CN1034743C - Making rare-earth material liquid from bastnae site - Google Patents
Making rare-earth material liquid from bastnae site Download PDFInfo
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- CN1034743C CN1034743C CN93114910A CN93114910A CN1034743C CN 1034743 C CN1034743 C CN 1034743C CN 93114910 A CN93114910 A CN 93114910A CN 93114910 A CN93114910 A CN 93114910A CN 1034743 C CN1034743 C CN 1034743C
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- acidleach
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- rare earth
- leach liquor
- bastnasite
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 82
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 title claims description 89
- 239000000463 material Substances 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 80
- 239000003513 alkali Substances 0.000 claims abstract description 62
- 239000002893 slag Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 48
- 229910017604 nitric acid Inorganic materials 0.000 claims description 48
- 238000004140 cleaning Methods 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 45
- 229910052684 Cerium Inorganic materials 0.000 claims description 41
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000005554 pickling Methods 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 29
- 239000007790 solid phase Substances 0.000 claims description 29
- 230000002829 reductive effect Effects 0.000 claims description 27
- 238000003672 processing method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000013019 agitation Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 38
- 239000012141 concentrate Substances 0.000 description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 25
- 239000011737 fluorine Substances 0.000 description 25
- 229910052731 fluorine Inorganic materials 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 238000000354 decomposition reaction Methods 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 235000011121 sodium hydroxide Nutrition 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 16
- 239000011575 calcium Substances 0.000 description 16
- 229910052791 calcium Inorganic materials 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 16
- 229910052749 magnesium Inorganic materials 0.000 description 16
- 229910052788 barium Inorganic materials 0.000 description 15
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 15
- 239000006210 lotion Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000011343 solid material Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 235000021110 pickles Nutrition 0.000 description 8
- -1 sulfuric acid rare earth Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241001504664 Crossocheilus latius Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910002637 Pr6O11 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000906946 Sphingomonas carri Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- YTSDVWYUJXKXCC-UHFFFAOYSA-L zinc;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Zn+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O YTSDVWYUJXKXCC-UHFFFAOYSA-L 0.000 description 1
Classifications
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a method for preparing raw material solution of rare earth from bastnaesite, which comprises: rare earth ore and sodium carbonate or sodium hydroxide are mixed according to a proper proportion, calcined, washed by water and washed by acid. Leach solution of the primary acid leaching, leach solution of the secondary acid leaching and primary slag are obtained from the primary acid leaching and the secondary acid leaching. The leach solution of the secondary acid leaching is used as extracting solution of the primary acid leaching, and after the primary slag is washed by alkali and water, the primary acid leaching and secondary acid leaching are respectively carried out. The technical method of the present invention has the advantages of strong adaptability, no environmental pollution, high ore opening rate, high recovery rate of rare earth, small slag quantity, low acid degree of raw material solution of rare earth and high rare earth concentration.
Description
The present invention relates to wet method from rare earth ore concentrate, more specifically say so from f_c_ce_la concentrate, produce the processing method of rare earth mineral acid stock liquid by the roasting leaching.
In existing technology, decompose the method that bastnasite is produced rare earth raw material liquid, sulfuric acid process is arranged.Processing methodes such as water flowing vapor-phase oxidation roasting method, sodium carbonate roasting method.
The sulfuric acid roasting method of Chinese patent literature CN86105043.6 report decomposes the processing method of producing the sulfuric acid rare earth stock liquid, be to be raw material with the Baotou rare earth ore deposit of containing more phosphorus, add sulfuric acid and carry out roasting, through the Baotou rare earth ore deposit behind the sulfuric acid baking, adding entry leaches, and add magnesium oxide and remove impurity element, and obtain the vitriolic rare earth raw material liquid.This processing method is easy, is the good flow process of decomposing the Baotou rare earth ore deposit of containing more phosphorus.But, fluorine is enriched in contaminate environment in the tail gas in this technical process, the health of harmful human body, and the concentration of resulting sulfuric acid rare earth stock liquid middle-weight rare earths is lower, the mixed rare-earth oxide that only contains tens grams in this stock liquid of every liter, need obtain denseer rare earth raw material liquid will make the transition with the organic extraction method.
The molybdenum company of the U.S. carries out the decomposition of hamartite with the oxidizing roasting method that feeds water vapor, this technology is raw material with the hamartite that contains 60% rare earth oxide, hydrochloric acid with 10% carries out pickling to it, is dissolved in the impurity element of hydrochloric acid in the flush away ore, forms the pickling concentrate.Under the condition that feeds water vapor, in 800 ℃ the hamartite after overpickling is carried out oxidizing roasting, in the process that feeds steam roasting, remove fluorine (with hydrofluoric form), through the concentrate after the oxidizing roasting, leach with hydrochloric acid, after the solid-liquid separation, and obtain the rare earth chloride stock liquid of liquid phase, though can obtain containing the higher rare earth raw material liquid of rare-earth oxidation substrate concentration with this technical process, but, with hydrofluoric form defluorination, be furnished with the hydrofluoric equipment of recovery and favorable protection measure, well-known, hydrogen fluoride has huge poison, do not reclaim it, do not have the favorable protection measure that health of operators is had very big influence, major polluting atmosphere environment again.
The people was also once arranged, and (" rare earth " rare earth is write group, the first volume 1978P219-P220 of metallurgical industry press) rare earth ore concentrate with the rare earth oxide that contains 50-60% is a raw material, at first carries out oxidizing roasting, leaches with sulfuric acid again, filter, and obtain leach liquor, and in leach liquor, add a certain amount of sodium sulfate, carry out the double salt precipitation of rare earth, filter, in the double salt of rare earth that obtains precipitation, add sodium hydroxide, carry out carrying out solid-liquid separation again after alkali changes, dissolve with hydrochloric acid, filter, and make the rare earth chloride stock liquid, can obtain containing the big rare earth raw material liquid of concentration of rare earth oxide with this technical process, but, this technical process is long, cause the loss of rare earth through the sedimentation and filtration that repeatedly makes the transition, and, the solubleness of double salt of rare earth is bigger, needs the free acid of higher concentration again, operation inconvenience, in addition, because the solubleness of the double salt of heavy rare earths is bigger than the solubleness of the double salt of light rare earths, so the loss of heavy rare earths is even more serious, so the rare earth total recovery of this technical process is lower.
There is report to say that (" rare earth " rare earth is write group again, the first volume 1978P211-P212 of metallurgical industry press) to containing the collective concentrate that rare earth oxide is 20-35%, mix mutually with concentrate with the industrial sodium carbonate that is equivalent to concentrate weight 15-30%, roasting collective concentrate and sodium carbonate mixture when temperature is 600-700 ℃, in baked concentrate, add entry and carry out wet ball mill, in the concentrate of crossing through the roasting wet ball mill, add about 80 ℃ water, mix and stir half an hour, wash, filter, the hydrochloric acid that adds 0.3-0.6N in filter cake stirs in 60-70 ℃ and carried out pickling in 0.5 hour, filtration obtains the filter cake through pickling, sulfuric acid with 4-5N carries out acidleach in 60-70 ℃ to the filter cake of crossing through overpickling, in leaching process, constantly stir the carrying out of accelerated reaction, filter, obtain the leach liquor that sulfuric acid concentration is approximately 3N, sulfuric acid with 0.5N washs slag, filter, washing lotion and leach liquor merge and obtain rare earth raw material liquid, the advantage of this processing method is that cerium is oxidized to tetravalence when roasting is decomposed, for the extraction separation of cerium creates conditions, and certain adaptability is all arranged for dissimilar rare earth ore concentrates, in roasting process, do not produce obnoxious flavour, atmospheric environment is not polluted, the weak point of this technical process is that technical process is still longer, the rare earth concentration of resulting leach liquor (rare earth raw material liquid) is low, and the acidity of sulfuric acid of leach liquor high (approximately 3N), is not easy to the carrying out of later purification separation technology, cost is higher, and wastewater flow rate is more.
Purpose of the present invention just is to work out one and is applicable to the processing method of producing rare earth raw material liquid from bastnasite, the bastnasite that are produced from various places all has certain adaptability, in the roasting decomposition course, do not produce obnoxious flavour yet, and shortened process again, reduce and filter number of times, the rate of decomposition of bastnasite and the rate of recovery of rare earth are all increased significantly, the concentration of resulting rare earth raw material liquid middle-weight rare earths is big, and its acidity is low, is convenient to next step the purification and the carrying out of separating technology.
A kind of processing method of producing rare earth raw material liquid from bastnasite of the present invention, bastnasite and yellow soda ash or sodium hydroxide are mixed with 100/10～100/40 weight ratio, roasting, wash the calcining matter of ore deposit and yellow soda ash (or sodium hydroxide) with water, after the washing, after under agitation carrying out pickling with nitric acid or aqueous solution of hydrochloric acid, carry out solid-liquid separation, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time a kind of leaching liquid wherein as acidleach for the first time, under agitation solid phase is carried out the acidleach first time, in the acidleach process, add reductive agent simultaneously, doubly (the cerium amount is to contain the cerium amount in the ore for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount for the amount of the reductive agent that is added, down together), the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, it is 0.01 mol-0.6 mol that the amount of mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time makes the concentration of the free acid in the leach liquor of acidleach for the first time, carry out solid-liquid separation, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid a kind of leaching liquid wherein as acidleach for the second time, under agitation solid phase is carried out the acidleach second time, in the acidleach process, add reductive agent simultaneously, the reduction dosage that is added is for becoming the quadrivalent cerium Restore All 0.7-4 times (the cerium amount is to contain the cerium amount in the ore) of trivalent cerium theoretical amount, the aqueous nitric acid that is added, aqueous hydrochloric acid wherein a kind of amount of solution to make the concentration of the free acid in the leach liquor of acidleach for the second time be 0.7 mol-2.5 mol, isolate the leach liquor and the primary slag of acidleach for the second time after the filtration, the leach liquor of acidleach for the second time is used for acidleach for the first time, aqueous sodium hydroxide solution with 5%-40% (weight percentage), to carrying out alkali cleaning through the primary slag behind the secondary pickling, washing again, with the above-mentioned acidleach first time, the condition of acidleach is for the second time carried out acidleach for the first time and acidleach for the second time (leach liquor of second acidleach is used for acidleach for the first time) to the primary slag after the alkali cleaning washing, will be through alkali cleaning, the leach liquor of the acidleach first time of the primary slag after the washing and the leach liquor of the above-mentioned acidleach first time are merged into the stock liquid of rare earth, the bastnasite aboundresources of China, wherein contain RE phosphate hardly, general bastnasite contains rare earth oxide 20-60% (weight percentage), used mineral are good with f_c_ce_la concentrate, employed bastnasite is the bastnasite through the Sichuan Province of ore dressing Mianning and other places in the technology of the present invention, its tap density of the bastnasite of Sichuan Province's Mianning is 3.03 gram/cubic centimetres, loose density is 2.3 gram/cubic centimetres, its size-grade distribution is as follows: contain 58.02% (weight percentage in particle diameter (micron)＞720＜720＜216＜100＜61＜44 accumulation % 4.4 95.6 60.5 28.4 10.1 9.5 bastnasites, rare earth oxide down together), contain 29.46% cerium dioxide, contain 3.85% iron, contain 6.74% fluorine.Consisting of of its ore middle-weight rare earths oxide compound, La2O3 is 35.35% (weight percentage, down together), and CeO2 is 50.08%, and Pr6O11 is 4.03%, and Nd2O3 is 10.09%, and Sm2O3 is 0.45%, and remaining rare earth oxide is all less than 0.10%.
The weight ratio of bastnasite and alkali (yellow soda ash or sodium hydroxide) is, 100/10-100/40 (ore deposit alkali than), alkali ratio in ore deposit is lower than at 100/16 o'clock, the rate of decomposition of concentrate is low, with ore deposit alkali than in the raising of alkali number, its rate of decomposition increases gradually; Ore deposit alkali is than in the scope of 100/20-100/40, and little to the influence of rate of decomposition along with the increase of alkali number, used alkali is good with yellow soda ash, and what influence is the granularity of concentrate almost do not have to its rate of decomposition.
The maturing temperature of the mixture after f_c_ce_la concentrate and yellow soda ash or sodium hydroxide mix is controlled between 500-800 ℃, roasting time 0.5-3 hour, in 500-750 ℃ temperature range, along with the raising of maturing temperature, the increase of roasting time, its rate of decomposition increases thereupon; When roasting time one timing, its rate of decomposition improves with the raising of maturing temperature, and maturing temperature one regularly, its rate of decomposition improves with the increase of roasting time, but, when selecting roasting condition, should consider to reduce the consumption of industrial chemicals as far as possible, guarantee that full technical process carries out smoothly.
Calcining matter through baked f_c_ce_la concentrate and yellow soda ash or sodium hydroxide, water washs it, fluorochemical and unreacted yellow soda ash that the flush away energy is water-soluble, its method is in stirring down, add entry (tap water, distilled water, wherein a kind of of ion exchanged water), under 30-80 ℃ temperature, wash, temperature is lower than 30 ℃, and to wash fluorine efficient low, the high more fluorine efficient of washing of temperature is high more, stopping to stir and treat to carry out solid-liquid separation with dumping method or siphonage after the sedimentation, so carry out 1-8 time, is good with 3-6 time again, till washing is 7-8 to the PH of its water lotion, the speed that stirs when washing with water is as the criterion to have stirred solid materials, and the speed of stirring is little to the washing effect influence, and the water that is added during washing makes solid-to-liquid ratio be controlled at 1: 1.5-5 (grams per milliliter), again with 1: 1-2 (grams per milliliter) is for well, the concentrate amount of the amount of solid phase to be added.
Carry out pickling after the washing, the method of pickling is under the temperature of room temperature to 80 ℃, in stirring, add entry (tap water, distilled water, a kind ofly in the ion exchanged water) and nitric acid or hydrochloric acid, it is 4.5-6 that the amount of adding nitric acid or hydrochloric acid makes the pH value of last pickle solution, solid-to-liquid ratio during pickling is controlled at 1: 1.5-5 (grams per milliliter), again with 1: 2-3 (grams per milliliter) is good, the amount of solid phase is in the amount of the f_c_ce_la concentrate that added, when pickling, the speed that stirs also is to be as the criterion to have stirred solid materials, the speed that stirs is little to the pickling effect influence, stop to stir and treat to carry out solid-liquid separation with dumping method or siphonage after the solid materials sedimentation, the pH value of isolated liquid phase pickle solution is 4.5-6, carries out a pickling usually.
Carry out the acidleach first time after the pickling, its method is, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time a kind of leaching liquid wherein as acidleach for the first time, under agitation solid phase is carried out the acidleach first time in 50-100 ℃, in acidleach first time process, add reductive agent simultaneously, the amount of the reductive agent that is added for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, 1-2.5 with its theoretical amount doubly is advisable again, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, it is 0.01 mol-0.6 mol that the amount of mixed solution a kind of solution wherein of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time makes the concentration of free acid in the leach liquor of acidleach for the first time, again with 0.1 mol-0.6 mol for well, the reductive agent that is added can be a hydrogen peroxide, Sulfothiorine, S-WAT, sulfurous gas, Sodium Nitrite, wherein a kind of of water-soluble divalent iron salt, but to add hydrogen peroxide (hydrogen peroxide) is good, because corresponding impurity element is introduced in the affiliation that adds of other reductive agents, can produce adverse influence to later technology, added hydrogen peroxide (hydrogen peroxide) can be that concentration is the hydrogen peroxide of 5-30% (weight percentage), again with 30% hydrogen peroxide for well, the amount of used hydrogen peroxide for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, 1-2.5 with theoretical amount doubly is advisable again, the hydrogen peroxide add-on is The more the better, but make cost up, because except that the discrete bastnasite, the content of cerium dioxide is between 20-35% in most of bastnasites, can also be controlled at 20 kilograms of-110 kilograms/bastnasites per ton so add the amount of hydrogen peroxide, again be controlled at 60 kilograms-90 kilograms/whenever ram the loose soil with a stone-roller after sowing bastnasite for well, be that reductive agent is when carrying out first time acidleach with the hydrogen peroxide, the acidleach temperature generally is controlled at 50-100 ℃, the temperature of acidleach is high more, help the leaching of rare earth element more, but, hydrogen peroxide its decomposition reaction below 70 ℃ the time is very slow, surpassing 85 ℃ of its decomposition rates accelerates, so the temperature of acidleach for the first time and acidleach for the second time is controlled at 70-85 ℃ and is advisable, the stirring velocity of (acidleach for the first time and acidleach for the second time) is as the criterion to have stirred solid materials when acidleach, its stirring velocity influences not quite the result of acidleach, the solid phase of (acidleach for the first time and acidleach for the second time) and the solid-to-liquid ratio of leaching liquid are controlled at 1 during acidleach: 1.5-4.5 (grams per milliliter), again in 1: 2.0-3.0 (grams per milliliter) is (the concentrate amount of the amount of solid phase to be added), the extraction time of (acidleach for the first time and acidleach for the second time) was controlled at 0.1-2 hour when acidleach, was advisable with 0.5-1.1 hour again.
When acidleach for the first time finishes, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with dumping method or siphonage, the leach liquor of isolated liquid phase acidleach for the first time places container interior stand-by.
After carrying out the acidleach first time, carry out the acidleach second time, the aqueous solution with nitric acid, aqueous solution of hydrochloric acid a kind of leaching liquid wherein as acidleach for the second time, under agitation solid phase is carried out the acidleach second time, in the acidleach process, add reductive agent simultaneously, the amount of the reductive agent that is added (for example hydrogen peroxide) for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, 1-2.5 in theoretical amount doubly is advisable again, and (the cerium amount is to contain the cerium amount in the ore, the aqueous nitric acid that is added down together), it is 0.7 mol-2.5 mol that the amount of aqueous hydrochloric acid makes the concentration of the leach liquor free acid of acidleach for the second time, be advisable with 0.7 mol-2 mol again, the reductive agent that is added can be a hydrogen peroxide, Sulfothiorine, S-WAT, sulfurous gas, Sodium Nitrite, wherein a kind of of water-soluble divalent iron salt, but is good to add hydrogen peroxide as reductive agent, added hydrogen peroxide can be that concentration is the hydrogen peroxide of 5-30% (weight percentage), hydrogen peroxide with 30% is for well, the amount of the hydrogen peroxide that is added for the 0.7-4 that the quadrivalent cerium Restore All become cerous theoretical amount doubly, 1-2.5 with theoretical amount doubly is advisable again, add hydrogen peroxide amount also can be controlled at 20 kilograms of-110 kilograms/bastnasites per ton, again to be controlled at 60 kilograms of-90 kilograms/bastnasites per ton for well, the temperature of acidleach for the second time also can be controlled in 50-100 ℃, again to be controlled at 70-85 ℃ for good, its stirring velocity is as the criterion to have stirred solid materials, its stirring velocity also influences not quite the result of the acidleach second time, the solid-to-liquid ratio of solid phase and leaching liquid is controlled at 1 during acidleach for the second time: 1.5-4.5 (grams per milliliter), again in 1: 2.0-3.0 (grams per milliliter) is (the concentrate amount of the amount of solid phase to be added), extraction time also was controlled at 0.1-2 hour when secondary pickling, again with 0.5-1.1 hour for well.
To process acidleach for the second time, primary slag after the filtration, carry out 1-2 washing again for good, filtering method has methods such as filter press technique, centrifuging, suction filtration, but be advisable with filter press technique, filter back water (distilled water, ion exchanged water, tap water wherein a kind of) washing 1-2 time, obtain through the leach liquor of the primary slag of water washing and the acidleach second time leach liquor as the acidleach first time.
Because through behind the secondary pickling, filtration also still contains 2 percent in the primary slag of water washing, rare earth oxide about 30, so must the primary slag after water washing be further processed, at first primary slag is carried out alkali cleaning, so-called alkali cleaning is exactly under agitation, the sodium hydroxide solution that adds 5-40% (weight percentage), under 70-110 ℃ temperature, stirred 0.5-4.0 hour, filter, wash again, general alkali cleaning is carried out once, the concentration of used sodium hydroxide solution is 5-40% (weight percentage) during alkali cleaning, the concentration of sodium hydroxide solution is lower than 5%, the rate that washes out of fluorine and the rate of decomposition of ore are all low, raising along with naoh concentration, the rate that washes out of fluorine and the rate of decomposition in ore deposit improve thereupon, concentration sodium hydroxide is high more good more, the temperature of alkali cleaning is high more good more, when concentration sodium hydroxide greater than 20% the time, fluorine wash out rate and rate of decomposition all reaches more than 98%, so concentration sodium hydroxide is good with 20-30% (weight percentage), concentration sodium hydroxide is tabulated in 1 to the rate that washes out of fluorine and the influence of ore resolution ratio.
Table 1 naoh concentration contains concentration and goes out rate % REO content REO% rate of decomposition % fluorine % the slag that slag in the acid leaching liquor heavily restrains slag content ore washed of the fluorine that influences alkali of the rate of decomposition of the rate that washes out of fluorine and ore
Grams per liter 5% 73.4 5 65.80 17.0 30.13 82.34--10% 80.21 68.4 5 16.5 28.93 83.54--15% 91.35 73.34 14.0 20.37 90.2 0 1.1320% 98.48 80.21 10.5 0.74 99.32 0.6725% 98.78 80.31 8.0 0.43 99.88 0.6530% 99.00 80.33 8.0 0.21 99.94 0.58
REO represents rare earth oxide in the table 1, the experimental technique of obtained data is to get 50 gram f_c_ce_la concentrates through roasting in the table 1, washing, acidleach for the first time, acidleach for the second time obtains primary slag, under 100 ℃ temperature, stirred 3 hours again, after carrying out alkali cleaning, carry out the acidleach first time with nitric acid, acidleach for the second time, filter, be washed with water to the PH-7 of washing water, rare-earth oxidation substrate concentration in the table 1 in the acid leaching liquor is the concentration after the leach liquor of the leach liquor of acidleach for the first time and acidleach for the second time merges, the rate of washing out of fluorine comprises the cumulative amount of data such as concentrate processing, the leach liquor volume is 370 milliliters, exhausted sodium hydroxide is recyclable during alkali cleaning recycles, temperature is high more good more during alkali cleaning, the speed that stirs is as the criterion to have stirred solid materials, its stirring velocity is little to the alkali cleaning effect influence, under agitation the time of carrying out alkali cleaning with sodium hydroxide solution generally was controlled at 0.5-4.0 hour, the rate of decomposition of the amount of washing out of fluorine and ore improves along with the increase of alkali cleaning time, so the alkali cleaning time is controlled at 2-4 hour for good, the alkali cleaning time sees Table 2 to the rate that washes out of fluorine and the influence of ore resolution ratio.
The time of table 2 alkali cleaning to the rate of decomposition of the rate that washes out of fluorine and ore influence alkali cleaning time fluorine wash that slag in the acid leaching liquor restrains heavily that slag includes ore hour go out rate % REO content REO% rate of decomposition
Grams per liter %0.5 76.34 69.89 16.0 32.50 82.071.0 79.41 72.35 15.5 28.41 84.821.5 81.28 74.21 15.0 26.30 86.402.0 84.51 76.40 14.0 22.50 88.362.5 90.45 79.92 13.0 10.11 95.463.0 99.28 83.01 10.0 0.23 99.923.5 99.37 83.41 10.0 0.47 99.844.0 99.50 83.39 10.0 0.11 99.96
The experiment condition and the table 1 of table 2 are basic identical, and only different is that other conditions are constant, and the time of alkali cleaning changes, and solid-to-liquid ratio is the bigger the better when carrying out alkali cleaning.
After the alkali cleaning under agitation water wash, the temperature of washing is controlled at 30-95 ℃, the speed of stirring the same during with alkali cleaning is as the criterion to have stirred solid materials, solid-to-liquid ratio is the bigger the better, wash 3-10 time, be good with 4-6 time, the PH that makes water lotion is 7-8,
Through alkali cleaning, the washing after primary slag with the above-mentioned acidleach first time, the second time acidleach condition, primary slag after alkali cleaning, washing is carried out the acidleach first time and acidleach for the second time (secondary acidleach leach liquor is used for acidleach for the first time), will be to the leach liquor of the acidleach first time of the primary slag after alkali cleaning, washing and the stock liquid of leach liquor merging the becoming rare earth of the above-mentioned acidleach first time, the acidity of the free acid in the rare earth raw material liquid is generally 0.01 mol-0.6 mol, again with 0.1 mol-0.6 mol for well.
The acidity of the free acid in the leach liquor of secondary pickling, measure with the neutralization titration that the those of ordinary skill under this area is all known, with Zn-EDTA or Ca-EDTA is sequestering agent, with the blue mixture indicator of methyl red-methyne, weakly acid soln carries out titration with standard caustic soda solution, if can be measured its pH value with the PH meter.
Our experiments show that, processing method of the present invention is applicable to the bastnasite that contains 20% rare earth oxide of each real estate fully, the bastnasite that contains 36.9% rare earth oxide, the bastnasite that contains 46.06% rare earth oxide, its rate of decomposition is all more than 99.9%, and rare earth yield is all more than 97%.
Resulting rare earth raw material liquid can be through the raw material of suitable purification as the promotor of the raw material of agricultural rare earth nitrate and other plant-growths that contain rare earth, add oxalic acid and generate the rare-earth oxalate precipitation, become rare earth oxide in 800 ℃ of calcinations again, also it can be concentrated and make rare earth chloride crystallization or rare earth nitrate crystallization, can be used as the raw material of extracting and separating single rare earth again.
The advantage of processing method of the present invention just is:
1. processing method suitability of the present invention is strong, be applicable to that the bastnasite that produces from various places produces rare earth raw material liquid, in the process of roasting decomposing ore, do not produce the obnoxious flavour that contains fluorochemical, avoided pollution, help operator's health environment.
2. compare with existing technology and reduced filtering number of times, shortened technical process, simplified operating process, the consumption and the cost of industrial chemicals have been reduced, improved the rate of decomposition of bastnasite and the rate of recovery of rare earth, greatly reduced the quantity of slag, slag middle-weight rare earths constituent content is little.
Since with nitric acid, salt acid substitution sulfuric acid as leaching liquid, the rare earth raw material liquid middle-weight rare earths concentration of gained is big; Owing to taked secondary pickling, with the leach liquor of the acidleach second time leaching liquid as the acidleach first time, reduced sour consumption, reduced the acidity in the rare earth raw material liquid, increase the concentration of rare earth raw material liquid middle-weight rare earths, be convenient to next step the purification and the carrying out of separating technology.
4. fluorine is washed out with the form of Sodium Fluoride, has improved the concentration that washes out of fluorine, is convenient to the recovery and the comprehensive utilization of fluorine.
With following embodiment processing method of the present invention is further described, will helps the understanding of the present invention and advantage thereof, and not as the qualification to protection domain of the present invention, protection scope of the present invention is decided by claims.
Embodiment 1
F_c_ce_la concentrate 250 gram and the yellow soda ash that will contain 58.01% rare earth oxide, mix than 100/20 (weight ratio) with ore deposit alkali, carried out roasting 1 hour in 650 ℃, under agitation with the fluorine of tap water in the calcining matter of 70 ℃ of washing ore deposits and yellow soda ash, solid-to-liquid ratio is 1: 2 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), each washing 20 minutes, stop to stir and treat to carry out solid-liquid separation with the siphonage or the method for dumping after the sedimentation, so carry out 3 times, wash to the PH of water lotion be 7.5, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.19 grams per liters, washing back add entry and drip 4 mol under 80 ℃ aqueous nitric acid carries out the PH-5 that pickling makes last pickle solution, pickling 20 minutes, solid-to-liquid ratio during pickling is 1: 2.5 (grams per milliliter, the amount of solid phase is in the amount of the bastnasite that added), pickling once, pickle solution is 480 milliliters, wherein contain 1.28 grams per liter rare earth oxides, 0.89 grams per liter calcium, 0.33 grams per liter magnesium, 5.79 grams per liter barium.
Carry out the acidleach first time after the pickling, its method is to use the leaching liquid of the leach liquor of the acidleach second time that contains free acid 1 mol nitric acid of preparation already as the acidleach first time, under agitation the solid phase after separating is carried out the acidleach first time in 82 ℃, in acidleach first time process, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium one times of three cerium theoretical amount, add the amount of the leach liquor of the acidleach second time that contains free acid 1 mol nitric acid of preparation already, making the free acid in the leach liquor of acidleach for the first time is 0.1 mol nitric acid, solid-to-liquid ratio during acidleach for the first time is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 1 hour, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contain 173.7 grams per liter rare earth oxides, 0.96 grams per liter calcium, 0.24 grams per liter magnesium, 0.24 grams per liter barium, 0.19 grams per liter iron.
For the first time after the acidleach, stop to stir treat the solid materials sedimentation after, carry out solid-liquid separation with dumping method or siphonage, the leach liquor of the isolated liquid phase acidleach first time places in the container.
With the nitric acid of 9 mol leaching liquid as the acidleach second time, under agitation solid phase is carried out the acidleach second time in 80 ℃, in the acidleach process, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1 times of trivalent cerium theoretical amount, the amount that adds the nitric acid of 9 mol, making the concentration of free acid of the leach liquor of acidleach for the second time is 1 mol, the solid-to-liquid ratio of solid phase and leaching liquid is 1: 2.0 (grams per milliliter during acidleach for the second time, the concentrate amount of the amount of solid phase to be added), the extraction time of acidleach for the second time is 0.5 hour, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contain 145.5 grams per liter rare earth oxides, 0.14 grams per liter calcium, 0.21 grams per liter magnesium, 0.51 grams per liter barium.
Get the back through acidleach for the second time and filter, wash secondary with water, obtain the leach liquor of primary slag and acidleach for the second time with press filtration.
Primary slag through water washing is carried out an alkali cleaning, and alkali cleaning is exactly the solution that under agitation adds 30% sodium hydroxide, stirs 3 hours in 101 ℃, filters, and water washs again, and the temperature of washing is 90 ℃, washes 6 times, and the PH that makes water lotion is 7.5.
Through alkali cleaning, primary slag after the washing condition of the above-mentioned acidleach first time and the acidleach for the second time of present embodiment, to through alkali cleaning, primary slag after the washing carries out the acidleach first time and acidleach for the second time, will be through the leach liquor of the acidleach first time of the primary slag after the alkali cleaning washing stock liquid with leach liquor merging the becoming rare earth of the above-mentioned acidleach first time, acidity is 0.1 mol nitric acid, slag weighs 36.0 grams, slag rate 14.4%, contain rare earth oxide 0.17% in the slag, the rate of recovery of ore resolution ratio 99.96% rate rare earth is 97.5%.
Embodiment 2
Its operation is substantially with embodiment 1, and only different is that ore deposit alkali is than 100/30 (weight ratio), carried out roasting 0.7 hour in 750 ℃, with tap water wash to PH be 7.2, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.88 grams per liters, the PH of the pickle solution of pickling is 6, pickle solution is 480 milliliters, wherein contains 0.86 grams per liter rare earth oxide, 0.87 grams per liter calcium, 0.20 grams per liter magnesium, 5.60 grams per liter barium.
Carry out the acidleach first time after the pickling, the acidleach temperature is 75 ℃, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 1.5 times of trivalent cerium theoretical amount, add the leach liquor that contains the acidleach second time of free acid 1 mol nitric acid among the embodiment 1, making the free acid in the leach liquor of acidleach for the first time is 0.2 mol nitric acid, solid-to-liquid ratio is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 0.7 hour, the volume of the leach liquor of acidleach for the first time is 700 milliliters, wherein contains 172.4 grams per liter rare earth oxides, 1.02 grams per liter calcium, 0.18 grams per liter magnesium, 0.29 grams per liter barium, 0.34 grams per liter iron.
After the acidleach for the first time, with 10 mol nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 75 ℃, in the acidleach process, add 30% hydrogen peroxide simultaneously, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1.5 times of trivalent cerium theoretical amount, the amount that adds the nitric acid of 10 mol, making the concentration of free acid of the leach liquor of acidleach for the second time is 2 mol, solid-to-liquid ratio is 1: 2.0 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), the extraction time of acidleach is 1 hour, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contains 148.6 grams per liter rare earth oxides, 0.21 grams per liter calcium, 0.66 grams per liter magnesium, 0.34 grams per liter barium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 20% aqueous sodium hydroxide solution, stirs 2.5 hours in 90 ℃, and water washs again, and the temperature of washing is 95 ℃, washes 4 times, and the PH that makes water lotion is 8.0.
Through alkali cleaning, primary slag after the washing above-mentioned acidleach first time of present embodiment and the condition of second acidleach, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.2 mol nitric acid, slag weighs 36.0 grams, and slag rate 14.4% contains rare earth oxide 0.14% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 99%.
Embodiment 3
Its operation is substantially with embodiment 1, only different is ore deposit alkali is than 100/16 (weight ratio), in 550 in ℃ carrying out roasting 3 hours, washs to PH7 with tap water, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.89 grams per liters, the PH of the pickle solution of pickling are 5.5, and the pickling volume is 480 milliliters, wherein contain 0.84 grams per liter rare earth oxide, 0.88 grams per liter calcium, 0.21 grams per liter magnesium, 5.64 grams per liter barium.
Carry out the acidleach first time after the pickling, 70 ℃ of acidleach temperature, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 3.0 times of trivalent cerium theoretical amount, the mixed solution that adds the aqueous nitric acid of the leach liquor of the acidleach second time that contains free acid 2 mol nitric acid among the embodiment 2 and 7 mol, making the free acid in the leach liquor of acidleach for the first time is 0.4 mol nitric acid, solid-to-liquid ratio during acidleach for the first time is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 2 hours, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contain 177 grams per liter rare earth oxides, 1.24 grams per liter calcium, 0.38 grams per liter magnesium, 0.49 grams per liter barium, 0.15 grams per liter iron.
After the acidleach for the first time, with concentrated nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 70 ℃, the hydrogen peroxide of adding 30% in the acidleach process, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 3.0 times of trivalent cerium theoretical amount, the amount that adds concentrated nitric acid, making the concentration of free acid of the leach liquor of acidleach for the second time is 2.5 mol, solid-to-liquid ratio is 1: 2.0 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), and the extraction time of acidleach is 0.6 hour, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contain 138 grams per liter rare earth oxides, 0.17 grams per liter calcium, 0.64 grams per liter magnesium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 20% aqueous sodium hydroxide solution, stirs 2.5 hours in 90 ℃, and water washs again, and the temperature of washing is 95 ℃, washes 5 times, and the PH that makes water lotion is 7.
Through alkali cleaning, primary slag after the washing above-mentioned acidleach first time of present embodiment and the condition of second acidleach, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.4 mol nitric acid, slag weighs 32 grams, and slag rate 12.8% contains rare earth oxide 0.12% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 98.5%.
Embodiment 4
Its operation is substantially with embodiment 1, and only different is that ore deposit alkali is than 100/25 (weight ratio), in 750 ℃, carried out roasting 0.7 hour, wash to PH-7 with tap water, the cumulative volume of water lotion is 1475 milliliters, wherein fluorine-containing 5.83 grams per liters, the PH of the pickle solution of pickling is 6, the pickling volume is 480 milliliters, wherein contains 0.89 grams per liter rare earth oxide, 0.86 grams per liter calcium, 0.22 grams per liter magnesium, 5.65 grams per liter barium.
Carry out the acidleach first time after the pickling, 80 ℃ of acidleach temperature, the amount that hydrogen peroxide added is for being reduced into quadrivalent cerium 1.1 times of trivalent cerium theoretical amount, add the leach liquor that contains the acidleach second time of free acid 2.5 mol nitric acid among the embodiment 3, making the free acid in the leach liquor of acidleach for the first time is 0.3 mol nitric acid, solid-to-liquid ratio during acidleach for the first time is 1: 2.5 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), acidleach 1.5 hours, the volume of the leach liquor of acidleach is for the first time merged into 700 milliliters, wherein contains 170.0 grams per liter rare earth oxides, 0.68 grams per liter calcium, 0.59 grams per liter magnesium, 0.54 grams per liter barium, 0.13 grams per liter iron.
After the acidleach for the first time, with 10 mol nitric acid is the leaching liquid of acidleach for the second time, under agitation solid phase is carried out the acidleach second time in 80 ℃, the hydrogen peroxide of adding 30% in the acidleach process, the amount that hydrogen peroxide added is for becoming the quadrivalent cerium Restore All 1.1 times of trivalent cerium theoretical amount, the amount that adds 10 mol nitric acid, making the leach liquor of acidleach for the second time is 0.8 mol, solid-to-liquid ratio is 1: 2.0 (grams per milliliter, the concentrate amount of the amount of solid phase to be added), the extraction time of acidleach is 1.1 hours, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contains 161.2 grams per liter rare earth oxides, 0.16 grams per liter calcium, 0.47 grams per liter magnesium, 0.09 grams per liter barium.
Primary slag is carried out an alkali cleaning, and alkali cleaning is with 23% aqueous sodium hydroxide solution, stirs 2.5 hours in 93 ℃, and water washs again, and the temperature of washing is 89 ℃, washes 6 times, and the PH that makes water lotion is 7.
Through alkali cleaning, primary slag after the washing condition of the above-mentioned acidleach first time of present embodiment and acidleach for the second time, primary slag after alkali cleaning, washing is carried out the acidleach first time, acidleach for the second time, the acidity of the stock liquid of rare earth is 0.3 mol nitric acid, slag weighs 31.0 grams, and slag rate 12.4% contains rare earth oxide 0.23% in the slag, ore resolution ratio 100%, the rate of recovery of rare earth are 97%.
Embodiment 5
Its working method and condition are substantially the same manner as Example 1, only different is to contain rare earth oxide 46.06%200 grams in the ore, the merging volume of the leach liquor of acidleach for the first time is 400 milliliters, wherein contain 185.8 grams per liter rare earth oxides, 0.99 grams per liter calcium, 0.12 grams per liter magnesium, 1.35 grams per liter barium, 0.53 grams per liter iron, the volume of the leach liquor of acidleach is for the second time merged into 200 milliliters, wherein contains 106.5 grams per liter rare earth oxides, 0.40 grams per liter calcium, 0.25 grams per liter magnesium, barium trace, 0.43 grams per liter iron, slag weighs 31.5 grams, contain rare earth oxide 0.34% in the slag, ore resolution ratio 99.9%, the rate of recovery of rare earth is 97.7%.
Embodiment 6
Its working method and condition are substantially the same manner as Example 1, only different has been with salt acid substitution nitric acid, the merging volume of the leach liquor of acidleach for the first time is 900 milliliters, wherein contain 176.9 grams per liter rare earth oxides, 1.3 grams per liter calcium, 0.85 grams per liter magnesium, 11.7 grams per liter barium, 8.7 grams per liter iron, the volume of the leach liquor of acidleach is for the second time merged into 300 milliliters, wherein contains 144.2 grams per liter rare earth oxides, 0.8 grams per liter calcium, 0.33 grams per liter magnesium, 5.9 grams per liter barium, 5.9 grams per liter iron, slag rate 12.6%, contain rare earth oxide 0.57% in the slag, rare earth ore rate of decomposition 99.9%, the rate of recovery of rare earth are 98.3%.
Claims (13)
1. processing method of from bastnasite, producing rare earth raw material liquid, it is characterized in that, with bastnasite and yellow soda ash or sodium hydroxide, weight ratio with 100/10～100/40 mixes, roasting washes the calcining matter of ore deposit and yellow soda ash or sodium hydroxide with water, under agitation carries out pickling with nitric acid or aqueous solution of hydrochloric acid after the washing, solid-liquid separation
(1) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time a kind of leaching liquid wherein as acidleach for the first time, under agitation solid phase is carried out the acidleach first time, add reductive agent in the acidleach process, the amount of the reductive agent that is added for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, the aqueous nitric acid that is added, aqueous hydrochloric acid, the leach liquor of acidleach for the second time, the mixed solution of the leach liquor of nitric acid or hydrochloric acid and acidleach for the second time is a kind of amount of solution wherein, making the concentration of free acid in the leach liquor of acidleach for the first time is 0.01 mol-0.6 mol, carry out solid-liquid separation
(2) aqueous solution of usefulness nitric acid, aqueous solution of hydrochloric acid a kind of leaching liquid wherein as acidleach for the second time, under agitation solid phase is carried out the acidleach second time, add reductive agent in the acidleach process, the amount of the reductive agent that is added for the 0.7-4 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly, the aqueous nitric acid that is added, the amount of aqueous hydrochloric acid, making the concentration of the free acid in the leach liquor of acidleach for the second time is 0.7 mol-2.5 mol, isolate the leach liquor and the primary slag of acidleach for the second time after the filtration, the leach liquor of acidleach for the second time is used for acidleach for the first time
(3) with the aqueous solution of the sodium hydroxide of 5-40% (weight percentage), to carrying out alkali cleaning through the primary slag behind the secondary pickling, washing again,
(4) with the condition of the above-mentioned acidleach first time, acidleach for the second time the primary slag after alkali cleaning, washing is carried out the acidleach first time and acidleach for the second time, the leach liquor of acidleach for the second time is used for acidleach for the first time.
(5) will be through the leach liquor merging of leach liquor and the above-mentioned acidleach first time of the acidleach first time of the primary slag after alkali cleaning, the washing.
2. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that the reductive agent that is added is a hydrogen peroxide.
3. produce the processing method of rare earth raw material liquid according to a kind of of claim 2 from bastnasite, it is characterized in that the concentration of hydrogen peroxide is 5-30% (weight percentage).
4. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, when acidleach for the first time, acidleach for the second time, the temperature of acidleach is 50-100 ℃.
5. produce the processing method of rare earth raw material liquid according to a kind of of claim 4 from bastnasite, it is characterized in that, the temperature of acidleach for the first time, acidleach for the second time is 70-85 ℃.
6. produce the processing method of rare earth raw material liquid according to a kind of of claim 4 from bastnasite, it is characterized in that the solid-to-liquid ratio of solid phase and leaching liquid is 1 during acidleach: 1.5-4.5 (grams per milliliter).
7. produce the processing method of rare earth raw material liquid according to a kind of of claim 6 from bastnasite, it is characterized in that solid-to-liquid ratio is 1: 2.0-3.0 (grams per milliliter).
8. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, the concentration of the free acid of the leach liquor of acidleach for the first time is 0.1 mol-0.6 mol.
9. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, the concentration of the free acid of the leach liquor of acidleach for the second time is 0.7 mol-2 mol.
10. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that, the primary slag to after filtering through the acidleach second time carries out 1-2 time and washes.
11. produce the processing method of rare earth raw material liquid according to a kind of of claim 1 from bastnasite, it is characterized in that concentration sodium hydroxide is 20-30% (weight percentage) during alkali cleaning.
12. produce the processing method of rare earth raw material liquid from bastnasite according to a kind of of claim 1 or 11, it is characterized in that the temperature during alkali cleaning is 70-110 ℃, stirred 0.5-4 hour.
13. produce the processing method of rare earth raw material liquid from bastnasite according to a kind of of claim 2, it is characterized in that, the amount of the hydrogen peroxide of the reductive agent that is added for the 1-2.5 that the quadrivalent cerium Restore All become the trivalent cerium theoretical amount doubly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114910A CN1034743C (en) | 1993-11-26 | 1993-11-26 | Making rare-earth material liquid from bastnae site |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114910A CN1034743C (en) | 1993-11-26 | 1993-11-26 | Making rare-earth material liquid from bastnae site |
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| Publication Number | Publication Date |
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| CN1103111A CN1103111A (en) | 1995-05-31 |
| CN1034743C true CN1034743C (en) | 1997-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93114910A Expired - Lifetime CN1034743C (en) | 1993-11-26 | 1993-11-26 | Making rare-earth material liquid from bastnae site |
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| CN (1) | CN1034743C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101824554B (en) * | 2010-03-12 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Liquid alkali roasting decomposition extraction process of mixed rare earth concentrates |
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| CN102409164A (en) * | 2011-12-02 | 2012-04-11 | 中国科学院过程工程研究所 | Anti-caking roasting method for mixed rare earth ore |
| CN103725870B (en) * | 2014-01-20 | 2016-04-06 | 包头稀土研究院 | A kind of liquid alkali roasting decomposes the method that rare earth ore concentrate prevents ring formation |
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| CN104946887A (en) * | 2015-07-22 | 2015-09-30 | 中国恩菲工程技术有限公司 | Method for treating bastnasite concentrate |
| CN104962762A (en) * | 2015-07-22 | 2015-10-07 | 中国恩菲工程技术有限公司 | Processing method of fine bastnaesite |
| CN106191454B (en) * | 2016-07-05 | 2018-06-22 | 江西理工大学 | A kind of method of Extraction of rare earth in rare-earth smelting slag from calciothermic reduction |
| CN106048265B (en) * | 2016-08-17 | 2018-05-25 | 成都理工大学 | A kind of extracting method of bastnaesite rare earth elements |
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| CN109517974B (en) * | 2019-01-11 | 2020-05-29 | 四川江铜稀土有限责任公司 | Smelting method for comprehensively recovering rare earth and fluorine from bastnaesite |
| CN113234921A (en) * | 2021-05-10 | 2021-08-10 | 贵州轻工职业技术学院 | Method for extracting tungsten and fluorine from fluorine-containing tungsten ore and application |
-
1993
- 1993-11-26 CN CN93114910A patent/CN1034743C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1103111A (en) | 1995-05-31 |
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