CN115232960A - Method for treating mixed rare earth concentrate and application of quartz - Google Patents
Method for treating mixed rare earth concentrate and application of quartz Download PDFInfo
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- CN115232960A CN115232960A CN202210869691.3A CN202210869691A CN115232960A CN 115232960 A CN115232960 A CN 115232960A CN 202210869691 A CN202210869691 A CN 202210869691A CN 115232960 A CN115232960 A CN 115232960A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 175
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 141
- 239000012141 concentrate Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000010453 quartz Substances 0.000 title claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 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 abstract description 7
- 229910052590 monazite Inorganic materials 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 239000007787 solid Substances 0.000 claims description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 238000002386 leaching Methods 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 25
- 239000001488 sodium phosphate Substances 0.000 claims description 20
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 20
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 11
- 238000006115 defluorination reaction Methods 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 40
- 239000011737 fluorine Substances 0.000 abstract description 40
- 239000000243 solution Substances 0.000 description 36
- 229910052698 phosphorus Inorganic materials 0.000 description 26
- 238000011084 recovery Methods 0.000 description 24
- 235000011121 sodium hydroxide Nutrition 0.000 description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 21
- 239000011574 phosphorus Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000003513 alkali Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- -1 rare earth chloride Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for treating mixed rare earth concentrate and application of quartz, wherein the method comprises the following steps: mixing the mixed rare earth concentrate with quartz, heating to 200-400 ℃, introducing water vapor, continuously heating to 850-950 ℃, reacting at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate; wherein the mass ratio of the quartz to the mixed rare earth concentrate is 0.04-0.06, and the mixed rare earth concentrate mainly comprises monazite and bastnaesite. The treatment method of the invention can obtain higher fluorine removal rate at lower treatment temperature.
Description
Technical Field
The invention relates to a method for treating mixed rare earth concentrate and application of quartz.
Background
The smelting process of the mixed rare earth concentrate mainly comprises a sulfuric acid roasting method and a caustic soda method. The roasting of sulfuric acid is divided into two processes of low-temperature concentrated sulfuric acid roasting and high-temperature concentrated sulfuric acid roasting. Mixed gas such as HF, SO produced in the course of roasting and decomposing concentrated sulfuric acid 3 、SO 2 And CO 2 CO, water vapor, sulfuric acid vapor and the like are difficult to treat, sulfuric acid roasting, water leaching, alkaline solution neutralization, extraction transformation, hydrochloric acid back extraction and the like are involved in the whole process, and finally the obtained rare earth chloride solution is subjected to multistage extraction grouping of rare earth. The roasting process of the sulfuric acid has the problems of long flow, various and large using amount of raw materials, high cost, large generation amount of three wastes, high treatment difficulty, difficult effective separation and recovery of a large amount of phosphorus elements in the concentrate after entering the rare earth mixed solution and the like, thereby causing the waste of phosphorus and fluorine resources. The caustic soda process comprises the steps of rare earth concentrate, decalcification treatment, caustic soda decomposition, filtering and washing, hydrochloric acid dissolution, mixed rare earth chloride, multistage extraction and the like. The process has the problems of high requirement on the grade of rare earth concentrate, long process flow, large washing water consumption, difficult treatment of a large amount of sodium fluoride and sodium phosphate entering washing liquor and the like.
Therefore, a process capable of sufficiently recovering the resources such as fluorine, phosphorus, rare earth and the like in the mixed rare earth concentrate and simultaneously reducing the generation of waste water, waste slag and waste gas is needed.
CN106586992A discloses a process for comprehensively recovering fluorine and phosphorus by liquid alkali decomposition of mixed rare earth concentrate: mixing the high-grade mixed rare earth concentrate with a sodium hydroxide solution with the concentration of more than 60wt% according to the weight ratio of the mixed rare earth concentrate to the sodium hydroxide of 1.5-7.5, reacting for 0.2-1 h at 150-160 ℃, carrying out hot filtration to obtain a concentrated alkali solution and an alkali cake, cooling the concentrated alkali solution, and then carrying out filtration to obtain a sodium phosphate product; the alkali cake is washed by water for size mixing and is filtered to obtain primary washing alkali liquor; continuously washing the alkali cake with water to neutrality, dissolving with hydrochloric acid, and controlling pH value to obtain rare earth chloride solution; and concentrating and filtering the primary alkali washing liquid to obtain a sodium fluoride product. Although the process can recover fluorine and phosphorus respectively, the fluorine removal rate and the phosphorus recovery rate in the process are still to be improved; the obtained sodium phosphate has high fluorine content and is difficult to remove in the subsequent step; and part of sodium fluoride is remained in the rare earth filter cake, so that the rare earth yield is reduced when rare earth fluoride precipitate is produced in the hydrochloric acid leaching process, and the energy consumption is large when the alkali washing liquid is concentrated.
CN109837385A discloses a method for heating, melting, converting and decomposing rare earth ore, adding carbon material into a furnace, melting the rare earth ore of endosperm dephosphorization and fluorine fixation material by utilizing the functions of heating of carbonic acid material and generating electric arc heating, wherein the fluorine fixation material adopts calcium carbonate. The fluorine-containing substances generated by the process are not beneficial to cyclic utilization, and the fluorine removal rate is still to be improved.
CN114480835A discloses a decomposition method of mixed rare earth concentrate, which comprises roasting and decomposing the mixed rare earth concentrate, magnesium chloride and carbon powder under the action of microwave to obtain roasted ore; leaching the roasted ore by adopting first inorganic acid to obtain acid leaching slag and a first rare earth solution; separating acid leaching residues to respectively obtain magnesium fluoride and undecomposed rare earth concentrate; performing alkaline decomposition on the undecomposed rare earth concentrate to obtain alkaline wastewater and alkaline hydrolysis ore; cooling, concentrating and crystallizing the alkali wastewater to obtain sodium phosphate and recovered alkali liquor; and leaching the alkaline hydrolyzed ore by adopting second inorganic acid to obtain a second rare earth solution. The decomposition method can obtain magnesium fluoride, but the fluorine removal rate is still to be improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for treating a misch metal concentrate, which can achieve a higher fluorine removal rate at a lower treatment temperature. Another object of the present invention is to provide the use of quartz for treating mixed rare earth concentrates to obtain fluosilicic acid. The invention adopts the following technical scheme to achieve the purpose.
In one aspect, the invention provides a method for treating mixed rare earth concentrate, which comprises the following steps:
mixing the mixed rare earth concentrate with quartz, heating to 200-400 ℃, introducing water vapor, continuously heating to 850-950 ℃, reacting at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate;
wherein the mass ratio of the quartz to the mixed rare earth concentrate is 0.04-0.06;
wherein, the rare earth minerals in the mixed rare earth concentrate mainly comprise monazite and bastnaesite.
According to the treatment method, the mass ratio of the quartz to the mixed rare earth concentrate is preferably 0.045-0.055.
According to the treatment method, the heating is preferably continued to 850-950 ℃, and the reaction is carried out for 1-4 h at the temperature.
According to the treatment method, the granularity of the mixed rare earth concentrate is preferably less than or equal to 200 meshes; the granularity of the quartz is less than or equal to 200 meshes.
According to the treatment method of the present invention, the condensation temperature is preferably 45 ℃ or lower.
According to the processing method of the present invention, preferably, the method further includes the steps of:
leaching the defluorinated rare earth concentrate by using a sodium hydroxide solution, and performing solid-liquid separation to obtain a sodium phosphate solution and a solid containing rare earth elements;
and (3) leaching the solid containing the rare earth element by hydrochloric acid, and performing solid-liquid separation to obtain a rare earth leachate and solid slag.
According to the processing method of the present invention, preferably, the method further comprises the following specific steps:
leaching the defluorinated rare earth concentrate with a sodium hydroxide solution at the temperature of 140-170 ℃ for 3-7 h, and carrying out solid-liquid separation to obtain a sodium phosphate solution and a solid containing rare earth elements;
leaching the solid containing the rare earth elements for 2-4 h at 75-85 ℃ by using hydrochloric acid, and carrying out solid-liquid separation to obtain rare earth leachate and solid slag.
According to the treatment method of the invention, preferably, the concentration of the sodium hydroxide solution is 45-65 wt%; the solid-liquid mass ratio of the defluorination rare earth concentrate to the sodium hydroxide solution is 1 (0.8-1.5).
According to the treatment method, the concentration of the hydrochloric acid is preferably 4.5-7 mol/L; the solid-liquid mass ratio of the solid containing the rare earth elements to the hydrochloric acid is 1: (3.5-6.5).
In another aspect, the present invention also provides the use of quartz in the treatment of a mixed rare earth concentrate to obtain fluorosilicic acid, comprising the steps of: mixing the mixed rare earth concentrate with quartz, heating to 200-400 ℃, introducing water vapor, continuously heating to 850-950 ℃, reacting at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate;
wherein the mass ratio of the quartz to the mixed rare earth concentrate is 0.04-0.06;
wherein the misch metal concentrate mainly comprises monazite and bastnaesite.
The treatment method of the mixed rare earth concentrate can obtain higher fluorine removal rate at lower treatment temperature. In addition, the treatment method can also recover sodium phosphate solution, so that the phosphorus recovery rate is higher, and meanwhile, the higher rare earth recovery rate can be ensured. The invention realizes the respective recovery of fluorine, phosphorus and rare earth by adopting a shorter process flow. The invention does not add any chloride (including magnesium chloride and ammonium chloride), ammonium sulfate, carbon powder or carbon material, boric acid and the like, thus improving the purity of the obtained fluosilicic acid and reducing the introduction of other impurities.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
In one aspect, the invention provides a method for treating a misch metal concentrate. In another aspect, the present invention provides the use of quartz in the treatment of a misch metal concentrate to obtain fluorosilicic acid. In the above method or use, the various steps are identical and are therefore described in general terms below. The treatment method or the application of the invention comprises the steps of forming fluosilicic acid and defluorination rare earth concentrate, alkaline leaching and acid leaching. Optionally, the method also comprises the step of crushing and/or grinding the mixed rare earth concentrate and/or the quartz.
The misch metal concentrate refers to a mixed rare earth ore mainly composed of monazite and bastnaesite, such as a baiyunebo mixed rare earth ore. Although the misch metal concentrate also contains bastnaesite, the treatment processes of misch metal concentrate and bastnaesite are significantly different due to the presence of other minerals such as monazite. If the two are treated by the same process, the treatment effect is greatly different.
< step of pulverization and/or grinding >
And respectively crushing and/or grinding the mixed rare earth concentrate and/or quartz to be treated to respectively obtain mixed rare earth concentrate particles and quartz particles.
In certain embodiments, the misch metal concentrate is ground to a particle size of 200 mesh or less, preferably 200 to 230 mesh, to produce misch metal concentrate particles. In other embodiments, the quartz is ground to a particle size of 200 mesh or less, preferably 200 to 230 mesh, to obtain quartz particles. Therefore, the mixed rare earth concentrate is not influenced to remove fluorine, and the ore grinding energy consumption is reduced.
< formation of fluosilicic acid and defluorination rare earth concentrate >
In the invention, the mixed rare earth concentrate and quartz are mixed, heated to a first temperature, steam is introduced, the mixture is continuously heated to a second temperature, the mixture reacts at the first temperature, and fluoride gas is condensed and recovered at the same time to obtain fluosilicic acid and defluorination rare earth concentrate. Preferably, the mixed rare earth concentrate particles and the quartz particles are uniformly mixed, heated to a first temperature, introduced with water vapor, continuously heated to a second temperature, and reacted at the first temperature, and simultaneously fluoride gas is condensed and recovered to obtain fluosilicic acid and the defluorination rare earth concentrate.
The present invention has surprisingly found that by adding quartz and controlling its amount and reaction temperature under the condition of introducing steam, the fluorine removal rate can be significantly increased and fluosilicic acid of higher purity can be obtained.
In the invention, the mixed rare earth concentrate particles and quartz particles can be placed into a gas-solid reaction furnace for heating or reaction. The gas-solid reaction furnace can be a fluidized bed, a fluidized bed furnace or a rotary kiln, and preferably is a gas-solid reaction furnace fluidized bed.
The first temperature may be 200 to 400 deg.c, preferably 250 to 350 deg.c, more preferably 280 to 320 deg.c. Then introducing water vapor, wherein the flow rate of the water vapor is 0.5-1.5 m when the temperature is lower than 700 DEG C 3 /(t min) (steam input/ton ore/min)Clock), preferably 0.8 to 1.2m 3 V (t.min); when the temperature is higher than 700 ℃, the water vapor flow is 2 to 5m 3 /(t.min), preferably 3 to 4m 3 /(t · min). t represents ton.
The second temperature may be 850 to 950 ℃, preferably 850 to 930 ℃, more preferably 850 to 920 ℃, still more preferably 880 to 920 ℃, and still more preferably 900 to 920 ℃. The reaction time may be 1 to 4 hours, preferably 1.5 to 3.5 hours, more preferably 2 to 3 hours. This is advantageous in improving the fluorine removal rate. In the prior art, the fluorine removal treatment temperature is usually above 1000 ℃ to obtain higher fluorine removal rate, but the dead burning phenomenon of rare earth minerals is easily caused by overhigh temperature, so that the activity is obviously reduced. According to the invention, by adding quartz, a higher fluorine removal rate can be obtained at a lower treatment temperature, and a higher rare earth recovery rate is ensured.
The mass ratio of the quartz to the misch metal concentrate is 0.04-0.06, preferably 0.045-0.055, more preferably 0.045-0.05. Thus being beneficial to improving the fluorine removal rate and improving the content of the fluosilicic acid.
The temperature of condensation is 45 ℃ or lower, preferably 40 ℃ or lower, and more preferably 30 ℃ or lower. Thus being beneficial to improving the recovery rate of fluorine and obtaining the fluosilicic acid with higher yield.
And after the reaction is finished, closing the heating system, closing the steam system, cooling and recovering the high-quality defluorinated rare earth concentrate. The fluorine content in the fluorine-removing rare earth concentrate is less than or equal to 0.45wt%.
The calculation formula of the fluorine removal rate is as follows: (amount of fluorine in the mixed rare earth concentrate-amount of fluorine in the defluorinated rare earth concentrate)/amount of fluorine in the mixed rare earth concentrate x 100%. The fluorine removal rate of the present invention is 95% or more, preferably 96% or more.
< alkaline Leaching step >
And leaching the defluorinated rare earth concentrate by using a sodium hydroxide solution, and performing solid-liquid separation to obtain a sodium phosphate solution and a solid containing rare earth elements.
According to one embodiment of the invention, the defluorination rare earth concentrate is leached for 3 to 7 hours at the temperature of between 140 and 170 ℃ by using a sodium hydroxide solution, and solid-liquid separation is carried out to obtain a sodium phosphate solution and a solid containing rare earth elements.
The concentration of the sodium hydroxide solution may be 45 to 65wt%, preferably 50 to 65wt%, more preferably 55 to 65wt%. The amount of sodium hydroxide solution used was: the solid-liquid mass ratio of the defluorination rare earth concentrate to the sodium hydroxide solution is 1 (0.8-1.5), preferably 1 (1.0-1.5), and more preferably 1 (1.0-1.3). The leaching temperature may be 140 to 170 ℃, preferably 145 to 170 ℃, more preferably 150 to 160 ℃. The leaching time may be 3 to 7 hours, preferably 3.5 to 6 hours, more preferably 4.5 to 5.5 hours. Thus being beneficial to separating the sodium phosphate from the solid containing the rare earth elements and respectively improving the recovery rate of the sodium phosphate and the solid containing the rare earth elements. And the consumption of the sodium hydroxide solution is less, so that the generation amount of waste liquid can be obviously reduced.
The solid-liquid separation can be filtration, and a small amount of water can be used for leaching filter cakes during filtration. The solid containing rare earth elements is mainly water-insoluble rare earth hydroxide and oxide, and the separation of rare earth and phosphorus elements is realized by filtering.
The purity of the sodium phosphate solution is more than 50%, the sodium phosphate solid with the purity of more than 98% can be obtained by subsequent alkali (NaOH) removal, purification and crystallization, and the phosphorus recovery rate can reach more than 86%, preferably more than or equal to 87%. The phosphorus recovery is calculated as follows: the amount of the phosphorus element in the sodium phosphate solution/the amount of the phosphorus element in the mixed rare earth concentrate is multiplied by 100 percent.
< acid leach step >
And (3) leaching the solid containing the rare earth elements by using hydrochloric acid, and performing solid-liquid separation to obtain a rare earth leaching solution and solid residues.
According to one embodiment of the invention, the solid containing rare earth elements is leached for 2-4 h at 75-85 ℃ by hydrochloric acid, and solid-liquid separation is carried out to obtain rare earth leachate and solid slag.
The concentration of hydrochloric acid may be 4.5 to 7mol/L, preferably 5 to 7mol/L, and more preferably 5.5 to 6.5mol/L. The dosage of the hydrochloric acid is as follows: the solid-liquid mass ratio of the solid containing the rare earth elements to the hydrochloric acid is 1: (3.5 to 6.5), preferably 1: (4.0 to 6.0), more preferably 1: (4.5-5.5).
The leaching temperature with hydrochloric acid may be 75 to 85 deg.c, preferably 78 to 85 deg.c, more preferably 80 to 85 deg.c. The leaching time can be 2 to 4 hours, preferably 2.2 to 3.5 hours, and more preferably 2.5 to 3 hours. This is beneficial to improving the recovery rate of rare earth.
The solid-liquid separation method is not particularly limited, and filtration is preferable.
The rare earth leachate is a solution containing rare earth chloride. The rare earth leachate can be used for extraction grouping of rare earth elements after impurity removal. The solid slag is solid containing aluminosilicate.
The rare earth recovery rate of the invention is higher, more than or equal to 92 percent, preferably more than or equal to 94 percent. The calculation formula of the rare earth recovery rate is as follows: the REO amount in the rare earth leachate/the REO amount in the mixed rare earth concentrate is multiplied by 100 percent.
According to the invention, fluorine is removed firstly, so that the subsequent leaching is facilitated, a large amount of rare earth fluoride precipitate is not generated and enters the solid, and the production problems of pipeline blockage due to fluoride precipitation and the like are avoided; in addition, the method is favorable for improving the phosphorus recovery rate.
< measuring method >
The measurement is carried out in the research of the Bayan Obo rare earth resource and the comprehensive utilization of the national laboratory detection center.
And (3) determination of fluorine content: adopts a fluorine evaporation method.
And (3) determination of the content of the phosphorus element: the ICP method was used.
Determination of REO content: plasma method and volumetric method are adopted.
In the following examples and comparative examples, the water vapor flow rates were as follows: at a reaction temperature of less than 700 ℃, the water vapor flow rate is 0.5m 3 V (t.min); at a temperature higher than 700 ℃, the water vapor flow is 3m 3 /(t·min)。
Example 1
Grinding the mixed rare earth concentrate (Baiyunebo mixed rare earth ore) to obtain mixed rare earth concentrate particles with the particle size of less than 200 meshes; the chemical components of the catalyst are 60.10 percent of REO, 3.20 percent of Sigma Fe, 7.80 percent of F, 3.50 percent of P, 4.35 percent of CaO, 3.71 percent of BaO, 1.26 percent of S, and ThO 2 :1.23％、Nb 2 O 5 0.06 percent and the rest is 14.79 percent (the mass percentage content).
And grinding the quartz to the particle size of less than 200 meshes to obtain quartz particles.
Uniformly mixing the mixed rare earth concentrate particles and quartz particles, heating the mixture in a fluidized bed of a gas-solid reaction furnace to a first temperature of 300 ℃, introducing steam, continuously heating the mixture to a second temperature, reacting the mixture for 3 hours at the second temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate; wherein, the mass ratio of the quartz to the mixed rare earth concentrate is recorded as M.
Leaching the defluorinated rare earth concentrate by adopting a 60wt% sodium hydroxide solution (the solid-liquid mass ratio is 1.2) at 150 ℃ for 5 hours, filtering and washing to obtain a sodium phosphate solution and a solid containing rare earth elements.
Leaching the solid containing the rare earth elements for 3 hours at 85 ℃ by using 6mol/L hydrochloric acid (the solid-liquid mass ratio is 1:5), and filtering to obtain rare earth leachate and solid slag.
Comparative example 1
The only difference from example 1 is that the condensed fluoride gas was absorbed directly with 0.5mol/L NaOH solution without adding quartz.
Comparative example 2
The only difference from example 1 is the mass ratio M of quartz to misch metal concentrate.
Comparative example 3
The only difference from example 1 is the second temperature.
Comparative example 4
The only difference from example 1 is that the second temperature is different.
Some process parameters and results of example 1 and comparative examples 1 to 4 are shown in Table 1 below.
TABLE 1
| Numbering | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Second temperature/. Degree.C | 900 | 900 | 900 | 750 | 1200 |
| Reaction time/h | 3 | 3 | 3 | 3 | 3 |
| M | 0.045:1 | 0 | 0.08:1 | 0.045:1 | 0.045:1 |
| Percent fluorine removal | 95 | 70 | 93 | 55 | 99 |
| Percent recovery of phosphorus | 87 | 50 | 70 | 45 | 70 |
| Recovery rate of rare earth% | 93 | 85 | 89 | 82 | 75 |
Note: the mass ratio of the quartz to the mixed rare earth concentrate was recorded as M.
As can be seen from the comparison between example 1 and comparative example 1, if quartz is not added, the fluorine removal rate is obviously reduced, sodium fluoride in the immersion liquid seriously exceeds the standard, the fluorine removal process is increased, phosphorus loss is caused, the recovery rate is reduced, and in addition, a small amount of fluorine is brought into a filter cake to influence the recovery rate of rare earth.
As can be seen from the comparison between example 1 and comparative example 2, if the amount of quartz added is too large, the silicon content in the sodium phosphate solution after alkaline leaching is large, and the silicon removal process needs to be added, resulting in a decrease in the phosphorus recovery rate.
As can be seen from comparison between example 1 and comparative example 3, when the second temperature is too low, the fluorine removal rate is significantly reduced, and the fluorine removal process is increased, resulting in a low phosphorus recovery rate and an adverse effect on the rare earth recovery rate.
As can be seen from the comparison between example 1 and comparative example 4, the second temperature is too high, although the fluorine removal rate is high, the dead burning phenomenon of the rare earth minerals is obvious, the activity is obviously reduced, and the subsequent recovery rates of phosphorus and rare earth are greatly reduced.
Example 2
Grinding the mixed rare earth concentrate to a granularity of less than 200 meshes to obtain mixed rare earth concentrate particlesGranulating; the chemical components of the catalyst are 65.10 percent of REO, 3.20 percent of Sigma Fe, 7.80 percent of F, 4.10 percent of P, 4.35 percent of CaO, 2.15 percent of BaO, 1.36 percent of S, and ThO 2 :1.03％、Nb 2 O 5 0.06 percent and the rest 10.85 percent (the mass percentage content).
And grinding the quartz to the particle size of less than 200 meshes to obtain quartz particles.
Uniformly mixing the mixed rare earth concentrate particles and quartz particles, heating the mixed materials in a fluidized bed of a gas-solid reaction furnace to a first temperature of 300 ℃, introducing steam, continuously heating to a second temperature of 950 ℃, reacting for 2.5 hours at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorination rare earth concentrate; wherein, the mass ratio M of the quartz to the mixed rare earth concentrate is 0.045.
And leaching the cooled defluorinated rare earth concentrate for 5 hours at 160 ℃ by adopting 55wt% of sodium hydroxide solution (the solid-liquid mass ratio is 1:1), filtering and washing to obtain sodium phosphate solution and rare earth element-containing solid.
Leaching the solid containing the rare earth elements for 2.5h at 80 ℃ by using 7mol/L hydrochloric acid (the solid-liquid mass ratio is 1:4), and filtering to obtain rare earth leachate and solid slag.
Example 3
Grinding the mixed rare earth concentrate to obtain mixed rare earth concentrate particles with the granularity of less than 200 meshes; the chemical components of the catalyst are 65.10 percent of REO, 3.20 percent of Sigma Fe, 7.80 percent of F, 4.10 percent of P, 4.35 percent of CaO, 2.15 percent of BaO, 1.36 percent of S, and ThO 2 :1.03％、Nb 2 O 5 0.06 percent and the rest 10.85 percent (the mass percentage content).
And grinding the quartz to the particle size of less than 200 meshes to obtain quartz particles.
Uniformly mixing the mixed rare earth concentrate particles and quartz particles, heating the mixed materials in a fluidized bed of a gas-solid reaction furnace to a first temperature of 200 ℃, introducing steam, continuously heating to a second temperature of 950 ℃, reacting for 2 hours at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate; wherein, the mass ratio M of the quartz to the mixed rare earth concentrate is 0.045.
And leaching the cooled defluorinated rare earth concentrate for 3 hours at 170 ℃ by adopting a 65wt% sodium hydroxide solution (the solid-liquid mass ratio is 1.
Leaching the solid containing the rare earth elements by using 7mol/L hydrochloric acid (the solid-liquid mass ratio is 1.
Example 4
Grinding the mixed rare earth concentrate to obtain mixed rare earth concentrate particles with the granularity of less than 200 meshes; the chemical components of the catalyst are 52.05% REO, 3.90% Sigma Fe, 6.80% F, 3.10% P, 6.37% CaO, 5.80% BaO, 1.57% S, thO 2 :1.15％、Nb 2 O 5 0.04 percent and the rest is 19.22 percent (the mass percentage content).
And grinding the quartz to the particle size of less than 200 meshes to obtain quartz particles.
Uniformly mixing the mixed rare earth concentrate particles and quartz particles, heating the mixed material in a fluidized bed of a gas-solid reaction furnace to a first temperature of 300 ℃, introducing steam, continuously heating to a second temperature of 950 ℃, reacting for 2.5 hours at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate; wherein the mass ratio M of the quartz to the mixed rare earth concentrate is 0.05.
Leaching the cooled defluorinated rare earth concentrate for 5 hours at 170 ℃ by adopting a 60wt% sodium hydroxide solution (the solid-liquid mass ratio is 1.
Leaching the solid containing the rare earth elements for 3 hours at 85 ℃ by using 6mol/L hydrochloric acid (the solid-liquid mass ratio is 1:5), and filtering to obtain rare earth leachate and solid slag.
Example 5
Grinding the mixed rare earth concentrate to obtain mixed rare earth concentrate particles with the granularity of less than 200 meshes; the chemical components of the catalyst are 52.05% REO, 3.90% Sigma Fe, 6.80% F, 3.10% P, 6.37% CaO, 5.80% BaO, 1.57% S, thO 2 :1.15％、Nb 2 O 5 0.04% and the rest 19.22% (all mass percentage)。
And grinding the quartz to the particle size of less than 200 meshes to obtain quartz particles.
Uniformly mixing the mixed rare earth concentrate particles and quartz particles, heating the mixed material in a fluidized bed of a gas-solid reaction furnace to a first temperature of 400 ℃, introducing steam, continuously heating to a second temperature of 900 ℃, reacting for 2.5 hours at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorination rare earth concentrate; wherein the mass ratio M of the quartz to the mixed rare earth concentrate is 0.05.
And leaching the cooled defluorinated rare earth concentrate for 7 hours at 140 ℃ by adopting a 45wt% sodium hydroxide solution (the solid-liquid mass ratio is 1: 1.5), filtering and washing to obtain a sodium phosphate solution and a solid containing rare earth elements.
Leaching the solid containing the rare earth elements for 2 hours at 85 ℃ by using 4.5mol/L hydrochloric acid (the solid-liquid mass ratio is 1.
TABLE 2
| Number of | Example 2 | Example 3 | Example 4 | Example 5 |
| The fluorine removal rate% | 97 | 95 | 98 | 95 |
| Percent recovery of phosphorus | 89 | 86 | 86 | 87 |
| Percent recovery of rare earth | 95 | 92 | 94 | 92 |
From examples 1 to 5, it can be seen that the treatment method of the present application is applicable to mixed rare earth concentrates of different tastes.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. The method for treating the mixed rare earth concentrate is characterized by comprising the following steps of:
mixing the mixed rare earth concentrate with quartz, heating to 200-400 ℃, introducing water vapor, continuously heating to 850-950 ℃, reacting at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate;
wherein the mass ratio of the quartz to the mixed rare earth concentrate is 0.04-0.06;
wherein, the mixed rare earth concentrate mainly comprises monazite and bastnaesite.
2. The treatment method according to claim 1, characterized in that the mass ratio of quartz to misch metal concentrate is 0.045 to 0.055.
3. The process according to claim 2, wherein the heating is continued to 850 to 950 ℃ and the reaction is carried out at this temperature for 1 to 4 hours.
4. The treatment method according to claim 1, wherein the particle size of the misch metal concentrate is 200 mesh or less; the granularity of the quartz is less than or equal to 200 meshes.
5. The process according to claim 1, wherein the condensation temperature is 45 ℃ or less.
6. The process of any one of claims 1 to 5, further comprising the steps of:
leaching the defluorinated rare earth concentrate by using a sodium hydroxide solution, and performing solid-liquid separation to obtain a sodium phosphate solution and a solid containing rare earth elements;
and (3) leaching the solid containing the rare earth element by hydrochloric acid, and performing solid-liquid separation to obtain a rare earth leachate and solid slag.
7. The treatment method according to any one of claims 1 to 5, further comprising the specific steps of:
leaching the defluorinated rare earth concentrate with a sodium hydroxide solution at the temperature of 140-170 ℃ for 3-7 h, and carrying out solid-liquid separation to obtain a sodium phosphate solution and a solid containing rare earth elements;
leaching the solid containing the rare earth elements for 2-4 h at 75-85 ℃ by using hydrochloric acid, and carrying out solid-liquid separation to obtain rare earth leachate and solid slag.
8. The process according to claim 7, characterized in that the concentration of the sodium hydroxide solution is between 45 and 65% by weight; the solid-liquid mass ratio of the defluorination rare earth concentrate to the sodium hydroxide solution is 1 (0.8-1.5).
9. The process according to claim 7, characterized in that the concentration of hydrochloric acid is between 4.5 and 7mol/L; the solid-liquid mass ratio of the solid containing the rare earth elements to the hydrochloric acid is 1: (3.5-6.5).
10. Use of quartz for the treatment of a mixed rare earth concentrate to obtain fluosilicic acid, characterized in that it comprises the following steps: mixing the mixed rare earth concentrate with quartz, heating to 200-400 ℃, introducing water vapor, continuously heating to 850-950 ℃, reacting at the temperature, and simultaneously condensing and recovering fluoride gas to obtain fluosilicic acid and defluorinated rare earth concentrate;
wherein the mass ratio of the quartz to the mixed rare earth concentrate is 0.04-0.06;
wherein, the mixed rare earth concentrate mainly comprises monazite and bastnaesite.
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| CN117604281A (en) * | 2024-01-23 | 2024-02-27 | 内蒙古科技大学 | Method for promoting fluorine escape in rare earth ore concentrated sulfuric acid decomposition process |
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