CN115340116A - Method for recovering sodium and fluorine in alkali-to-wastewater - Google Patents
Method for recovering sodium and fluorine in alkali-to-wastewater Download PDFInfo
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- CN115340116A CN115340116A CN202210765356.9A CN202210765356A CN115340116A CN 115340116 A CN115340116 A CN 115340116A CN 202210765356 A CN202210765356 A CN 202210765356A CN 115340116 A CN115340116 A CN 115340116A
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering sodium and fluorine in alkali-to-wastewater, which comprises the following steps: s1, roasting, acid leaching and alkali conversion are carried out on bastnaesite, then, alkali conversion mother liquor and alkali conversion slag are obtained through filtration, and the alkali conversion slag is washed for multiple times; s2, heating the alkali-conversion mother liquor and then introducing CO 2 Performing aluminum removal reaction, standing for clarification, generating cryolite-containing precipitate at the bottom of the alkali conversion mother liquor, siphoning supernatant to obtain fluorine-containing alkali water, transferring filtrate into fluorine-containing alkali water, and transferring the cryolite-containing precipitate for landfill or purifying to obtain a cryolite product; and S3, adding quicklime or/and hydrated lime into the fluorine-containing alkaline water, filtering to obtain filtrate and filter residue, concentrating the filtrate, recycling the concentrated filtrate as liquid alkaline, and treating the filter residue as calcium fluoride mixed residue for the next step. The method realizes the recovery of sodium and fluorine in the alkali-conversion wastewater without increasing the treatment cost, obtains byproducts with economic value, and reduces the wastewater of enterprisesThe treatment cost avoids the waste of fluorine resources and sodium resources.
Description
Technical Field
The invention relates to the technical field of rare earth hydrometallurgy, in particular to a method for recovering sodium and fluorine in alkali-to-wastewater.
Background
At present, rare earth hydrometallurgy enterprises in Sichuan mainly use bastnaesite which is concentrated in yak plateau mines in crown ning county of Sichuan province, and the prior mature production process of the bastnaesite is to obtain mixed rare earth chloride and acid leaching slag after the bastnaesite is oxidized and roasted and treated by an acid-base combination method. The mixed rare earth chloride is subjected to extraction separation, precipitation and calcination, and then is mixed to obtain a single rare earth oxide production process, waste water generated in the production process is treated by a rare earth recovery process and then is discharged up to the standard, hazardous waste residues are treated by a rare earth recovery process and then are temporarily stored in a hazardous waste storehouse, and the common solid waste is transported and buried. The produced waste water mainly comprises three parts of fluorine-containing waste water, precipitated high-salinity waste water and extracted acidic waste water, the waste gas mainly comprises toxic and harmful gases such as chlorine, hydrogen chloride, hydrogen sulfide and the like, and the waste residue mainly comprises dangerous waste residues of lead slag and iron thorium slag, common water treatment mud, coal slag and other common solid wastes.
At present, the environmental protection emission requirements of the national enterprises producing the rare earth by the wet method are more and more strict, so the emission requirements of three wastes, especially sewage, are higher, the emission is allowed after the high salt in the wastewater is recycled and treated to reach the standard, then many production enterprises change the sodium precipitation of the rare earth precipitation into the ammonium precipitation, extract organic calcium soap and sodium soap into the ammonium soap, then recover ammonia chloride by adopting a concentration crystallization mode, and the wastewater is treated to reach the standard and is discharged. Compared with the process for recycling sodium chloride, the method has simple process requirements and better economic benefits of recycling, but for the influence of the process property on the alkaline fluorine-containing wastewater (namely, the alkali-to-mother liquor) generated in the acid leaching process, the optimal process for treating the bastnaesite at present can ensure the yield of the acid leaching process of the bastnaesite only by adopting a mode of leaching with hydrochloric acid, then performing alkali-to-alkali conversion with sodium hydroxide and then performing acid leaching, so that the used raw auxiliary material is poor in sodium hydroxide substitutability, sludge slag is easy to form and difficult to treat in the subsequent process of treating the fluorine-containing alkaline wastewater, and more impurities are carried in the process of recycling sodium salt and are difficult to recycle.
For the treatment of fluorine-containing alkaline wastewater generated after the alkali conversion, the more advanced treatment technology in recent years is to add lime or calcium chloride into the wastewater, and reduce the fluorine ions in the wastewater to the discharge standard of the rare earth industry and discharge the fluorine ions in a manner that calcium ions and fluorine ions are combined to form precipitates. However, the calcium fluoride slag formed by the treatment method has high impurities, the purity of the calcium fluoride is only 76-85%, and the calcium fluoride contains a considerable part of impurities such as barium, radium, lead and the like, has no economic value and can only be directly transported to a mine landfill. Meanwhile, the generated alkaline wastewater and the extraction waste acid water form high-salinity wastewater after the pH value is adjusted, and sodium chloride can be recovered only by adopting a concentration and crystallization mode subsequently, so that the salt content of the wastewater is reduced, the economic value of sodium resources is reduced, and the wastewater treatment cost of enterprises is increased.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a method for recovering sodium and fluorine in alkali-to-waste water, which realizes the recovery of sodium and fluorine in the alkali-to-waste water without increasing the treatment cost, obtains a high-purity byproduct with economic value, reduces the waste water treatment cost of enterprises, increases the profits of the enterprises, avoids the waste of fluorine resources and sodium resources, and overcomes the defects of the traditional treatment process.
The technical scheme adopted by the invention is as follows: a method for recovering sodium and fluorine from a caustic shift wastewater, comprising the steps of:
s1, roasting, acid leaching and alkali transferring bastnaesite, filtering to obtain an alkali transferring mother liquor and alkali transferring slag, washing the alkali transferring slag for multiple times, transferring water washing liquor to a water washing liquor treatment process for treatment, and treating the washed alkali transferring slag in the next process;
s2, heating the alkali-transfer mother liquor to 50-70 ℃, and then introducing CO 2 Performing aluminum-removing reaction for 1-3h, standing for clarification, transferring the supernatant to give fluorine-containing alkaline solution, filtering the mother solution, collecting the precipitate, transferring the filtrate to fluorine-containing alkaline water, and transferring the precipitate to landfill or purificationDrying the cryolite into a byproduct;
s3, measuring the concentration of fluorine ions in the fluorine-containing alkaline water, adding quicklime or/and hydrated lime into the fluorine-containing alkaline water, reacting for 1-3h, filtering to obtain filtrate and filter residue, concentrating the filtrate to be used as liquid alkali for recycling, and using the filter residue as calcium fluoride mixed residue for the next step.
And further, adding hydrochloric acid into the calcium fluoride mixed slag for pickling for multiple times, then filtering to obtain filtrate and calcium fluoride filter residues, recycling the filtrate as a defluorination agent in the washing liquid treatment process, and drying the calcium fluoride filter residues to obtain a calcium fluoride product.
Further, in the working procedure of water washing liquid treatment, filtrate obtained by acid washing of the calcium fluoride mixed slag is added into the water washing liquid of the alkali conversion slag, the mixture is stirred, mixed and then kept stand for precipitation, then the filtrate is filtered to obtain the calcium fluoride slag and defluorination wastewater, the calcium fluoride slag is treated in the next working procedure or is buried, and the defluorination wastewater is treated and then is discharged after reaching the standard.
Further, during the alkali conversion, heating liquid alkali to a boiling state, wherein the alkali conversion time is more than 6h, and the solid-liquid ratio during the alkali conversion is 1:4 to 6, and the concentration of the residual alkali after the alkali conversion is controlled to be 0.4mol/L to 0.8mol/L.
Further, when the alkali-transferring slag is washed by water, the 1 st and 2 nd water washing liquids are combined into the alkali-transferring mother liquid, and the subsequent water washing liquid is transferred to the water washing liquid treatment process for treatment.
Further, in S2, the precipitate containing cryolite in the alkali-transfer mother liquor is enriched, and then the precipitate is filtered.
Furthermore, the concentration of sodium fluoride in the alkali-conversion mother liquor is controlled to be 30-40g/L.
Further, when washing alkali and transferring slag, controlling the solid-liquid ratio to be 1:4-6 (within the range, the fluorine removal rate of the acid leaching residue can be effectively ensured), and the ratio of 1:4.
in summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, sodium ions in the fluorine-containing waste alkali water are recycled again to form auxiliary materials in production, namely, high-purity liquid alkali is obtained, so that the problem that the subsequent formation of high-salt waste water increases the treatment difficulty is solved, the production cost is greatly saved, the purpose of recycling resources is achieved, and meanwhile, the profit growth point is increased for enterprises;
2. the recycled calcium fluoride is purified after repeated acid washing to obtain a high-purity calcium fluoride product (meeting the requirements of second-class industrial grade and first-class products), so that the calcium fluoride slag generates economic value, the acid washing solution can be used for removing fluorine, a fluorine removing agent is not required to be additionally used, no new waste water and waste are generated, the treatment raw materials are fully utilized, the calcium fluoride slag can be sold as a product, and the problems of increased treatment cost and environmental pollution caused by the burying treatment of the calcium fluoride slag are solved;
3. the method effectively reduces sodium salt and fluoride ions in the wastewater, so that the sodium salt can be recycled, and simultaneously, the slag amount of the wastewater is effectively reduced by purifying calcium fluoride slag;
drawings
FIG. 1 is a schematic process flow diagram of a method for recovering sodium and fluorine from the waste water from the caustic conversion of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, a method for recovering sodium and fluorine in the acid-base combined process for treating bastnaesite alkali conversion wastewater comprises the following steps:
s1, oxidizing and roasting rare earth bastnaesite, adding acid to dissolve the rare earth bastnaesite, filtering, transferring filtrate serving as a product to an impurity removal process for impurity removal, wherein the main component of filter residue is rare earth fluoride;
s2, placing the filter residue in alkali liquor, heating to boil, converting the alkali for more than 6 hours, standing after the alkali conversion is finished, and siphoning supernatant; after the alkali conversion is finished, the solid-liquid ratio in the feed liquid is 1: (4-6), the concentration of residual alkali is 0.4-0.8 mol/L, the concentration of sodium fluoride is about 35g/L, and the alkali conversion reaction equation is as follows:
2REF 3 +3NaOH＝RE 2 (OH) 3 +3Na + +6F －
2CeF 3 +3NaOH＝Ce 2 (OH) 3 +3Na + +6F －
Ce 2 (OH) 3 +O 2 +H 2 O＝2Ce(OH) 4
Al 2 O 3 +2NaOH＝2NaAlO 2 +H 2 O
s3, transferring the supernatant (namely the alkali-transfer mother liquor) obtained by siphoning in the step S2 into a reaction kettle, washing the alkali-transfer slag for multiple times, and keeping the solid-to-liquid ratio in washing to be 1: (4-6), filtering, continuously washing filter cakes with water, combining the washing solutions for 1 time and 2 times, transferring the washing solutions into an alkali transfer mother solution, wherein the concentration of sodium fluoride in the reaction kettle is about 20g/L, and transferring the subsequent washing solutions into a washing solution treatment process for treatment;
s4, heating the alkali-transfer mother liquor to 50-70 ℃ (preferably 60 ℃, but also 50 ℃, 55 ℃, 58 ℃, 65 ℃, 70 ℃ and the like), and introducing CO 2 The aluminum removing reaction is carried out, and the reaction equation is as follows:
NaAlO 2 +NaF+CO 2 ＝Na 3 AlF 6 ↓+3H 2 0+3Na 2 C0 3
the reaction time is 1-3h, then the mixture is stood still and clarified to produce cryolite (Na) 3 AlF 6 ) The precipitate sinks into the bottom of the reaction kettle, the supernatant (namely fluorine-containing alkaline water) is siphoned into another reaction kettle, the bottom of the cryolite-containing precipitate is reserved for next use, and the cryolite-containing precipitate is enriched and filtered, or can be directly filtered, and then is purified and dried to form a cryolite byproduct or is directly transported and buried;
s5, adding 1-1.5 times of calx or/and hydrated lime in calculated amount into the fluorine-containing wastewater, reacting for 1-3 hours, then filtering, recovering the filtrate into an MRV concentration system for concentration, transferring the filter residue (namely calcium fluoride mixed residue) into a reaction tank, wherein the reaction equation of the system is as follows:
reaction of quicklime and sodium fluoride: caO +2H 2 O+2NaF＝CaF 2 +2NaOH
Reaction of slaked lime with sodium fluoride: ca (OH) 2 +2NaF＝CaF 2 ↓+2NaOH
Note that: the reaction is endothermic reaction, excessive quicklime or hydrated lime is added to remove fluorine in the system as much as possible, sodium ions are left to produce sodium hydroxide solution, and after MRV concentration, the concentration of sodium hydroxide in the filtrate reaches the concentration required by alkali conversion of acid leaching residue, the sodium hydroxide solution is directly used as liquid alkali for alkali conversion;
s6, adding hydrochloric acid into filter residues in the reaction tank for washing, repeating for multiple times, filtering, drying the filter residues, and packaging to obtain a calcium fluoride product; in this step, the main reason for washing the filter residue with hydrochloric acid is to wash clean part of the soluble impurities in the filter residue, and the reaction equation is as follows:
and (3) dissolving and removing unreacted hydrated lime or quick lime by using hydrochloric acid:
CaO+2HCl＝CaCl 2 +H 2 O
Ca(OH) 2 +2HCl＝CaCl 2 +2H 2 O
the rest of barium, radium, lead and the like react with hydrochloric acid to generate soluble salt to be removed, so that the purity of the calcium fluoride slag is improved.
In order to better illustrate the invention, specific examples are listed below:
example 1
A method for recovering sodium and fluorine from a caustic shift wastewater, comprising the steps of:
s1, oxidizing and roasting rare earth bastnaesite, adding hydrochloric acid (the concentration of hydrochloric acid is more than or equal to 31 percent), stirring and dissolving, filtering after acid leaching reaction is finished, taking filtrate as acid leaching solution, transferring the acid leaching solution to an impurity removal process for impurity removal, taking filter residue as acid leaching residue (detected, the acid leaching residue amount is 2000kg (dry basis), the water content is about 58 percent, and the fluorine content is 11.23 percent), and transferring the acid leaching residue to an alkali transfer process for alkali transfer;
s2, carrying out alkali conversion on the acid leaching residue, wherein the alkali liquor is liquid alkali with NaOH concentration being more than or equal to 45%, heating the alkali liquor to boiling, then carrying out alkali conversion for more than 6 hours, and after the alkali conversion is finished, the solid-liquid ratio in the material liquid is 1:4, standing, siphoning supernatant, taking the supernatant as an alkali-transfer mother liquor, wherein the concentration of residual alkali in the alkali-transfer mother liquor is 0.6mol/L, the concentration of fluorine ions is 0.93mol/L, the concentration of sodium ions is 1.53mol/L, and transferring alkali-transfer residues (alkali cakes) into a water washing process for continuous treatment;
s3, washing the alkali-treated slag for multiple times with water, wherein the solid-to-liquid ratio is kept at 1:4, combining the water washing liquid obtained by the first and second water washing with the alkali transfer mother liquor, and transferring the water washing liquid obtained by the subsequent water washing to a water washing liquid treatment process for treatment;
s4, heating the alkali-to-mother liquor to 60 ℃, and then introducing CO 2 Reacting for 1.5h, standing for clarification, generating cryolite precipitate at the bottom of feed liquid, siphoning supernatant to obtain fluorine-containing alkaline water, wherein the concentration of fluorine ions in the fluorine-containing alkaline water is 0.35mol/L, the concentration of sodium ions in the sodium ions is 0.93mol/L, directly filtering the cryolite, and drying to obtain 53kg of cryolite byproduct with higher impurity content;
and S5, adding 1.2 times of calx in calculated amount into the fluorine-containing alkaline water, reacting for 1.5 hours, filtering, recovering the filtrate into an MRV concentration system, concentrating to obtain liquid alkali with NaOH concentration more than or equal to 45%, directly recovering the liquid alkali as alkali-to-liquid alkali, and treating the filter residue as calcium fluoride mixed residue for the next step.
According to statistics, 2000kg of dry-based acid leaching residue (with the water content of 58% and the fluorine content of 11.23%) can generate 53kg of cryolite (with the purity of about 57%) and liquid caustic soda with the NaOH concentration of not less than 45% of about 1400L after the treatment of the steps, wherein in the liquid caustic soda, the fluorine ion concentration is only 20mg/L, the recovery rate of sodium is 93%, and the calcium fluoride content in the obtained calcium fluoride mixed residue is 87%.
Example 2
Example 2 the same as example 1, except that the calcium fluoride mixed slag obtained in example 1 was treated as follows:
adding hydrochloric acid (the concentration of the hydrochloric acid is more than or equal to 31%) into the calcium fluoride mixed slag for acid washing, repeatedly carrying out acid washing for 2 times, then filtering to obtain a calcium chloride solution and calcium fluoride filter residues, transferring the calcium chloride solution to a washing liquid treatment process for treatment, drying and packaging the calcium fluoride filter residues to obtain about 550kg of calcium fluoride products, and detecting that the calcium fluoride products meet the requirements of two types of industrial grade first-class products and can be directly sold to the outside.
Through comprehensive statistics, the alkali-conversion mother liquor originally contains 0.93mol/L of fluoride ions, and after treatment (forming purified cryolite and calcium fluoride products), the concentration of the fluoride ions in the calcium chloride solution is 20mg/L, and the recovery rate of the fluoride ions reaches 98%.
Example 3
Example 3 is the same as example 2 except that the aqueous washing solution treatment process includes the steps of:
the calcium chloride solution generated by the calcium fluoride mixed slag is used as defluorination liquid, the defluorination liquid is stirred and mixed with water washing liquid generated by washing alkali to slag, after the calcium chloride solution is subjected to precipitation reaction for a period of time, the calcium chloride solution is stood, then the calcium fluoride slag (the content of calcium fluoride is 78%) and defluorination wastewater are obtained by filtering, the concentration of fluorine ions in the defluorination wastewater is below 8mg/L, the defluorination wastewater completely meets the discharge requirement, and the standard discharge can be realized only by simply treating the fluorine-containing wastewater subsequently.
In the embodiment, the fluorine content in the cryolite product, the calcium fluoride product and the calcium fluoride slag is combined, and the calculation result shows that the recovery rate of fluorine in the acid leaching slag reaches 92.5 percent on the whole, and the recovery rate is considerable.
Comparative example 1
Comparative example 1 is the same as example 1 except that the alkali conversion mother liquor is not fed with CO 2 The reaction is carried out, but quicklime is directly added for treatment, and other conditions are the same.
Through detection, in the liquid caustic soda with the same concentration obtained by concentration, the concentration of fluorine ions reaches 80mg/L, the content of aluminum impurities in the liquid caustic soda is about 3.6g/L, and the quality requirement of the liquid caustic soda cannot be met.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. A method for recovering sodium and fluorine in alkali-conversion wastewater is characterized by comprising the following steps:
s1, roasting, acid leaching and alkali transferring bastnaesite, filtering to obtain an alkali transferring mother liquor and alkali transferring slag, washing the alkali transferring slag for multiple times, transferring the washing liquid to a washing liquid treatment process for treatment, and treating the washed alkali transferring slag in the next process;
s2, heating the alkali-transfer mother liquor to 50-70 ℃, and then introducing CO 2 Performing aluminum removal reaction for 1-3h, standing for clarification, generating a precipitate containing cryolite at the bottom of an alkali conversion mother liquor, siphoning supernatant to obtain fluorine-containing alkali water, filtering the mother liquor, taking the precipitate containing cryolite, transferring filtrate into fluorine-containing alkali water, and transferring the precipitate containing cryolite to landfill or purifying the cryolite into a byproduct;
s3, measuring the concentration of fluorine ions in the fluorine-containing alkaline water, adding quicklime or/and slaked lime into the fluorine-containing alkaline water, reacting for 1-3h, filtering to obtain filtrate and filter residue, concentrating the filtrate, recycling the filtrate as liquid alkali, and treating the filter residue as calcium fluoride mixed residue for the next step.
2. The method for recovering sodium and fluorine in the waste water from alkali conversion according to claim 1, wherein hydrochloric acid is added into the calcium fluoride mixed residue for acid washing for a plurality of times, and then the calcium fluoride mixed residue is filtered to obtain filtrate and calcium fluoride filter residue, the filtrate is recycled as a fluorine removal agent in the treatment process of the washing liquid, and the calcium fluoride filter residue is dried to obtain a calcium fluoride product.
3. The method for recovering sodium and fluorine in the alkali-shift wastewater according to claim 2, wherein in the step of treating the washing liquid, the filtrate obtained by acid-washing the calcium fluoride mixed slag is added into the washing liquid of the alkali-shift slag, the mixture is stirred and then is kept stand for precipitation, then the calcium fluoride slag and the defluorination wastewater are obtained by filtration, the calcium fluoride slag is treated in the next step or is buried, and the defluorination wastewater is treated and then is discharged after reaching the standard.
4. The method for recovering sodium and fluorine in the waste water from the caustic conversion according to any one of claims 1 to 3, wherein the liquid caustic is heated to boiling state during the caustic conversion, the caustic conversion time is 6 hours or more, and the solid-to-liquid ratio during the caustic conversion is 1:4 to 6, and the concentration of the residual alkali after the alkali conversion is controlled to be 0.4mol/L to 0.8mol/L.
5. The method for recovering sodium and fluorine in the waste water from alkali-shift according to claim 4, wherein the 1 st and 2 nd water washing liquids are combined into the mother liquor from alkali-shift during the washing of the alkali-shift slag, and the subsequent water washing liquid is transferred to the water washing liquid treatment process for treatment.
6. The method for recovering sodium and fluorine in the waste water of alkali-shift conversion according to claim 5, wherein the precipitate containing cryolite in the mother liquor of alkali-shift conversion is enriched in S2 and then the precipitate is filtered.
7. The method for recovering sodium and fluorine in the alkaline shift waste water according to claim 6, wherein the concentration of sodium fluoride in the alkaline shift mother liquor is controlled to be 30 to 40g/L.
8. The method for recovering sodium and fluorine in the waste water from the caustic conversion according to claim 7, wherein the solid-to-liquid ratio is controlled to be 1:4-6.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5867836A (en) * | 1981-10-15 | 1983-04-22 | Dowa Mining Co Ltd | Decomposition of bastnaesite ore |
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN110512098A (en) * | 2019-08-29 | 2019-11-29 | 包头钢铁（集团）有限责任公司 | A kind of method that bastnaesite wet process prepares rare earth chloride |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5867836A (en) * | 1981-10-15 | 1983-04-22 | Dowa Mining Co Ltd | Decomposition of bastnaesite ore |
| CN102146512A (en) * | 2010-02-08 | 2011-08-10 | 北京有色金属研究总院 | Hamartite smelting separation process |
| CN110512098A (en) * | 2019-08-29 | 2019-11-29 | 包头钢铁（集团）有限责任公司 | A kind of method that bastnaesite wet process prepares rare earth chloride |
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