CN103184477A - Technology method for producing rare earth magnesium alloy by dolomite - Google Patents
Technology method for producing rare earth magnesium alloy by dolomite Download PDFInfo
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- CN103184477A CN103184477A CN 201310097726 CN201310097726A CN103184477A CN 103184477 A CN103184477 A CN 103184477A CN 201310097726 CN201310097726 CN 201310097726 CN 201310097726 A CN201310097726 A CN 201310097726A CN 103184477 A CN103184477 A CN 103184477A
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- magnesium
- rare earth
- dolomite
- magnesium chloride
- rhombspar
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 79
- 239000010459 dolomite Substances 0.000 title claims abstract description 9
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 229910000861 Mg alloy Inorganic materials 0.000 title abstract description 10
- 238000005516 engineering process Methods 0.000 title abstract description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 38
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 37
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 31
- 229940091250 magnesium supplement Drugs 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229960002337 magnesium chloride Drugs 0.000 claims abstract description 17
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 17
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- -1 rare earth chloride Chemical class 0.000 claims abstract description 14
- 239000004816 latex Substances 0.000 claims abstract description 13
- 229920000126 latex Polymers 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 56
- 239000002994 raw material Substances 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229940039748 oxalate Drugs 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003839 salts Chemical group 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 241000209456 Plumbago Species 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 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 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000005242 forging Methods 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 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
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 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
- 239000007787 solid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 210000002249 digestive system Anatomy 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000001095 magnesium carbonate Substances 0.000 abstract description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- DARFZFVWKREYJJ-UHFFFAOYSA-L magnesium dichloride dihydrate Chemical compound O.O.[Mg+2].[Cl-].[Cl-] DARFZFVWKREYJJ-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical class Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a technology method for producing rare earth magnesium alloy by dolomite, which comprises the following steps: crushing and calcining dolomite, digesting, filtering, carbonizing magnesium latex and carring out solid-liquid separation, pyrolyzing heavy magnesium water, pickling basic magnesium carbonate, evaporating and crystallizing magnesium chloride, mixing magnesium chloride hexahydrate and hydrous rare earth chloride, heating, dropwise-adding and feeding, and carrying out direct-current electrolysis through taking liquid state rare earth magnesium alloy as a subsiding cathode and taking graphite crucible as an anode to gain rare earth magnesium alloy with more than 5 percent to 90 percent of rare earth content. Through the calcination-carbonation-pickling preprocessing method of dolomite, the technology method has the characteristic that dolomite is subjected to direct current electrolysis on the basis of gaining high purity magnesium chloride hexahydrate intermediate material, and has the advantages that the technology is fluent, the cost is low, the product quality is stable, the quality is good, high-grade light calcium carbonate byproduct is gained, and the popularization and application values are high.
Description
Technical field
The present invention relates to a kind of production method of magnesium-rare earth, refer in particular to the processing method that a kind of rhombspar is produced magnesium-rare earth.
Background technology
Magnesium alloy has low density, high specific strength, high specific stiffness, high elastic coefficient, high damping properties, also has characteristics such as good machinability, thermal conductivity and anti-electromagnetic interference.Magnesium alloy is easy to reclaim than aluminium alloy, can accomplish 100% recycling, so magnesium alloy materials is described as " green engineering structural metallic materials ".Rare earth element is owing to have unique configuration of extra-nuclear electron, show unique character, O, S and other non-metallic elements there is stronger avidity, in metallurgical, material field, unique effect is arranged, have the alloy solution of purification, improve alloy structure, improve alloy room temperature and mechanical behavior under high temperature, function such as enhancing alloy corrosion resistance energy.Magnesium-rare earth not only has the intrinsic advantage of magnesium alloy, also have simultaneously anti-oxidant, anticorrosive, high-temperature capability is high, high temperature resistance wriggling and reclaim advantages such as pollution-free, can satisfy Aeronautics and Astronautics, automobile, military project to loss of weight and requirements of saving energy, and replacing engineering plastics to the requirements such as light, thin, little, highly integrated and environmental protection of 3C (computer, communication, consumer electronics) product, application prospect is very extensive.
Because magnesium and rare earth have resources advantage in China, therefore, the exploitation magnesium-rare earth constantly improves existing magnesium-rare earth system, and develop low cost, high performance novel rare-earth magnesium alloy, will have great pushing effect to the development in China's magnesium alloy materials and rare earth material field.Because China has taked the limiting protecting policy to the development and use of magnesite, is mainly used in the production of high-temperature refractory and highly-purity magnesite.In order to solve the source problem that comes of magnesium, adopt the relatively low dolomite mineral of magnesium content, be a good selection.Therefore, with the rhombspar be having a extensive future of raw material production magnesium-rare earth.
At present, the preparation method of magnesium-rare earth mainly is smelting process and fused salt electrolysis process.Smelting process is to carry out melting with MAGNESIUM METAL and metal-rare-earth, obtains forming suitable alloy, makes component with various forming techniques then.Fused salt electrolysis process generally is in atmosphere, is anode with graphite, is negative electrode with metal molybdenum or tungsten, or is negative electrode with liquid metal magnesium, liquid metal rare earth, liquid magnesium-rare earth, the electrolytic preparation magnesium-rare earth.Wherein, have tangible unpolarizing with liquid cathode electrolytic preparation magnesium-rare earth, make rare earth ion be easy to separate out at negative electrode, be conducive to improve current efficiency, reduce bath voltage and power consumption.The liquid cathode electrolytic process comprises come-up negative electrode and two kinds of methods of sinking negative electrode, the former can produce the low magnesium-rare earth of content of rare earth, even MAGNESIUM METAL, the latter can produce the high magnesium-rare earth of content of rare earth, be convenient to the separation of electrolysate, simultaneously can reduce power consumption, improve the output of magnesium-rare earth.Fused salt electrolysis process prepares magnesium-rare earth and has advantages such as alloying constituent reduced in segregation, quality product height, preparation cost are low, has been subjected to widely and has paid close attention to.
Traditional fused salt electrolysis process is produced magnesium-rare earth, and the electrolysis raw material that adopts is Magnesium Chloride Anhydrous, but Magnesium Chloride Anhydrous is because preparing difficulty, the production cost height, thus cause the magnesium-rare earth cost height produced, lack the market competitiveness.Application number 201110191455.2 discloses a kind of preparation method of magnesium-rare earth, its feature comprises: adopt closing down magnesium electrolysis bath, be that 2%～15% mixture is the ionogen fused salt with magnesium eletrolysis molten salt system and rare earth chloride content, carry out electrolysis at 650 ℃～720 ℃, simultaneously add weight ratio in the closing down magnesium electrolysis bath and be (1.5～11): 1 Magnesium Chloride Anhydrous and rare earth chloride, because this processing method must adopt Magnesium Chloride Anhydrous and anhydrous chlorides of rase earth elements, thereby manufacturing cost is higher, and the content of the magnesium-rare earth middle-weight rare earths that obtains is lower, is no more than 10%.Application number 201010100139.5 discloses a kind of method with hydrated magnesium chloride and rare earth chloride electrolytic preparation magnesium-rare earth alloy, and it is characterized in that: this method is with MgCl
22H
2O and CeCl
33H
2O or MgCl
22H
2O and NdCl
33H
2O is the electrolysis raw material, with MgCl
2-NaCl-KCl-CeCl
3System or MgCl
2-NaCl-KCl-NdCl
3System is ionogen, is that sinking negative electrode, graphite are anode with the molybdenum bar, is that 4.0～8.0V, temperature are to carry out dc electrolysis under 680 ℃～800 ℃ the condition at voltage, obtains magnesium-rare earth at negative electrode.This process using not exclusively magnesium chloride dihydrate and the three water rare earth chlorides of dehydration is the electrolysis raw material, has avoided removing in the traditional method water of constitution in the muriate crystal, simplifies technological process, has reduced the raw material production cost.Application number 200910117402.9 discloses a kind of method of preparing magnesium-rare earth alloy by fused salt electrolysis process, it is characterized in that with hydrated magnesium chloride and moisture rare earth chloride be the electrolysis raw material, be ionogen with Repone K, be negative electrode with the molybdenum bar or be the sinking negative electrode with liquid metal rare earth or liquid magnesium-rare earth, exhausting with the graphite mandarin orange is anode, be 1000A～2000A in electric current, voltage is 5V～15V, temperature is to carry out dc electrolysis under 800 ℃～1000 ℃, obtain containing the magnesium-rare earth of rare earth 5wt%～95wt% at negative electrode, this processing method even can adopt magnesium chloride hexahydrate and seven water rare earth chlorides are the electrolysis raw material, significantly reduced the preparation cost of electrolysis raw material, and the magnesium-rare earth product that obtains is formed evenly, segregation-free, quality is good, thereby certain technical superiority is arranged.The preparation method of above magnesium-rare earth is can not be directly used in main electrolysis raw material rhombspar and prepare magnesium-rare earth at the magnesium chloride of anhydrous, partial dehydration or six water etc.
Summary of the invention
The technical problem to be solved in the present invention provides the processing method that a kind of rhombspar is produced magnesium-rare earth, and adopting rhombspar is raw material through the intermediates magnesium chloride hexahydrate after transforming, and uses fused salt electrolysis process to prepare magnesium-rare earth.The invention solves the calcium magnesium separation problem in the rhombspar raw material, directly adopt the electrolysis of intermediates magnesium chloride hexahydrate, reduced production cost, simultaneously by-product the light calcium carbonate of high added value, its technology smoothness, benefit is more remarkable, constant product quality, easy to utilize.
The technical problem to be solved in the present invention is realized by following steps:
(1) rhombspar fragmentation: rhombspar is carried out Mechanical Crushing to 1cm～10cm, preferably be crushed to 2cm～5cm;
(2) dolomite calcination: with the rhombspar of fragmentation 850 ℃～1100 ℃ down calcining 0.5～5h obtain forging white, optimum temps is 900 ℃～1000 ℃, calcination time is preferably 1h～3h;
(3) forge white digestion: will forge white is 1: 30～70 to add water by mass ratio, be preferably 1: 40～50 add water, adding thermal control digestion temperature is 50 ℃～80 ℃, fully stirs 0.5h～4h, the hot digestion temperature is preferably 60 ℃～70 ℃, and digestion time is preferably 1h～3h;
(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; Add oxalic acid or solubility oxalate when being easy to act as pH most and reaching 8～9, add-on remains on and makes the concentration of oxalate be preferably 0.001mol/L～0.01mol/L, continues carbonization to pH=6.5～7.0;
(6) magnesium latex emulsion filters: the emulsion after the carbonization, to filter, and residual residue is light calcium carbonate, filtrate is refining heavy magnesium water;
(7) heavy magnesium water pyrolysis: heavy magnesium water is at 90 ℃～100 ℃ following pyrolysis 1h～4h, obtain the basic carbonate magnesium precipitate, obtain the magnesium basic carbonate filter cake after the filtration, its filtrate is salts solution, continue to add water and be used for the new white digestion of forging, the optimum temps of pyrolysis is 95 ℃～100 ℃, and the pyrolysis Best Times is 2h～3h.Filtrate continuation after the pyrolysis recycle in digestion new forge white;
(8) magnesium basic carbonate acidleach: the magnesium basic carbonate filter cake after will filtering is put into stirred autoclave, according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that 1: 10～15 to add concentration be that 30% hydrochloric acid carries out stirring reaction, and stir speed (S.S.) is 10r/min～40r/min, treats to obtain magnesium chloride solution after solid dissolves fully; 4MgCO
3Mg (OH)
24H
2The optimum mole ratio of O and HCl is 1: 11～1: 14, and best stir speed (S.S.) is 20r/min～30r/min.
(9) magnesium chloride evaporative crystallization: be 40.0%～41.3% through heating evaporation, the massfraction that is concentrated into magnesium chloride with the gained magnesium chloride solution, control speed of cooling then and be 2 ℃/min～4 ℃/min, be cooled to 20 ℃～40 ℃ and separate out crystal, crystallization when being cooled to 25 ℃～35 ℃, separate through suction filtration, obtain highly purified magnesium chloride hexahydrate crystal at 70 ℃～80 ℃ dry 1h～1.5h;
(10) mixed material feeding: being the electrolysis raw material with the highly purified magnesium chloride hexahydrate of evaporative crystallization gained and moisture rare earth chloride, is 1: 0.1～12 to mix according to weight ratio, in the plumbago crucible of packing into, feeds intake through being added drop-wise in the ionogen continuously after the heat fused; The optimum weight ratio of highly purified magnesium chloride hexahydrate and moisture rare earth chloride is 1: 0.30～1;
(11) dc electrolysis: be that 1: 1～3 Repone K and sodium chloride mixture are ionogen with mass ratio, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, be 1000A～1600A at electric current, voltage is 5V～15V, and temperature is to carry out dc electrolysis under 800 ℃～1100 ℃ conditions, obtain magnesium-rare earth at negative electrode, electric current the best is 1200A～1500A, and voltage the best is 7V～13V, and temperature the best is 850 ℃～1000 ℃.
Used oxalic acid or solubility oxalate are one or more the mixture in oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate in the step (5).
The invention has the advantages that: 1, be the raw material production magnesium-rare earth with the rhombspar, abundant raw material, production cost are low; 2, with dolomite calcination-carbonization-acidleach-electrolysis production magnesium-rare earth, its technology smoothness, be easy to suitability for industrialized production; 3, adding concentration in the rhombspar carbonization system is oxalic acid or the solubility oxalate of 0.001mol/～0.01mol/L, solve calcium magnesium and be difficult to the thoroughly problem of separation, improved the purity of intermediates magnesium chloride hexahydrates, made the steady quality of the magnesium-rare earth product of final acquisition, quality better; 4, directly adopted the electrolysis of intermediates magnesium chloride hexahydrate, reduced production cost, thereby had application value, had a extensive future.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
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 obtains the magnesium basic carbonate filter cake.Filter cake is put into stirred autoclave, according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that to add concentration at 1: 10 be that 30% hydrochloric acid carries out stirring reaction, stir speed (S.S.) is 10r/min, treat to obtain magnesium chloride solution after solid dissolves fully, be 40.1% through heating evaporation, the massfraction that is concentrated into magnesium chloride, be cooled to 20 ℃ with the speed of 2 ℃/min then and separate out crystal, suction filtration separates, and obtains highly purified magnesium chloride hexahydrate crystal at 70 ℃ of dry 1.5h.Be to mix at 1: 0.10 the highly purified magnesium chloride hexahydrate of gained and seven water Lanthanum trichlorides according to weight ratio, as the electrolysis raw material, pack in the plumbago crucible, be that 1: 1 Repone K and sodium chloride mixture is ionogen with mass ratio, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, to be added drop-wise in the ionogen continuously through the electrolysis raw material after the heat fused, be 1000A at electric current, voltage is 5V, and temperature is to carry out dc electrolysis under 800 ℃ of conditions, obtains magnesium-rare earth at negative electrode, detect through EDS, the lanthanum content of magnesium-rare earth is about 5%.
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 obtains the magnesium basic carbonate filter cake.Filter cake is put into stirred autoclave, according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that to add concentration at 1: 15 be that 30% hydrochloric acid carries out stirring reaction, stir speed (S.S.) is 40r/min, treat to obtain magnesium chloride solution after solid dissolves fully, be 40.2% through heating evaporation, the massfraction that is concentrated into magnesium chloride, be cooled to 40 ℃ with the speed of 4 ℃/min then and separate out crystal, suction filtration separates, and obtains highly purified magnesium chloride hexahydrate crystal at 80 ℃ of dry 1h.Be to mix at 1: 12 the highly purified magnesium chloride hexahydrate of gained and three water Neodymium trichlorides according to weight ratio, as the electrolysis raw material, pack in the plumbago crucible, be that 1: 3 Repone K and sodium chloride mixture is ionogen with mass ratio, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, to be added drop-wise in the ionogen continuously through the electrolysis raw material after the heat fused, be 1500A at electric current, voltage is 15V, and temperature is to carry out dc electrolysis under 1100 ℃ of conditions, obtains magnesium-rare earth at negative electrode, detect through EDS, the neodymium content of magnesium-rare earth is more than 90%.
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; N=4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl; The o=stir speed (S.S.); P=is concentrated into the massfraction of magnesium chloride; The q=speed of cooling; The r=recrystallization temperature; The s=bake out temperature; The t=drying time; The kind of the moisture rare earth chloride of u=; The weight ratio of v=magnesium chloride hexahydrate and moisture rare earth chloride; The mass ratio of w=Repone K and sodium-chlor; The x=Faradaic current; The y=electrolysis voltage; The z=electrolysis temperature; 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 content of rare earth of the magnesium-rare earth for preparing of embodiment 3～embodiment 8.By the content of rare earth data of magnesium-rare earth listed in embodiment 1, embodiment 2 and the table 2 as can be seen, constant product quality of the present invention, content of rare earth is more than 5%～90%.
Table 2
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 |
| The content of rare earth of magnesium-rare earth | 55％ | Praseodymium 6% | Gadolinium 64% | 85％ | Scandium 8% | Yttrium 28% |
Claims (2)
1. a rhombspar is produced the processing method of magnesium-rare earth, it is characterized in that comprising following step:
(1) rhombspar fragmentation: rhombspar is carried out Mechanical Crushing to 1cm～10cm;
(2) dolomite calcination: the rhombspar of fragmentation is calcined 0.5～5h 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 system medium-height grass acid group 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 acidleach: the magnesium basic carbonate filter cake after will filtering is put into stirred autoclave, according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that 1: 10～15 to add concentration be that 30% hydrochloric acid carries out stirring reaction, and stir speed (S.S.) is 10r/min～40r/min, treats to obtain magnesium chloride solution after solid dissolves fully;
(9) magnesium chloride evaporative crystallization: be 40.0%～41.3% through heating evaporation, the massfraction that is concentrated into magnesium chloride with the gained magnesium chloride solution, control speed of cooling then and be 2 ℃/min～4 ℃/min, be cooled to 20 ℃～40 ℃ and separate out crystal, separate through suction filtration, obtain highly purified magnesium chloride hexahydrate crystal at 70 ℃～80 ℃ dry 1h～1.5h;
(10) mixed material feeding: being the electrolysis raw material with the highly purified magnesium chloride hexahydrate of evaporative crystallization gained and moisture rare earth chloride, is 1: 0.1～12 to mix according to weight ratio, in the plumbago crucible of packing into, feeds intake through being added drop-wise in the ionogen continuously after the heat fused;
(11) dc electrolysis: be that 1: 1～3 Repone K and sodium chloride mixture are ionogen with mass ratio, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, be 1000A～1600A at electric current, voltage is 5V～15V, temperature is to carry out dc electrolysis under 800 ℃～1100 ℃ conditions, obtains magnesium-rare earth at negative electrode.
2. a kind of rhombspar according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that oxalic acid used in the step (5) or solubility oxalate are one or more the mixture in oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738986A (en) * | 2013-12-20 | 2014-04-23 | 周骏宏 | Method for producing magnesium hydroxide and calcium carbonate in manners of burning dolomite and dissolving into water to separate calcium and magnesium |
| CN104894603A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院青海盐湖研究所 | Method for preparing magnesium-lead alloy through electrolysis |
| CN104911635A (en) * | 2015-05-05 | 2015-09-16 | 中国科学院过程工程研究所 | Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt |
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2013
- 2013-03-11 CN CN 201310097726 patent/CN103184477A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103738986A (en) * | 2013-12-20 | 2014-04-23 | 周骏宏 | Method for producing magnesium hydroxide and calcium carbonate in manners of burning dolomite and dissolving into water to separate calcium and magnesium |
| CN103738986B (en) * | 2013-12-20 | 2016-03-09 | 周骏宏 | A kind of dolomite calcination water-soluble separating calcium and magnesium produce the method for magnesium hydroxide and calcium carbonate |
| CN104894603A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院青海盐湖研究所 | Method for preparing magnesium-lead alloy through electrolysis |
| CN104911635A (en) * | 2015-05-05 | 2015-09-16 | 中国科学院过程工程研究所 | Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt |
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