CN105803187A - Microwave-assisted decomposition method for Baotou mixed rare earth concentrates - Google Patents

Microwave-assisted decomposition method for Baotou mixed rare earth concentrates Download PDF

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CN105803187A
CN105803187A CN201610334204.8A CN201610334204A CN105803187A CN 105803187 A CN105803187 A CN 105803187A CN 201610334204 A CN201610334204 A CN 201610334204A CN 105803187 A CN105803187 A CN 105803187A
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rare earth
microwave
packet header
mixed rare
assisted
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豆志河
张廷安
刘燕
黄宇坤
吕国志
刘江
张子木
牛丽萍
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Northeastern University China
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    • 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
    • C22B1/02—Roasting processes
    • 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
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a microwave-assisted decomposition method for Baotou mixed rare earth concentrates, and belongs to the technical field of mineral extraction metallurgy. The microwave-assisted decomposition method includes the following steps that (1) microwave-assisted alkaline decomposition is carried out to obtain a mixture containing rare earth oxide; (2) water leaching is carried out to separate out sodium fluoride, wherein water for water leaching is circulated and reused; and (3) hydrochloric acid leaching is carried out. According to the decomposition method, in the microwave-assisted decomposition process, fluorine is converted into sodium fluoride, and generation of fluorine-containing exhaust gas is avoided; phosphorus is converted into calcium phosphate, and rare earth exists in the manner of the oxide; the fluorine can be effectively separated from the rare earth and the phosphorus through water leaching, the fluorine-containing waste water amount is reduced, recovery of the fluorine and circulated utilization of the water for water leaching can be achieved, the production efficiency is improved, and meanwhile the environmental pollution is reduced; and the microwave-assisted decomposition method is an economical, environment-friendly and efficient method and is of actual guiding significance in a Baotou mixed rare earth concentrate smelting process.

Description

A kind of decomposition method of the packet header mixed rare earth concentrates of microwave-assisted
Technical field
The invention belongs to mineral Extraction metallurgy technical field, particularly to the decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted.
Technical background
China is rare earth resources big country, focus primarily upon the Inner Mongol, Sichuan, Jiangxi and four, Shandong province (district), wherein the mischmetal ore deposit in packet header, the Inner Mongol is a kind of polymetallic ore collecting ferrum, niobium, rare earth and thorium, is China's compound rare-earth mineral of distinctive one.Its reserves are huge, are the first in the world big light rare earth resource and second largest thorium resources, and proved reserves are more than 43,000,000 tons.
In the process technique of packet header mixed rare earth concentrates, concentrated sulfuric acid roasting decomposition method and sodium hydroxide caustic leaching process are main processes.In concentrated sulfuric acid roasting catabolic process, rare earth ore concentrate mix with concentrated sulphuric acid after through high temperature (500～600 DEG C) roasting, be decomposed into rare earth sulfate, be all introduced in infusion through water logging.But in concentrated sulfuric acid roasting process, a large amount of waste gas containing fluoride is produced while Rare Earth Concentrate Decomposition, need to use the tail gas treatment devices such as packed tower, spray tower, atomization absorption room for processing these waste gas, considerably increase production cost, and tail gas is also more serious to the etching problem of equipment.Adopting sodium hydroxide caustic leaching process Extraction of rare earth technique that Rare Earth Mine grade requirement is higher, need to be higher than 60%, remain a need for pickling deliming before caustic digestion, operation is longer；It addition, in washing fluorine removal after caustic digestion, phosphorus process, produce a large amount of alkalescence fluoride waste, it is difficult to process, be unfavorable for the recovery of fluorine.Therefore, in the existing production technology of rare earth exist subject matter be: (1) in catabolic process, the process of waste water and gas；(2) the recovery problem of valuable element in the Rare Earth Mine such as fluorine, phosphorus.How to utilize Rare Earth Mine efficiently, cleaning produces rare earth, is the strategic problem that must solve of China's rare-earth industry.
Current China produces with mixed rare earth concentrates, the method for Extraction of rare earth is more." liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates; publication number CN101824531A " that Xu Yanhui of Baotou tombar thite institute et al. proposes discloses the technique that liquid caustic soda low-temperature bake decomposes mixed rare earth concentrates, at 150～550 DEG C to mass ratio 1:(0.5～1.5) mixed rare earth concentrates and sodium hydroxide carry out roasting, the continuous prodution in caustic digestion mischmetal ore deposit can be realized, technical process, without waste gas and ammonia nitrogen waste water, reaches cleaning and produces the purpose with comprehensive utilization of resources." Baotou rare earth ore deposit mixed base roasting method decomposes Extraction of rare earth method; CN103397213A " that Ge Xinfang proposes discloses Baotou rare earth ore concentrate through chemical mineral processing, deliming, ferrum, adopt sodium hydroxide and sodium carbonate mixed base that ore deposit is carried out Roasting Decomposition, through washing fluorine removal, phosphorus；Again with the excellent leaching trivalent rare earth of hydrochloric acid, prepare few cerium greening rare earth and rich cerium ore deposit.The method fluorine removal, phosphorus are effective, and " three wastes " amount solving and avoiding the generation of existing technique is big, reduces the purpose of production cost." microwave-assisted rare earth ore concentrate low temperature acidleach; CN102978392A " that Lee's solution of University Of Science and Technology of the Inner Mongol et al. proposes discloses employing Microwave-assisted firing, rare earth ore concentrate is mixed homogeneously by a certain percentage with concentrated sulphuric acid, decompose at 90～200 DEG C, generate rare earth sulfate, obtain rare earth sulfate solution by water logging.The method reduce acid agent consumption, reduce energy consumption, decrease the discharge of harmful gas, while improving production efficiency, alleviate environmental pollution.
Although process above can improve rare earth leaching rate to a certain extent and alleviate problem of environmental pollution, but it is big to there is waste water and gas amount, and the problem such as fluorine, phosphorus comprehensive recovery be low, still undesirable in actual production.
Summary of the invention
For the deficiency that existing method exists, the present invention provides the decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, the method is decomposing Baotou mixed rare earth concentrates when low temperature, low alkali, it it is the production technology of a kind of clean separation, high efficiency extraction rare earth, pollution-free toxic emission, and wastewater flow rate is relatively low.
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:(0.3～0.5 according to mass ratio), mix homogeneously；Adopting microwave frequency is the microwave oven of 2.3～2.5GHz, after heating 5～15min, constant temperature 10～30min under 140～300 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is (15～20): 1, leaches 50～70min under 60～90 DEG C of conditions, solable matter fully dissolves, after filtration, solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
The hydrochloric acid of water logging slag and 2.5～3mol/L presses liquid-solid ratio (10～15): 1 mixing, leaches 60～90min under 80～90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned packet header mixed rare earth concentrates refers to the Rare Earth Mine product that packet header baiyunebo concentrate is formed through ore dressing, mainly contain bastnaesite and monazite, the mass content sum of cerium oxide, lanthana and Dineodymium trioxide is 45～55wt%, and mineral granularity is 100～300 orders.
In above-mentioned steps 1, described Rare Earth Mine and sodium hydroxide being mixed evenly refers to pulverizes after Rare Earth Mine, sodium hydroxide being mixed in proportion in the lump；Packet header mixed rare earth concentrates and preferred 1:(0.35～0.50 of sodium hydroxide mass ratio), microwave heating time is 5～15min preferably, and microwave heating temperature preferably 140～240 DEG C, constant temperature time is 10～30min preferably；The preferred 15:1 of water logging liquid-solid ratio in above-mentioned steps 2, water soaking temperature preferably 70～80 DEG C, water logging time preferred 60min；The preferred 3mol/L of concentration of hydrochloric acid of above-mentioned steps 3 Leaching in Hydrochloric Acid, acidleach liquid-solid ratio preferred (10～15): 1, acidleach temperature preferably 80～90 DEG C, leaching time is 60～70min preferably.
In above-mentioned steps 1, bastnaesite and monazite are all decomposed generation rare earth oxide, and RE is Ce, La, Nd, and its reaction is as follows:
2REFCO3+ 6NaOH=RE2O3+2NaF+2Na2CO3+3H2O；
2REPO4+ 6NaOH=RE2O3+2Na3PO4+3H2O；
2Ce2O3+O2=4CeO2；
2CeO2+Nd2O3=4Ce0.5Nd0.5O1.75；
CaF2+ 2NaOH=Ca (OH)2+2NaF；
9CaF2+4Na3PO4+3Na2CO3+Ca(OH)2=Ca10(PO4)4(CO3)3(OH)2+18NaF。
Beneficial effects of the present invention:
1, the decomposition method of the packet header mixed rare earth concentrates of microwave-assisted of the present invention, Rare Earth Mine decomposition efficiency is high, generates the rare earth oxide being easily leached after decomposition, only has steam in waste gas, pollution-free.
2, compared to existing production technology, the present invention has that decomposition temperature is low, capacity usage ratio is high, Rare Earth Mine decomposition efficiency advantages of higher；In existing roasting process of sulfuric acid, temperature is all more than 500 DEG C, and the present invention passes through microwave-assisted, under lower temperature (140～300 DEG C), can realize the decomposition of packet header mixed rare earth concentrates；Decomposing the product obtained in prior art is acidifying rare earth or alkalization rare earth, and it is rare earth oxide that middle wrapping head mixed rare earth concentrates of the present invention decomposes the product obtained.
3, the present invention only needs a set of microwave heating equipment, converting electrical energy into microwave by ore deposit sorption enhanced is heat energy, technological operation is simple and environmentally-friendly, and eliminate the pre-deliming operation of pickling in tradition alkali decomposition process, reduce the consumption of chemical industry supplementary material, shorten technological process, improve the production efficiency of rare earth ore concentrate, rare-earth smelting technique is had actual directive significance.
4, adopting microwave heating technique decomposing Baotou mixed rare earth concentrates, its heating mechanism is to act on polar molecule, has firing rate fast, and the advantage improving mineral active is conducive to decomposition and the leaching of rare earth ore concentrate；Microwave also has selectivity heat characteristic, and stone-like pulse can not absorb microwave and heat up, and therefore adopts microwave heating can reduce alkali consumption, improves capacity usage ratio；Being 60～72% compared to the mass percent of NaOH addition in traditional method, the mass percent of NaOH addition of the present invention is 40～50%, and microwave heating 10min, constant temperature 30min, and the leaching rate of rare earth can reach more than 95%.
5, in tradition alkali roasting decomposition process, fluorine, phosphorus are washed out by washing simultaneously, adopt microwave-assisted to process packet header mixed rare earth concentrates, and bastnaesite and monazite are decomposed generation rare earth oxide；Fluorine is converted into sodium fluoride, and phosphorus is converted into calcium phosphate；By water logging, fluorine can be washed out, and rare earth oxide and calcium phosphate enter into next step acidleach operation, it is achieved that the independent extraction of fluorine；Fluorine extraction rate up to more than 95%, and water for industrial use is existing industrial water consumption 1/3；Containing only there being sodium fluoride in infusion, be conducive to the recovery of fluorine and recycling of water diffusion water.
Accompanying drawing explanation
Fig. 1 is the process chart of the embodiment of the present invention.
Detailed description of the invention
The process chart of the embodiment of the present invention is as shown in Figure 1.
Embodiment 1
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.35 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.3GHz, after heating 10min, constant temperature 30min under 140 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 20:1, leaches 60min under 90 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 3mol/L, leaches 60min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculate the leaching rate of fluorine, wherein ηFFor the leaching rate of fluorine, %；CFFor the mass concentration of fluorine, g/L in infusion；V2For infusion volume, L；M2For the quality of the mixture containing rare earth oxide, g；ωFFor the mass percent of fluorine element, % in the mixture containing rare earth oxide；In the present embodiment, the leaching rate of fluorine is 92.18%.Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculate the leaching rate of phosphorus, wherein ηP1For the leaching rate of water logging process phosphorus, %；CP1For the mass concentration of phosphorus, g/L in infusion；ωP1For the mass percent of the mixture P elements containing rare earth oxide, %；In the present embodiment, now the leaching rate of phosphorus is 1.88%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculate rare earth leaching rate, wherein ηREFor the leaching rate of rare earth element, %；CREFor rare earth element mass concentration in leachate, g/L；V1For leachate volume, L；M1For water logging slag amount, g；ωREFor the mass percent of water logging slag rare earth elements, %；The present embodiment middle rare earth leaching rate is 92.67%.Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculate the leaching rate of phosphorus, wherein ηP2For the leaching rate of acidleach process phosphorus, %；CP2For the mass concentration of phosphorus, g/L in leachate；ωP2For the mass percent of P elements, % in water logging slag；In the present embodiment, now the leaching rate of phosphorus is 85.98%.
Embodiment 2
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.35 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.45GHz, after heating 10min, constant temperature 30min under 240 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 20:1, leaches 70min under 90 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 10:1 with the hydrochloric acid of 3mol/L, leaches 60min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 95.36%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 1.29%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 94.39%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 87.68%.
Embodiment 3
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.35 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.45GHz, after heating 10min, constant temperature 30min under 300 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 15:1, leaches 60min under 90 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 3mol/L, leaches 60min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 94.48%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 1.15%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 98.36%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 89.45%.
Embodiment 4
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.35 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.45GHz, after heating 5min, constant temperature 30min under 240 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 20:1, leaches 50min under 60 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 3mol/L, leaches 60min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 89.25%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 0.94%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 88.47%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 82.13%.
Embodiment 5
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.35 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.45GHz, after heating 15min, constant temperature 30min under 240 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 20:1, leaches 60min under 90 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 3mol/L, leaches 60min under 80 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 91.61%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 1.12%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 90.23%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 83.24%.
Embodiment 6
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.50 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.45GHz, after heating 10min, constant temperature 30min under 240 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is 20:1, leaches 70min under 90 DEG C of conditions, and solable matter fully dissolves, after filtration, and solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 3mol/L, leaches 90min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 97.21%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 1.78%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 97.48%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 92.64%.
Embodiment 7
The decomposition method of the packet header mixed rare earth concentrates of a kind of microwave-assisted, comprises the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:0.30 according to mass ratio, mix homogeneously；Adopting microwave frequency is the microwave oven of 2.5GHz, after heating 10min, constant temperature 10min under 240 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, water logging liquid-solid ratio is 20:1, leaches 70min, by slag-liquid separation, complete the leaching of fluorine under 90 DEG C of conditions；
Step 3, Leaching in Hydrochloric Acid:
Water logging slag mixes by liquid-solid ratio 15:1 with the hydrochloric acid of 2.5mol/L, leaches 90min under 90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
Above-mentioned steps 2 adopt lanthanum-alizarin complexation hydrazone method by the mass concentration of fluorine in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of fluorine, in the present embodiment, the leaching rate of fluorine is 83.34%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination infusion, and according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 1.56%.
Above-mentioned steps 3 adopts ProdigyXP type entirely compose direct reading emission spectrometer (ICP) and measure rare earth element mass concentration in leachate, and utilize chemical titration that measurement result is verified, according to formulaCalculating rare earth leaching rate, the present embodiment middle rare earth leaching rate is 85.49%；Adopt bismuth salt-molybdenum blue absorption photometry by the mass concentration of phosphorus in Optizen2120UV type ultraviolet/visible light photometric determination leachate, according to formulaCalculating the leaching rate of phosphorus, in the present embodiment, now the leaching rate of phosphorus is 83.24%.

Claims (5)

1. the decomposition method of the packet header mixed rare earth concentrates of a microwave-assisted, it is characterised in that comprise the following steps:
Step 1, microwave-assisted caustic digestion:
Adding sodium hydroxide in the mixed rare earth concentrates of packet header, packet header mixed rare earth concentrates and sodium hydroxide are 1:(0.3～0.5 according to mass ratio), mix homogeneously；Adopting microwave frequency is the microwave oven of 2.3～2.5GHz, after heating 5～15min, constant temperature 10～30min under 140～300 DEG C of conditions, fully decomposes packet header mixed rare earth concentrates, obtains the mixture containing rare earth oxide；
Step 2, water logging:
Adding deionized water in mixture containing rare earth oxide and carry out water logging, the liquid-solid ratio of water logging is (15～20): 1, leaches 50～70min under 60～90 DEG C of conditions, solable matter fully dissolves, after filtration, solid-liquid separation, obtain water logging slag and infusion；Infusion distillation crystallization, obtains NaF crystal, and the water that distillation crystallization obtains recycles as deionized water；
Step 3, Leaching in Hydrochloric Acid:
The hydrochloric acid of water logging slag and 2.5～3mol/L presses liquid-solid ratio (10～15): 1 mixing, leaches 60～90min under 80～90 DEG C of conditions；Acidleach is complete, is filtrated to get leachate and leached mud.
2. the decomposition method of the packet header mixed rare earth concentrates of the microwave-assisted according to claims 1, it is characterized in that: packet header mixed rare earth concentrates mainly contains bastnaesite and monazite, the mass content sum of cerium oxide, lanthana and Dineodymium trioxide is 45～55wt%, and mineral granularity is 100～300 orders.
3. the decomposition method of the packet header mixed rare earth concentrates of the microwave-assisted according to claims 1, it is characterized in that: in described step 1, packet header mixed rare earth concentrates and sodium hydroxide are 1:(0.35～0.50 according to mass ratio), after microwave heating, constant temperature 10～30min under 140～240 DEG C of conditions.
4. the decomposition method of the packet header mixed rare earth concentrates of the microwave-assisted according to claims 1, it is characterised in that: in described step 2, water logging liquid-solid ratio is 15:1, leaches 60min under 70～80 DEG C of conditions.
5. the decomposition method of the packet header mixed rare earth concentrates of the microwave-assisted according to claims 1, it is characterized in that: in described step 3, the hydrochloric acid of water logging slag and 3mol/L is by liquid-solid ratio (10～15): 1 mixes, and leaches 60～70min under 80～90 DEG C of conditions.
CN201610334204.8A 2016-05-19 2016-05-19 Microwave-assisted decomposition method for Baotou mixed rare earth concentrates Pending CN105803187A (en)

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Publication number Priority date Publication date Assignee Title
CN106586992A (en) * 2016-12-10 2017-04-26 包头稀土研究院 Comprehensive fluorine and phosphorous recovery technology for liquid caustic soda decomposition of mixed rare earth concentrate
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