnesium metal by dolomite Download PDFInfo
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- CN103184352A CN103184352A CN 201310097639 CN201310097639A CN103184352A CN 103184352 A CN103184352 A CN 103184352A CN 201310097639 CN201310097639 CN 201310097639 CN 201310097639 A CN201310097639 A CN 201310097639A CN 103184352 A CN103184352 A CN 103184352A
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- magnesium
- rhombspar
- oxalate
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000010459 dolomite Substances 0.000 title claims abstract description 8
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title abstract description 39
- 239000011777 magnesium Substances 0.000 claims abstract description 43
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 12
- 239000000571 coke Substances 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 11
- 230000005494 condensation Effects 0.000 claims abstract description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000009736 wetting Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 22
- 230000002829 reductive effect Effects 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 230000029087 digestion Effects 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000004816 latex Substances 0.000 claims description 12
- 229920000126 latex Polymers 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 229940039748 oxalate Drugs 0.000 claims description 9
- 238000003672 processing method Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000005242 forging Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 241000234435 Lilium Species 0.000 claims description 2
- 210000002249 digestive system Anatomy 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 abstract description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 32
- 239000000395 magnesium oxide Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 8
- 229910000676 Si alloy Inorganic materials 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a technique method for manufacturing magnesium metal by dolomite. The method is that the dolomite is subjected to crushing, calcining, digesting, filtering, carbonization, solid-liquid separation, pyrolysis, basic magnesium carbonate drying, mixing with ingredients of basic magnesium carbonate, reducing agent coke and catalyzer calcium fluoride, wetting performing, material decomposition, vacuum reduction, and magnesium vapour condensation to obtain magnesium metal with a purity above 90%. According to the technique method, the problem that calcium-magnesium separation of the dolomite is solved through the process of the intermediate product, basic magnesium carbonate, and the decomposition and the vacuum carbothermal reduction of the material are completed in a same vacuum furnace. Therefore, the technique method has the advantages of smooth technique, low cost, lower environmental pollution, high quality byproduct, and light calcium carbonate.
Description
Technical field
The present invention relates to a kind of production method of MAGNESIUM METAL, refer in particular to a kind of processing method of rhombspar production MAGNESIUM METAL.
Background technology
Magnesium is that a kind of lightweight has ductility and very active metal, is widely used in other industries such as automotive industry, 3C industry, aerospace and military affairs.The smelting process of metal current magnesium mainly is divided into hot reducing method and fusion electrolysis method, and hot reducing method comprises ferrosilicon hot reducing method (Pidgeon process), thermit reduction and aluminum silicon alloy hot reducing method etc.; Fusion electrolysis is to be raw material with the magnesium chloride, metal alloy is cathode and anode, feed direct current and carry out electrolysis under the magnesium chloride fusion, negative electrode obtains the MAGNESIUM METAL deposition, and anode is emitted chlorine, fusion electrolysis method environmental pollution is serious, and facility investment is big, and Technology falls behind, and equipment capacity is low, energy consumption height, direct current consumption are 14420KWh/tMg.The processing method that China uses always at present is hot reducing method, this method is with magnesite calcination under hot conditions, be reductive agent with ferro-silicon, aluminium, aluminum silicon alloy or aluminum magnesium alloy, under certain vacuum degree and temperature, obtain MAGNESIUM METAL through condensation again after will being reduced into magnesium vapor through the magnesite of high-temperature calcination, this method calcining temperature height, the energy consumption height, the magnesium rate of recovery is low, and the production cycle is long, deficiency in economic performance, environmental pollution is serious.In order to solve the source problem that comes of MAGNESIUM METAL, adopt the relatively low dolomite mineral of magnesium content, be a good selection, therefore, be having a extensive future of raw material production MAGNESIUM METAL with the rhombspar.It is the method for feedstock production MAGNESIUM METAL with the rhombspar that application number 201010126327.5 discloses a kind of, ferrosilicon hot reducing method, thermit reduction and aluminum silicon alloy reduction method have been comprised, but because containing more calcium in the rhombspar, if not carrying out calcium magnesium separates, then this processing method is got rid of a large amount of calcic waste residues, inefficiency has also increased the high temperature energy consumption simultaneously.In order to overcome the ferrosilicon reduction, the shortcoming of aluminium reducing or aluminum silicon alloy reduction method, cut down the consumption of energy, reduce the deslagging problem, it is the method that MAGNESIUM METAL is produced in the material vacuum reduction with the MgO/CaO mol ratio greater than 1 material that application number 201010144074.4 discloses a kind of, it is characterized in that with rhombspar, giobertite, brucite and Wingdale are raw material, carrying out satin respectively burns, be mixed with the MgO/CaO mol ratio again and be 1.5～18 raw material, the raw material of this arts demand exploitation is many and mix, the calcining process complexity, and its reductive agent still adopts expensive aluminium powder, aluminum silicon alloy powder or aluminium-magnesium alloy powder.Therefore, from aspect analyses such as reductive agent, energy consumption and efficient, the popularization difficulty of this class hot reducing method is difficult to realize sustainable development.
The fifties in last century, in order to adopt cheap carbonaceous reducing agent in the hot reducing method of MAGNESIUM METAL, some investigators have explored the vacuum carbothermal reduction method, have carried out the thermomechanical analysis than system, and have obtained some progress.Wherein the most representative is little experiment and the expansion experiment that R.Winand did in 1972～1976 years, has obtained metal magnesium powder.Application number 008100058928.X discloses a kind of method of preparing magnesium metal by giobertite vacuum carbon thermal reduction, it is characterized in that with magnesite for containing magnesium raw material, coal is reductive agent and adds Calcium Fluoride (Fluorspan) as catalyzer, control vacuum oven internal pressure is 20Pa～700Pa, be warming up to 500 ℃～700 ℃, insulation 20min～50min, finish material thermolysis and close-burning process, be warming up to retailoring 40min～60min under 1300 ℃～1500 ℃ the condition again, obtain reguline metal magnesium, this processing requirement adopts the magnesite of MgO content 〉=41% to be not suitable for rhombspar as raw material as raw material.Application number 200510011049.8 discloses a kind of method of vacuum, heat and coal reduction extracting metal magnesium from magnesium oxide ore, it is characterized in that adopting magnesium oxide or its mineral white marble is raw material, coal is made reductive agent, raw material is through mixing, after suppressing agglomerating material, in the internal heat type vacuum oven with vacuum tightness 5Pa～45Pa, 500 ℃～800 ℃ of temperature, time 30min～60min, finish the material close-burning, carried out reduction reaction 45 minutes～60 minutes for 1300 ℃～1600 ℃ in temperature again, at last in 600 ℃～800 ℃ condensations of temperature, obtain the crystal metal MAG block, but, this technology for contain magnesium raw material require high, must adopt the magnesium oxide of MgO content 〉=95%, perhaps adopting the higher-grade rhombspar of MgO content more than 30% to obtain the white magnesium oxide of forging of MgO 〉=40%～45% through calcining is raw material, and the MgO content of the natural dolomite mineral of actual China generally has only 18%～22%, the white MgO content of forging through the high-temperature calcination preparation only has 32～39%, thereby in fact this technology can not utilize rhombspar to prepare MAGNESIUM METAL as raw material.
Above-mentioned analysis revealed, adopt the key problem in technology of rhombspar production MAGNESIUM METAL to be the calcium magnesium isolation technique in the rhombspar and to use cheap carbonaceous reducing agent technology, how to utilize rhombspar as the raw material that contains magnesium, adopt the vacuum carbothermal reduction method, produce MAGNESIUM METAL low-cost high-efficiency, will restrict fairly large popularization and the application that rhombspar prepares the MAGNESIUM METAL technology.
Summary of the invention
The technical problem to be solved in the present invention provides the processing method that a kind of rhombspar prepares MAGNESIUM METAL, and it is raw material through the intermediates magnesium basic carbonate after transforming that this method adopts rhombspar, uses vacuum carbothermal reduction to make MAGNESIUM METAL.Present method has solved the calcium magnesium separation problem in the rhombspar raw material, has reduced the cost of reductive agent, by-product the light calcium carbonate of high added value, and technology smoothness, benefit is more remarkable, constant product quality is easy to utilize.
The technical problem to be solved in the present invention is realized by following steps:
1, a kind of processing method of rhombspar production MAGNESIUM METAL is characterized in that may further comprise the steps:
(1) rhombspar fragmentation: rhombspar is carried out Mechanical Crushing to 1cm～10cm;
(2) dolomite calcination: the rhombspar of fragmentation is calcined 0.5h～5h down at 850 ℃～1100 ℃ obtain forging white;
(3) forge white digestion: will forge white is 1: 30～70 to add water by mass ratio, and adding thermal control digestion temperature is 50 ℃～80 ℃, fully stirs 0.5h～4h;
(4) Digestive system filters: the filtrate of above-mentioned digestion is crossed 60 mesh sieves, remove the residue that can not fully digest, obtain thinner magnesium latex emulsion;
(5) magnesium latex emulsion carbonization: after the magnesium latex emulsion cooling, feed carbonic acid gas, keeping the flow velocity of carbonic acid gas is 0.5L/min～1L/min.And the pH of tracking and testing magnesium latex emulsion, when pH reaches 7.5～9.5, add oxalic acid or solubility oxalate in the system, the concentration that makes the oxalate in the system is 0.001mol/L～0.01mol/L, fully shake up the back continue carbonization to pH be 6.5～7.0;
(6) magnesium latex emulsion filters: the emulsion after the carbonization is filtered, and residual residue is light calcium carbonate, and filtrate is refining heavy magnesium water;
(7) heavy magnesium water pyrolysis: heavy magnesium water obtains the basic carbonate magnesium precipitate at 90 ℃～100 ℃ following pyrolysis 1h～4h, obtains the magnesium basic carbonate filter cake after the filtration, and its filtrate is salts solution, continues to add water and is used for the new white digestion of forging;
(8) magnesium basic carbonate oven dry: the magnesium basic carbonate filter cake after pyrolysis is filtered, dry by the fire 1h～5h down at 100 ℃～220 ℃ and obtain lily magnesium basic carbonate;
(9) batch mixes: be the magnesium source with the magnesium basic carbonate, coke is reductive agent, and Calcium Fluoride (Fluorspan) is catalyzer, mixes, and the coke mixed volume is the mole proportioning of C: MgO=1～4: 1, and the addition of Calcium Fluoride (Fluorspan) is 5%～15% of mixing raw material;
(10) wetting compressing tablet: with above-mentioned compound, add the wetting agent dehydrated alcohol, compound (g)/dehydrated alcohol (mL)=1: 1～3: 1 is stirred to bulk, is pressed into sheet material with the pressure of 5～20MPa;
(11) material decomposes: the sheet material that is pressed into is put into crucible, the vacuum oven of packing into, control furnace pressure＜100Pa, be 5 ℃/min at the temperature rise rate of control below 500 ℃, the control temperature rise rate is 1～2 ℃/min between 500～600 ℃, finishes material and decomposes;
(12) vacuum reducing: the temperature rise rate with 7～10 ℃/min continues to be warming up to 1300～1500 ℃, carries out carbothermic reduction reaction 90～120min, obtains magnesium steam;
(13) magnesium vapor condensation: utilize thermograde to make magnesium steam under 450～500 ℃, be condensed into the metal MAG block at the boiler tube condensation segment;
(14) obtain MAGNESIUM METAL: vacuum oven pressure＜100Pa, close vacuum pump, temperature is reduced to room temperature, obtains the MAGNESIUM METAL product.
Used oxalic acid or solubility oxalate are any one or more than one the mixture in oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate in the step (5).
The used wetting agent dehydrated alcohol of step (10) plays the effect that makes material become piece easily, and the sheet material that is pressed into is the disk of diameter 2～4cm, height 1～6mm.
The invention has the advantages that: be the high-purity magnesium basic carbonate of raw material production intermediate product with the rhombspar 1,, realized that the calcium magnesium of rhombspar separates, reduced waste sludge discharge, reduced the high temperature energy consumption; 2, adopting coke is reductive agent, compares with ferro-silicon, aluminium or aluminum silicon alloy, and the cost of reductive agent is very low, thereby economic benefit is more remarkable; 3, in same stove, finish material decomposition reaction and vacuum reducing reaction, shortened technical process, make production process be easy to control, reduced the investment of industrialization project; 4, entire reaction course is carried out in vacuum environment, and is little to the pollution of outside atmosphere.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is that the X-ray diffraction of rhombspar raw material is analyzed collection of illustrative plates.
Fig. 3 is the X-ray energy spectrum analysis chart (EDS) of the MAGNESIUM METAL product of embodiment 1.
Embodiment
Further set forth the present invention by the following examples, these embodiment are only presented for purposes of illustration, do not limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition.
Embodiment 1: the chemical constitution of rhombspar is MgO content 20.96%, and CaO content 30.06% is crushed to 2cm～5cm.Calcine 3h down at 900 ℃, must forge white.To forge white according to water: forging white mass ratio is mixing in 50: 1, and control digestion temperature is 60 ℃, and insulation digestion 1h gets emulsion.Emulsion is crossed 60 mesh sieves, obtains smart magnesium latex emulsion.Feed CO after being cooled to room temperature
2, CO
2Flow velocity is 0.5L/min, and tracking and testing carbonization system pH value.When carbonized bodies is pH=8.5, add ammonium oxalate, the concentration that makes system medium-height grass acid group is 0.002mol/L, continues carbonization to pH=6.5, stops carbonization.With the system solid-liquid separation after the carbonization, solid phase is light calcium carbonate, and liquid phase is heavy magnesium water.The gained heavy magnesium water is at 95 ℃ of following pyrolysis 2h, and cooling back solid-liquid separation, solid phase are dried by the fire 2h down at 150 ℃ and be magnesium basic carbonate.With magnesium basic carbonate, the coke of granularity 0～4mm, purity is that 99.5% Calcium Fluoride (Fluorspan) is as raw material, according to C: MgO mol ratio=3.5: 1 adds the reductive agent coke, add the catalyzer Calcium Fluoride (Fluorspan) that accounts for material total amount 10%, add dehydrated alcohol, after compound (g)/dehydrated alcohol (mL)=3: 1 mixes, under 10MPa pressure, be pressed into the disk of Φ 30 * 5mm, put into crucible, the vacuum oven of packing into, open vacuum pump, begin to heat up when pressure 85Pa, temperature rise rate is 5 ℃/min, temperature rise rate is 1 ℃/min when being warming up between 500～600 ℃, finishes material and decomposes.Stop heating behind the vacuum reducing 105min when continuing to be warming up to 1460 ℃ with the temperature rise rate of 7 ℃/min again, make the magnesium vapor condensation.When temperature is reduced to room temperature, close vacuum oven, obtain MAGNESIUM METAL from the boiler tube condensation segment, detect through EDS, the purity of MAGNESIUM METAL is 96%.
Embodiment 2: the chemical constitution of rhombspar is MgO content 20.96%, and CaO content 30.06% is crushed to 2cm～5cm.Calcine 2.5h down at 950 ℃, must forge white.To forge white according to water: forging white mass ratio is mixing in 40: 1, is heated with stirring to 70 ℃, and insulation digestion 1.5h gets emulsion.Emulsion is crossed 60 mesh sieves, obtains smart magnesium latex emulsion.Feed CO after being cooled to room temperature
2, CO
2Flow velocity is 0.8L/min, and tracking and testing carbonization system pH.When carbonized bodies is pH=9.0, add oxalic acid, the concentration that makes system medium-height grass acid group is 0.005mol/L, continues carbonization to pH=6.8, stops carbonization.With the system solid-liquid separation after the carbonization, solid phase is light calcium carbonate, and liquid phase is heavy magnesium water.The gained heavy magnesium water is at 100 ℃ of following pyrolysis 2h, and cooling back solid-liquid separation, solid phase are dried by the fire 1h down at 180 ℃ and be magnesium basic carbonate.With magnesium basic carbonate, the coke of granularity 0～2mm, purity is that 99.6% Calcium Fluoride (Fluorspan) is as raw material, according to C: MgO mol ratio=2.6: 1 adds the reductive agent coke, add the catalyzer Calcium Fluoride (Fluorspan) that accounts for material total amount 15%, add dehydrated alcohol, after compound (g)/dehydrated alcohol (mL)=3: 1 mixes, under 8MPa pressure, be pressed into the disk of Φ 35 * 4mm, put into crucible, the vacuum oven of packing into, open vacuum pump, begin to heat up when pressure 70Pa, temperature rise rate is 5 ℃/min, temperature rise rate is 2 ℃/min when being warming up between 500～600 ℃, finishes material and decomposes.Stop heating behind the vacuum reducing 110min when continuing to be warming up to 1460 ℃ with the temperature rise rate of 8 ℃/min again, make the magnesium vapor condensation.When temperature is reduced to room temperature, close vacuum oven, obtain MAGNESIUM METAL from the boiler tube condensation segment, detect through EDS, the purity of MAGNESIUM METAL is 93%.
Table 1 is the reaction conditions tabulation that embodiment 3～embodiment 5 adopts.
Table 1
A=globule size in the table 1; The b=calcining temperature; The c=calcination time; D=water with forge white mass ratio; E=hot digestion temperature; The f=digestion time; G=filters sieve aperture; H=CO
2Flow velocity; Carbonization system pH when i=adds oxalic acid or solubility oxalate; J=oxalate concentration; K=terminal point pH; The l=pyrolysis temperature; The m=pyrolysis time; The n=bake out temperature; The o=drying time; The p=coke size; Q=Calcium Fluoride (Fluorspan) purity; R=C: MgO mol ratio; The interpolation of s=Calcium Fluoride (Fluorspan) accounts for the material total amount; The ratio of t=wetting agent dehydrated alcohol is in compound (g)/dehydrated alcohol (mL); The pressure of u=material compressing tablet; V=disk size; Vacuum pump pressure when the w=material begins to heat up; Temperature rise rate when x=is warming up between 500～600 ℃; The temperature rise rate of y=vacuum reducing; The temperature of z=vacuum reducing; The soaking time of aa=vacuum reducing; Kind for the oxalic acid that adds in the carbonization process or oxalate, embodiment 3,4 and 5 is respectively sodium oxalate, potassium oxalate and oxalic acid, embodiment 6 is that oxalic acid and ammonium oxalate are according to 1: 1 mixture of mass ratio, embodiment 7 be oxalic acid and potassium oxalate according to 3: 1 mixture of mass ratio, embodiment 8 is that oxalic acid, sodium oxalate and ammonium oxalate are according to 1: 2: 4 mixture of mass ratio.Except the listed condition of table 1, all the other contents are with embodiment 1.
Table 2 is the purity of the MAGNESIUM METAL for preparing of embodiment 3～embodiment 8.By the purity data of MAGNESIUM METAL listed in embodiment 1, embodiment 2 and the table 2 as can be seen, constant product quality of the present invention, purity is stabilized in 92%～96%.
Table 2
Claims (3)
1. the processing method of a rhombspar production MAGNESIUM METAL is characterized in that may further comprise the steps:
(1) rhombspar fragmentation: rhombspar is carried out Mechanical Crushing to 1cm～10cm;
(2) dolomite calcination: the rhombspar of fragmentation is calcined 0.5h～5h down at 850 ℃～1100 ℃ obtain forging white;
(3) forge white digestion: will forge white is 1: 30～70 to add water by mass ratio, and adding thermal control digestion temperature is 50 ℃～80 ℃, fully stirs 0.5h～4h;
(4) Digestive system filters: the filtrate of above-mentioned digestion is crossed 60 mesh sieves, remove the residue that can not fully digest, obtain thinner magnesium latex emulsion;
(5) magnesium latex emulsion carbonization: after the magnesium latex emulsion cooling, feed carbonic acid gas, keeping the flow velocity of carbonic acid gas is 0.5L/min～1L/min.And the pH of tracking and testing magnesium latex emulsion, when pH reaches 7.5～9.5, add oxalic acid or solubility oxalate in the system, the concentration that makes the oxalate in the system is 0.001mol/L～0.01mol/L, fully shake up the back continue carbonization to pH be 6.5～7.0;
(6) magnesium latex emulsion filters: the emulsion after the carbonization is filtered, and residual residue is light calcium carbonate, and filtrate is refining heavy magnesium water;
(7) heavy magnesium water pyrolysis: heavy magnesium water obtains the basic carbonate magnesium precipitate at 90 ℃～100 ℃ following pyrolysis 1h～4h, obtains the magnesium basic carbonate filter cake after the filtration, and its filtrate is salts solution, continues to add water and is used for the new white digestion of forging;
(8) magnesium basic carbonate oven dry: the magnesium basic carbonate filter cake after pyrolysis is filtered, dry by the fire 1h～5h down at 100 ℃～220 ℃ and obtain lily magnesium basic carbonate;
(9) batch mixes: be the magnesium source with the magnesium basic carbonate, coke is reductive agent, and Calcium Fluoride (Fluorspan) is catalyzer, mixes, and the coke mixed volume is the mole proportioning of C: MgO=1～4: 1, and the addition of Calcium Fluoride (Fluorspan) is 5%～15% of mixing raw material;
(10) wetting compressing tablet: with above-mentioned compound, add the wetting agent dehydrated alcohol, compound (g)/dehydrated alcohol (mL)=1: 1～3: 1 is stirred to bulk, is pressed into sheet material with the pressure of 5～20MPa;
(11) material decomposes: the sheet material that is pressed into is put into crucible, and the vacuum oven of packing into, is 5 ℃/min at the temperature rise rate of control below 500 ℃ at control furnace pressure＜100Pa, and the control temperature rise rate is 1～2 ℃/min between 500～600, finishes material and decomposes;
(12) vacuum reducing: the temperature rise rate with 7～10 ℃/min continues to be warming up to 1300～1500 ℃, carries out carbothermic reduction reaction 90～120min, obtains magnesium steam; (13) magnesium vapor condensation: utilize thermograde to make magnesium steam under 450～500 ℃, be condensed into the metal MAG block at the boiler tube condensation segment;
(14) obtain MAGNESIUM METAL: vacuum oven pressure＜100Pa, close vacuum pump, temperature is reduced to room temperature, obtains the MAGNESIUM METAL product.
2. the processing method of a kind of rhombspar production MAGNESIUM METAL according to claim 1 is characterized in that: used oxalic acid or solubility oxalate are one or more the mixture in oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate in the described step (5).
3. the processing method of a kind of rhombspar production MAGNESIUM METAL according to claim 1 is characterized in that: the sheet material that described step (10) is pressed into is the disk of diameter 2～4cm, height 1～6mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981098A (en) * | 2021-02-02 | 2021-06-18 | 朱广东 | Dolomite smelting device and smelting method thereof |
| CN115141941A (en) * | 2022-06-27 | 2022-10-04 | 中铝郑州有色金属研究院有限公司 | Comprehensive utilization method of dolomite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981098A (en) * | 2021-02-02 | 2021-06-18 | 朱广东 | Dolomite smelting device and smelting method thereof |
| CN115141941A (en) * | 2022-06-27 | 2022-10-04 | 中铝郑州有色金属研究院有限公司 | Comprehensive utilization method of dolomite |
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