CN103397213A - Method for decomposing and extracting Baotou rare earth ore through mixed alkali roasting process - Google Patents
Method for decomposing and extracting Baotou rare earth ore through mixed alkali roasting process Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 165
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000003513 alkali Substances 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 103
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 89
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 71
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 48
- 239000011575 calcium Substances 0.000 claims abstract description 33
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 33
- 238000000605 extraction Methods 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 rare earth chloride Chemical class 0.000 claims abstract description 26
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- GJEZFXDASHZTRO-UHFFFAOYSA-N iron thorium Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Th] GJEZFXDASHZTRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 74
- 239000011707 mineral Substances 0.000 claims description 74
- 239000002585 base Substances 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 17
- 239000006210 lotion Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 11
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical class [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 238000005065 mining Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 6
- 229910052776 Thorium Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 229910052590 monazite Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 59
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000011775 sodium fluoride Substances 0.000 description 6
- 235000013024 sodium fluoride Nutrition 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000011008 sodium phosphates Nutrition 0.000 description 3
- 239000008234 soft water Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 229910001576 calcium mineral Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 1
- IRCLFDYSUFDCCZ-UHFFFAOYSA-J [Th+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Th+4].[O-]P([O-])(=O)OP([O-])([O-])=O IRCLFDYSUFDCCZ-UHFFFAOYSA-J 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
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- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a clean production method for extracting rare earth from Baotou rare earth concentrate. The method comprises the following steps: chemically concentrating the Baotou rare earth concentrate, removing calcium and iron, and drying; mixing the obtained Baotou rare earth concentrate with a mixed alkali according to an ore/alkali ratio of 1:0.2-0.3, uniformly mixing, and roasting at 500-550DEG C for 1-2h, wherein the mixed alkali comprises sodium hydroxide and sodium carbonate according to a weight ratio of 2-3:1; washing with water for removing fluorine and phosphorus; optically leaching trivalent rare earth through using hydrochloric acid to prepare cerium-less rare earth chloride for an extraction section and cerium-rich ore; and dissolving the cerium-rich ore in industrial hydrochloric acid in the presence of a reducing agent for impurity removal to produce a cerium chloride solution, precipitating by ammonium bicarbonate, and calcing to prepare cerium oxide. The method for processing the Baotou rare earth ore has the advantages of good fluorine and phosphorus removal effects, solving and avoiding of the large amount of three wastes generated by a concentrated sulfuric acid process and a caustic soda process, solving of the comprehensive recovery of calcium, phosphorus and acid dissolution slag and iron thorium slag, and benefiting for the comprehensive utilization of resources.
Description
The method field
The invention belongs to rare-earth wet method metallurgy and chemical field, relate to the production technique that cleans of Baotou rare earth ore deposit Extraction of rare earth.
Background method
The most representative mineral of China rare earth resource-packet header baiyunebo concentrate, its rare-earth mineral is mainly by hamartite and two kinds of mineral compositions of monazite, and the mixed rare earth concentrates that the rare earth ore concentrate that forms through ore dressing mainly is comprised of hamartite and monazite is Baotou rare earth ore concentrate.Due to singularity, the complicacy of its mineral composition, its mineral decomposition, transition and the technical process such as separate and have suitable difficulty.There is no such mineral abroad, not similar extraction, isolation technique yet.
With fastest developing speed in Rare-earth Industry is rare earth permanent-magnetic material, what value was the highest in rare-earth products is also rare earth permanent-magnetic material, the value of praseodymium neodymium oxides accounts for more than 70%, because the praseodymium neodymium oxides is the main raw material of rare earth permanent-magnetic material of total rare earth (TRE) value in the light rare earths resource.It is the production of neodymium-iron-boron magnetic material that praseodymium neodymium oxides more than 80% is used for rare earth permanent-magnetic material.The extracting and separating of the praseodymium of Baotou rare earth ore deposit separation at present neodymium is all to adopt full extraction and separation technology basically, namely first extract grouping, produce Sm Eu Gd concentrate, then carry out La, Ce, Pr, Nd separate entirely, produce four kinds of pure-oxides or three kinds of pure-oxides, wherein the praseodymium neodymium oxides can be combined into a kind of product.In actual production, during extracting and separating is produced, La/Ce separates 40 grades of extraction tanks of use, and Ce/Pr separates 80 grades of extraction tanks of use.That is to say, the separation between La/Pr needs 120 grades just can complete altogether.Because industrial scale is increasing, equipment is also just more and more, takies factory building also large, takies a large amount of fixed capital, fill simultaneously the groove rare earth content also very large, overstock substantial contribution, the consumption of the P507 in production process is also large, and maximum in the straight product of producing be again to account for half cerium oxide of rare-earth products, production cost is too high, the cerium oxide selling price is always very low, and distribution state causes anxiety, and has a strong impact on enterprise's production economy benefit.
Baotou rare earth mining and metallurgy sweetening process is mainly take " sulphate method " as main at present, and " soda processes " is auxiliary.Namely " three generations's sulphate method " production cost is relatively low for " the high-temperature concentrated sulfuric acid roasting method " that generally adopts, and adaptability to raw material is strong, but exists " three wastes " amount large, easily surrounding environment is caused severe contamination, and exists difficulty of governance large, the defects such as expense height.Simultaneously, because the precious resources thorium in mineral generates the thorium pyrophosphate that is difficult to recycling after concentrated sulfuric acid roasting, be scattered in waste residue, be difficult to reclaim and process, cause these precious resources to be wasted.On the other hand, " soda processes " production technique but is subjected to grade and the base composition of rare-earth mineral, and the production process energy consumption is too high in addition, uses the enterprise of alkaline process decomposition and other smelting technology less., although there are many great scientific payoffss in the Baotou rare earth ore deposit aspect hydrometallurgy, conclusive effect is played in the development of Chinese rare-earth industry, still be in so far world lead level.But, fast development and production-scale continuous expansion along with rare-earth industry, improvement to rare-earth smelting technique, comprise that the aspects such as environmental protection, consumption reduction, utilize resources synthetically still exist many technology and technological problems, especially the innovation of Rare Earth Production extraction process and perfect, it is extremely urgent also having many work and research of technique.
Trend: the research and development rare-earth mineral is smelted to separate and is cleaned production technique, solves " three wastes " pollution problem, reduces unit consumption, improves resource utilization; In rare earth mineral products Resource Development Process to the comprehensive utilization of symbiosis, associated mineral and valuable element; Waste gas, waste water, the waste residue that produces in the rare-earth mineral treating processes recycled; The comprehensive recovery and rationally utilization; Strengthen the research work of the secondary development of rare earth mineral resources comprehensive utilization and resource, solve the resource exhaustion problem.
Summary of the invention
The object of the invention is to provide a kind of Baotou rare earth mining and metallurgy refining separation is cleaned production technique, and namely mixed base roasting method in Baotou rare earth ore deposit is decomposed the Extraction of rare earth method, reduces the three wastes, reduces production costs.
Baotou rare earth ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, comprises the following steps:
(1) chemical mineral processing and concentrate drying
The Baotou rare earth ore deposit is through chemical mineral processing, and filter-press dehydration is dried after isolating acid bubble filtrate again, must hang down the calcium rare-earth mineral; The solid-to-liquid ratio of described chemical mineral processing is 1:5～8, and ore deposit acid weight ratio is 1:0.5～1.0, and hydrochloric acid is added to PH and is stabilized in 0.1～0.5,25～85 ℃ of temperature of reaction, and the reaction times is 2～4 hours; The temperature of oven dry is 100～550 ℃, drying time 1.0～1.5 hours;
(2) mixed base roasting:
Low calcium rare-earth mineral and the mixed base of gained in step (1) are mixed rear roasting, obtain the ripe ore deposit of alkali roasting;
Mixed base is the powdered mixture of sodium hydroxide and sodium carbonate; With the low calcium rare-earth mineral of gained in step (1) and mixed base by ore deposit: alkali=1:0.2～0.3(weight ratio) mix,, 500～550 ℃ of roastings 1～2 hour, obtain the ripe ore deposit of alkali roasting;
(3) washing
The ripe ore deposit of alkali roasting of step (2) gained, through being washed to PH7～PH8, dehydration, is obtained rare earth oxide ore deposit and water lotion;
(4) hydrochloric acid is excellent soaks
Sized mixing by solid-to-liquid ratio 1:2～3 in the rare earth oxide ore deposit that step (3) obtains, be REO by ore deposit acid weight ratio: hydrochloric acid=1:1.0～1.5 slowly add technical hydrochloric acid, 50～80 ℃ of excellent soaking 4 hours, when being stabilized in 1.0～2.0, PH stops excellent soaking, La in trivalent rare earth, Pr, Nd and Sm, Eu, Gd are preferentially leached, quadrivalent cerium is insoluble to dilute hydrochloric acid, and after the excellent immersion liquid removal of impurity, press filtration separates to obtain few cerium mischmetal solution and rich cerium ore deposit;
(5) preparation of cerium oxide
The mining technical hydrochloric acid of rich cerium that step (4) is obtained is REO by ore deposit acid weight ratio: hydrochloric acid=1:2.0～2.5, add simultaneously reductive agent to dissolve, under 65～95 ℃, reacted 2 hours, cerium is reduced to trivalent by tetravalence and is dissolved in hydrochloric acid, when the salt acidacidity was stabilized in 0.1～0.2M, acid was dissolved complete, filtered to obtain acid solution and sour molten slag; The acid molten slag returns to step (2) with recovering rare earth; Acid solution through removal of impurities, filter to such an extent that iron thorium slag removes to reclaim the thorium product; The filtrate that removal of impurities is filtered is solution of cerium chloride by oxidation, and solution of cerium chloride by oxidation is through ammonium bicarbonate precipitation, and calcination makes cerium oxide product; Or the direct condensing crystal of solution of cerium chloride by oxidation is made the Cerium II Chloride product.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, described Baotou rare earth ore deposit refers to the rare-earth mineral product that the packet header baiyunebo concentrate forms through ore dressing, its rare-earth mineral mainly is comprised of hamartite and monazite, and its content of rare earth REO is 40～60%.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, the concentrated calcium chloride of producing after the isolated acid bubble of the Baotou rare earth mineralising beneficiation steps in described step (1) filtrate removal impurity.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, and the mixed base in described step (2) is sodium hydroxide by weight by sodium hydroxide and sodium carbonate: sodium carbonate=2～3:1 forms;
PressLow calcium rare-earth mineral:
Mixed base=1:0.2～0.3(weight ratio) will hang down the calcium rare-earth mineral with
Mixed baseBe mixed evenly.
Above-mentioned Baotou rare earth ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, described will hang down the calcium rare-earth mineral with
Mixed baseBe mixed evenly and refer to after low calcium rare-earth mineral, sodium hydroxide, sodium carbonate is mixed in proportion pulverize in the lump; Or after solid sodium hydroxide and powdery sodium carbonate are pulverized and mixed, then and the low calcium rare-earth mineral of step (1) mix.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, and the water lotion that the middle ripe mineral water of alkali roasting of described step (3) is washed gained removes the concentrated sodium salt of producing of negative pressure, makes phosphorus, fluorine be reclaimed comprehensive utilization.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, and in described step (4), few cerium mischmetal solution condensing crystal must lack cerium rare earth chloride product or by extraction, produce praseodymium neodymium oxides and Sm Eu Gd concentrate; Rich cerium ore deposit is removed to produce cerium oxide or is dried to obtain rich cerium mineral products.
OnThe Baotou rare earth ore deposit mixed base roasting method of stating is decomposed the Extraction of rare earth method, and in described step (5), acid is dissolved to finish and filters to obtain acid solution and sour molten slag; Acid solution through removal of impurities, filter to obtain iron thorium slag; Make sour molten slag be separated with iron thorium slag, and comprehensive the recovery.
Advantage of the present invention
(1) adopt chemical mineral processing to anticipate Baotou rare earth ore concentrate, namely with diluted acid, destroy calcium mineral, calcium is leached and separates from rare-earth mineral, calcium, iron in ore deposit had both been removed, recyclable calcium again, avoid calcium, iron to produce harm to the separation and Extraction of follow-up rare-earth products, reduced the consumption of chemical industry supplementary material.
(2) process through the inventive method in the Baotou rare earth ore deposit, and defluorination, phosphorus are effective, through practice, confirms, can reach the rate of removing more than 97%; And the rare-earth mineral decomposition fully, through practice, confirms, rate of decomposition can reach more than 97%; In roasting process the cerium oxidation is good, and oxidation ratio confirms to reach more than 95% through practice; 500～550 ℃ of maturing temperatures, 1～2 hour time, equipment is simple and easy to realization, and energy consumption is low, and the production operability is good; Product of roasting is loose, and during washing, the material settling property is good, and filter dehydration is functional, and trivalent rare earth stripping that hydrochloric acid is excellent while soaking is good, and the industrial production operational condition is good.
(3) adopt processing method of the present invention to process the packet header rare-earth mineral, embodied light rare earths to produce the praseodymium neodymium oxides as main purpose.CeO in few cerium rare earth chloride
2/ REO=0～20% can be controlled arbitrarily, and the praseodymium neodymium is processed and is able to nearly one times of enrichment, Pr in rare-earth mineral through this processing method
6O
11+ Nd
2O
3/ REO22% left and right, Pr in the few cerium rare earth chloride that makes
6O
11+ Nd
2O
3/ REO can reach 40%～44%, and the content of sm-eu-gd is able to approximately one times of enrichment than also, greatly is conducive to the production of praseodymium neodymium oxides and sm-eu-gd, has avoided simultaneously the cerium of low value to take the work efficiency that extracts workshop section.Therefore the present invention can reduce in a large number facility investment and reduce production costs, and is real in hanging down facility investment, low cost movement, rare-earth mineral, short flow process, the splendid new process in processing packet header of high economic benefit.
(4) this invention also provides a kind of and has produced rich cerium mineral products with the Baotou rare earth ore deposit, or the novel process of cerium oxide.Rich cerium ore deposit can be used for the raw material of glass, pottery, rare earth ferrosilicon production, cerium purity 90～97%; Cerium oxide product, cerium purity are more than 95～98.5%, and its technical process is brief, and production cost is cheaper than extraction process, are the new breakthroughs that Baotou rare earth ore deposit chemical method is carried cerium.
(5) this invention " three wastes " amount of having solved and avoided " sulphate method ", " soda processes " to produce is large, solved the comprehensive recovery of fluorine, calcium, phosphorus, sour molten slag and iron thorium slag, be conducive to the comprehensive utilization of resource, realized simultaneously cleaning of Industrial processes, be the novel process that replaces " sulphate method ", " soda processes ", will bring great technical renovation and promotion in Baotou rare earth ore wet process metallurgical production.
(6) adopt the method for the invention, the rare earth total recovery can reach more than 90～95%.
Description of drawings
Fig. 1, Baotou rare earth ore deposit mixed base roasting method is decomposed the Extraction of rare earth method flow diagram.
Embodiment
Baotou rare earth of the present invention ore deposit, REO content are 40～60%, and its rare-earth mineral mainly forms with hamartite and monazite.Hydrochloric acid, sodium hydroxide and sodium carbonate are technical grade.The hydrochloric acid that adopts in following examples is the technical grade salable product, HCL 〉=31.0%; Sodium hydroxide is industrial solid sodium hydroxide seconds, NaOH 〉=95.0%; Sodium carbonate is technical grade III class salable product Na
2CO
3〉=98.0%.
Embodiment 1
4 tons, the Baotou rare earth ore deposit of adopting, major ingredient is: REO 41.50%; F 6.11%; P 4.05%; Fe 15.44%; CaO 7.98%.
(1) chemical mineral processing and concentrate drying
The Baotou rare earth ore deposit is through chemical mineral processing, and filter-press dehydration, dry to obtain low calcium rare-earth mineral.Filtrate is removed the assorted rear concentrated calcium chloride of producing.
Processing condition: solid-to-liquid ratio 1:4, ore deposit: hydrochloric acid is 1:1.0.4 tons, ore deposit, add water 12M
3, 4 tons of hydrochloric acid are added to PH and are stabilized in 0.1,25 ℃ of temperature of reaction, time 2 h. and bake out temperature: 500 ℃, 1.0 hours, do 3 tons, ore deposit, calcium chloride is 600kg approximately.
(2) mixed base roasting:
Mixed base is to be by weight by solid sodium hydroxide and powdery sodium carbonate: sodium hydroxide: sodium carbonate=2:1 forms through being pulverized and mixed.Low calcium rare-earth mineral and the mixed base of gained in step (1) are mixed roasting, obtain the ripe ore deposit of alkali roasting, ripe ore deposit middle-weight rare earths exists with oxide form, and cerium is oxidized to tetravalence, and fluorine generates Sodium Fluoride, and phosphorus generates sodium phosphate.
Processing condition: ore deposit: alkali=1:0.2(weight ratio), mixed base 600kg, sodium hydroxide 400kg wherein, sodium carbonate 200kg, maturing temperature: 500 ℃, 1.0 hours time.
(3) washing and waste water reclamation are processed
Through washing, the rare earth oxide ore deposit of dewatering to obtain, in approximately 1.62 tons of REO with the ripe ore deposit of alkali roasting of step (2) gained.
Processing condition: washing solid-to-liquid ratio=1:6, washing time 1 hour, 25 ℃ of temperature, washing terminal PH7.0.Water lotion goes the negative pressure condensing crystal to obtain sodium salt, with Na
2The O meter is 370kg approximately.Sodium salt contains sodium hydroxide, sodium carbonate, sodium phosphate, Sodium Fluoride, can be used for scale remover or other industrial raw material of industrial soft water processing and Industrial Boiler, thereby make phosphorus, fluorine in rare-earth mineral be reclaimed comprehensive utilization.
(4) hydrochloric acid is excellent soaks
The rare earth oxide ore deposit Jia Shui that step (3) is obtained sizes mixing, slowly add technical hydrochloric acid, quadrivalent cerium is owing to being insoluble to dilute hydrochloric acid, and the La in trivalent rare earth, Pr, Nd and Sm, Eu, Gd are preferentially leached, after the impurity such as deironing, press filtration separates to obtain few cerium mischmetal solution and rich cerium ore deposit.Few cerium mischmetal solution condensing crystal must lack cerium rare earth chloride product for extraction workshop section, and rich cerium ore deposit is removed to produce cerium oxide or dried to obtain rich cerium mineral products.
Processing condition: the excellent solid-to-liquid ratio 1:2 that soaks, ore deposit acid weight ratio is REO: hydrochloric acid=1:1.2, adds water 3M
3, 2 tons of hydrochloric acid, the excellent temperature of soaking: 50 ℃, the time: 4 hours, the excellent terminal PH1.0 that soaks, excellent immersion liquid removal of impurities terminal PH4.0～4.5.
Few cerium rare earth chloride: REO 45.32%, CeO
2/ REO 4.12%, Pr
6O
11+ Nd
2O
3/ REO 42.18%, and CaO+MgO 1.35%, Fe
2O
30.005%, SO
4 2-0.02%, 1.71 ton.Rich cerium ore deposit: CeO
2/ REO 95.21%, in 0.8 ton of REO.
(5) preparation of cerium oxide
The mining technical hydrochloric acid of rich cerium that step (4) is obtained dissolves, and with thiocarbamide, makes the cerium reductive agent, and cerium is reduced to trivalent by tetravalence and is dissolved in hydrochloric acid, and acid is dissolved to finish filters to obtain acid solution and sour molten slag.The acid molten slag returns to step (2) with recovering rare earth.Acid solution through removal of impurities, filter to such an extent that iron thorium slag removes to reclaim the thorium product.Filtrate is solution of cerium chloride by oxidation, and through ammonium bicarbonate precipitation, calcination makes cerium oxide product.
Acid molten processing condition: solid-to-liquid ratio 1:2, ore deposit acid weight ratio is REO: hydrochloric acid=1:2.5; The thiocarbamide consumption is CeO
20.05 times, add water 3 M
3, 2 tons of hydrochloric acid, thiocarbamide 40kg, 85～90 ℃ of temperature of reaction, time 2 h, reaction end: salt acidacidity 0.15M.Cerium oxide: REO 99.12%, CeO
2/ REO 98.54%, Fe
2O
30.02%, 0.773 ton.The Baotou rare earth ore deposit is through above art breading, rare earth total recovery η
REO93.25%.
Embodiment 2
4 tons, the Baotou rare earth ore deposit of adopting, major ingredient is: REO 50.18%; F 7.65%; P 4.58%;
Fe?6.10%?；CaO?10.68%。
(1) chemical mineral processing and ore deposit are dry
The Baotou rare earth ore deposit is through chemical mineral processing, and filter-press dehydration, dry to obtain low calcium rare-earth mineral, and filtrate is removed the assorted rear concentrated calcium chloride of producing.
Processing condition:
Solid-to-liquid ratio 1:5, ore deposit: hydrochloric acid (weight ratio) is 1:0.8,4 tons, ore deposit adds water 17 M
3, 3.2 tons of hydrochloric acid add rear PH to be stabilized in 0.1,60 ℃ of temperature of reaction, time 2 h.Bake out temperature: 520 ℃, 1.25 hours time.Dry to such an extent that low calcium rare-earth mineral is done approximately 3 tons, ore deposit, filtrate is removed the assorted rear concentrated approximately 800kg of calcium chloride that produces.
(2) mixed base roasting:
Mixed base by flaky sodium hydrate and powdery sodium carbonate is by weight: sodium hydroxide: sodium carbonate=2.5:1 forms.
The low calcium rare-earth mineral of gained in step (1) and mixed base are pulverized in the lump and mixed roasting, obtain the ripe ore deposit of alkali roasting.Ripe ore deposit middle-weight rare earths exists with oxide form, and cerium is oxidized to tetravalence, and fluorine generates Sodium Fluoride, and phosphorus generates sodium phosphate.
Processing condition: ore deposit: alkali=1:0.25(weight ratio), mixed base 750kg, sodium hydroxide 535kg wherein, sodium carbonate 215kg, maturing temperature: 520 ℃, 1.5 hours time.
(3) washing and waste water reclamation are processed
Through washing, the rare earth oxide ore deposit of dewatering to obtain, in 1.96 tons of REO with the ripe ore deposit of alkali roasting of step (2) gained.
Processing condition: washing solid-to-liquid ratio=1:8, washing time 1 hour, temperature 60 C, washing terminal PH7.0.Water lotion goes the negative pressure condensing crystal to obtain sodium salt, with Na
2The O meter is 430kg approximately, and sodium salt contains sodium hydroxide, sodium carbonate, sodium phosphate, Sodium Fluoride, can be used for scale remover or other industrial raw material of industrial soft water processing and Industrial Boiler, thereby make phosphorus, fluorine in rare-earth mineral be reclaimed comprehensive utilization.
(4) hydrochloric acid is excellent soaks
The rare earth oxide ore deposit Jia Shui that step (3) is obtained sizes mixing, slowly add technical hydrochloric acid, quadrivalent cerium is owing to being insoluble to dilute hydrochloric acid, and the La in trivalent rare earth, Pr, Nd and Sm, Eu, Gd are preferentially leached, must lack cerium mischmetal solution after the impurity such as deironing, throw out is through the rich cerium ore deposit of dewatering to obtain.Few cerium mischmetal solution condensing crystal must lack cerium rare earth chloride product for extraction workshop section, and rich cerium ore deposit is removed to produce cerium oxide or dried to obtain rich cerium mineral products.
Processing condition: the excellent solid-to-liquid ratio 1:3 that soaks, ore deposit acid weight ratio is REO: hydrochloric acid=1:1.4, adds water 5.2M
3, 2.8 tons of hydrochloric acid, the excellent temperature of soaking: 60 ℃, the time: 4 hours, the excellent terminal PH1.0 that soaks, excellent immersion liquid removal of impurities terminal PH4.0～4.5.
Few cerium rare earth chloride: REO 45.38%, CeO
2/ REO 4.34%, Pr
6O
11+ Nd
2O
3/ REO 42.35%, and CaO+MgO 1.13%, Fe
2O
30.005%, SO
4 2-0.02%, 2.1 ton.
Rich cerium ore deposit: CeO
2/ REO 96.45%.
(5) preparation of cerium oxide
The mining technical hydrochloric acid of rich cerium that step (4) is obtained dissolves, and with thiocarbamide, makes the cerium reductive agent, and cerium is reduced to trivalent by tetravalence and is dissolved in hydrochloric acid, and acid is dissolved to finish filters to obtain acid solution and sour molten slag.The acid molten slag returns to step (2) with recovering rare earth.
Acid solution through removal of impurities, filter to such an extent that iron thorium slag removes to reclaim the thorium product.Filtrate is solution of cerium chloride by oxidation, and through ammonium bicarbonate precipitation, calcination makes cerium oxide product.
The molten processing condition of acid: ore deposit acid weight ratio is REO: hydrochloric acid=1:2.3; The thiocarbamide consumption is CeO
20.05 times, solid-to-liquid ratio 1:2.Add water 2.7M
3, 2.3 tons of hydrochloric acid, thiocarbamide 50kg, 85～90 ℃ of temperature of reaction, time 2 h, reaction end: salt acidacidity 0.15M.
Cerium oxide: REO 99.05%, CeO
2/ REO 98.32%, Fe
2O
30.02%, 0.952 ton.
The Baotou rare earth ore deposit is through above art breading, rare earth total recovery η
REO94.95%.
Embodiment 3
Adopt 4 tons, Baotou rare earth ore deposit, major ingredient is: REO 60.12%; F 6.85%; P 4.31%; Fe 6.52%; CaO4.86%.
(1) chemical mineral processing and ore deposit are dry
The Baotou rare earth ore deposit is through chemical mineral processing, and filter-press dehydration, dry to obtain low calcium rare-earth mineral, and filtrate is removed the assorted rear concentrated calcium chloride of producing.
Processing condition: solid-to-liquid ratio 1:4; Hydrochloric acid weight ratio 1:0.5; 4 tons, ore deposit, add water 14M
3, 2 tons of hydrochloric acid are added to PH and are stabilized in 0.1,85 ℃ of temperature of reaction, time 2 h.Bake out temperature: 550 ℃, drying time 1.5 hours, do approximately 3 tons, ore deposit, and calcium chloride is 360kg approximately.
(2) mixed base roasting:
Mixed base connects weight ratio by sodium hydroxide and sodium carbonate: sodium hydroxide: sodium carbonate=3:1 forms.
Low calcium rare-earth mineral and the mixed base of gained in step (1) are mixed through pulverizing, and roasting obtains the ripe ore deposit of alkali roasting, and ripe ore deposit middle-weight rare earths exists with oxide form, and cerium is oxidized to tetravalence, and fluorine generates Sodium Fluoride, and phosphorus generates sodium phosphate.
Processing condition: ore deposit: alkali=1:0.3(weight ratio), mixed base 900kg, sodium hydroxide 675kg wherein, sodium carbonate 225kg.Maturing temperature: 550 ℃, time 2 h.
(3) washing and waste water reclamation are processed
Through washing, the rare earth oxide ore deposit of dewatering to obtain, in 2.35 tons of REO with the ripe ore deposit of alkali roasting of step (2) gained.
Processing condition: washing solid-to-liquid ratio=1:6, washing time 1 hour, 85 ℃ of temperature, washing terminal PH7.0, water lotion goes the negative pressure condensing crystal to obtain sodium salt, and sodium salt contains sodium hydroxide, sodium carbonate, sodium phosphate, Sodium Fluoride, can be used for scale remover or other industrial raw material of industrial soft water processing and Industrial Boiler, thereby, make phosphorus, fluorine in rare-earth mineral be reclaimed comprehensive utilization.
(4) the excellent of hydrochloric acid soaks
The rare earth oxide ore deposit Jia Shui that step (3) is obtained sizes mixing, slowly add technical hydrochloric acid, quadrivalent cerium is owing to being insoluble to dilute hydrochloric acid, La in trivalent rare earth, Pr, Nd and Sm, Eu, Gd are preferentially leached, after the impurity such as deironing, press filtration separates to obtain few cerium mischmetal solution and rich cerium ore deposit, and few cerium mischmetal solution condensing crystal must lack cerium rare earth chloride product for extraction workshop section, and rich cerium ore deposit is removed to produce cerium oxide or dried to obtain rich cerium mineral products.
Processing condition: the excellent solid-to-liquid ratio of soaking: 1:3; Ore deposit acid weight ratio is REO: hydrochloric acid=1:1.5; Add water 5.4M
3, 3.6 tons of hydrochloric acid, the excellent temperature of soaking: 80 ℃, the time: 4 hours, the excellent terminal PH1.0 that soaks, excellent immersion liquid removal of impurities terminal PH4.0～4.5.
Few cerium rare earth chloride: REO:45.36%, CeO
2/ REO:4.15%, Pr
6O
11+ Nd
2O
3/ REO:42.43%, CaO+MgO:1.07%, Fe
2O
3:0.005%, SO
4 2-0.02%, 2.56 ton.
Rich cerium ore deposit: CeO
2/ REO:96.72%, in 1.16 tons of REO.
(5) preparation of cerium oxide
The mining technical hydrochloric acid of rich cerium that step (4) is obtained dissolves, and with thiocarbamide, makes the cerium reductive agent, and cerium is reduced to trivalent by tetravalence and is dissolved in hydrochloric acid, and acid is dissolved to finish filters to obtain acid solution and sour molten slag.The acid molten slag returns to step (2) with recovering rare earth.Acid solution through removal of impurities, filter to such an extent that iron thorium slag removes to reclaim the thorium product.Filtrate is solution of cerium chloride by oxidation, and through ammonium bicarbonate precipitation, calcination makes cerium oxide product.
The molten processing condition of acid: ore deposit acid weight ratio is REO: hydrochloric acid=1:2.0; The thiocarbamide consumption is CeO
20.05 times, solid-to-liquid ratio 1:2.Add water 2.6M
3, 2.4 tons of hydrochloric acid, thiocarbamide 60kg, 85～90 ℃ of temperature of reaction, time 2 h, reaction end: salt acidacidity 0.15M.
Cerium oxide: REO99.12%, CeO
2/ REO98.53%, Fe
2O
30.02%, 1.13 ton.
The Baotou rare earth ore deposit is through above art breading, rare earth total recovery η
REO95.02%.
In above-described embodiment, mixed base is to form by sodium hydroxide and sodium carbonate are mixed, for being mixed evenly, can and step (1) low calcium rare-earth mineral be pulverized and mixed in the lump; After also solid sodium hydroxide and powdery sodium carbonate can being pulverized and mixed, then and the low calcium rare-earth mineral of step (1) be mixed evenly.
In above-described embodiment, washing is a kind of continuous process, but the water lotion that produces when in step (3), the ripe mineral water of alkali roasting is washed, be regarded as the higher water lotion of concentration to the water lotion that obtains in the ripe ore deposit the 1st of alkali roasting, 2 washings, and remaining water lotion is the lower water lotion of concentration; The water lotion that concentration is higher obtains sodium salt by the negative pressure condensing crystal; The water lotion that concentration is lower returns and again is used for washing.
In above-described embodiment, solid-to-liquid ratio refers to the ratio of solid solute weight and liquid solvent volume.
Size mixing and refer to solid solute and certain quantity of fluid solvent are mixed with the stirring way, its objective is the convenience that adds solvent for next step, be conducive to solute and dissolve (commonly used while particularly preferentially leaching).
Described chemical mineral processing, namely destroy calcium mineral with diluted acid, and calcium is leached and separates from rare earth ore concentrate.
Above-described embodiment is that foregoing of the present invention is further described, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to above-described embodiment.All technology that realizes based on foregoing all belong to scope of the present invention.
Claims (8)
1. mixed base roasting method in Baotou rare earth ore deposit is decomposed the Extraction of rare earth method, and it is characterized in that: the method is carried out as follows:
(1) chemical mineral processing and drying
The Baotou rare earth ore deposit is through chemical mineral processing, and filter-press dehydration is dried after isolating acid bubble filtrate again, must hang down the calcium rare-earth mineral; The solid-to-liquid ratio of described chemical mineral processing is 1:5～8, and ore deposit acid weight ratio is 1:0.5～1.0, and hydrochloric acid is added to PH and is stabilized in 0.1～0.5,25～85 ℃ of temperature of reaction, and the reaction times is 2～4 hours; The temperature of described oven dry is 100～550 ℃, drying time 1.0～1.5 hours;
(2) mixed base roasting:
Low calcium rare-earth mineral and the mixed base of gained in step (1) are mixed rear roasting, obtain the ripe ore deposit of alkali roasting; Described mixed base is the powdered mixture of sodium hydroxide and sodium carbonate; It is rear 500～550 ℃ of roastings 1～2 hour that described roasting refers to that low calcium rare-earth mineral and mixed base mix;
(3) washing
The ripe ore deposit of alkali roasting of step (2) gained, through being washed to PH7～PH8, dehydration, is obtained rare earth oxide ore deposit and water lotion;
(4) hydrochloric acid is excellent soaks
Sized mixing by solid-to-liquid ratio 1:2～3 in the rare earth oxide ore deposit that step (3) obtains, be REO by ore deposit acid weight ratio: hydrochloric acid=1:1.0～1.5 slowly add technical hydrochloric acid, 50～80 ℃ of excellent soaking 4 hours, when being stabilized in 1.0～2.0, PH stops excellent soaking, La in trivalent rare earth, Pr, Nd and Sm, Eu, Gd are preferentially leached, quadrivalent cerium is insoluble to dilute hydrochloric acid, and after the excellent immersion liquid removal of impurity, press filtration separates to obtain few cerium mischmetal solution and rich cerium ore deposit;
(5) preparation of cerium oxide
The mining technical hydrochloric acid of rich cerium that step (4) is obtained is REO by ore deposit acid weight ratio: hydrochloric acid=1:2.0～2.5, add simultaneously reductive agent to dissolve, under 65～95 ℃, reacted 2 hours, cerium is reduced to trivalent by tetravalence and is dissolved in hydrochloric acid, when the salt acidacidity was stabilized in 0.1～0.2M, acid was dissolved complete, filtered to obtain acid solution and sour molten slag; The acid molten slag returns to step (2) with recovering rare earth; Acid solution through removal of impurities, filter to such an extent that iron thorium slag removes to reclaim the thorium product; The filtrate that removal of impurities is filtered is solution of cerium chloride by oxidation, and solution of cerium chloride by oxidation is through ammonium bicarbonate precipitation, and calcination makes cerium oxide product; Or the direct condensing crystal of solution of cerium chloride by oxidation is made the Cerium II Chloride product.
2. Baotou rare earth described according to claims 1 ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, it is characterized in that: described Baotou rare earth ore deposit refers to the rare-earth mineral product that the packet header baiyunebo concentrate forms through ore dressing, its rare-earth mineral mainly is comprised of hamartite and monazite, and its content of rare earth REO is 40～60%.
3. Baotou rare earth ore deposit mixed base roasting method decomposition Extraction of rare earth method described according to claims 1, is characterized in that: concentrate production calcium chloride after the isolated acid bubble of the Baotou rare earth mineralising beneficiation steps in described step (1) filtrate is removed impurity.
4. Baotou rare earth described according to claims 1 ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, it is characterized in that: the mixed base in described step (2) by sodium hydroxide and sodium carbonate by weight being sodium hydroxide: sodium carbonate=2～3:1 forms;
PressLow calcium rare-earth mineral:
Mixed base=1:0.2～0.3(weight ratio) will hang down the calcium rare-earth mineral with
Mixed baseBe mixed evenly.
5. Baotou rare earth described according to claims 4 ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, it is characterized in that: described will hang down the calcium rare-earth mineral with
Mixed baseBe mixed evenly and refer to after low calcium rare-earth mineral, sodium hydroxide, sodium carbonate is mixed in proportion pulverize in the lump; Or after solid sodium hydroxide and powdery sodium carbonate are pulverized and mixed, then and the low calcium rare-earth mineral of step (1) mix.
6. Baotou rare earth described according to claims 1 ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, it is characterized in that: the water lotion that the middle ripe mineral water of alkali roasting of described step (3) is washed gained adopts the concentrated mode of negative pressure to produce sodium salt, makes phosphorus, fluorine be reclaimed comprehensive utilization.
7. Baotou rare earth ore deposit mixed base roasting method decomposition Extraction of rare earth method described according to claims 1, is characterized in that: lack cerium mischmetal solution condensing crystal in described step (4) and must lack cerium rare earth chloride product or by extraction, produce praseodymium neodymium oxides and Sm Eu Gd concentrate; Rich cerium ore deposit is removed to produce cerium oxide or is dried to obtain rich cerium mineral products.
8. Baotou rare earth described according to claims 1 ore deposit mixed base roasting method is decomposed the Extraction of rare earth method, it is characterized in that: in described step (5), acid is dissolved to finish and filters to obtain acid solution and sour molten slag; Acid solution through removal of impurities, filter to obtain iron thorium slag; Make sour molten slag be separated with iron thorium slag, and comprehensive the recovery.
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