CN101824531A - Liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates - Google Patents
Liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates Download PDFInfo
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Abstract
The invention relates to a liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, which comprises the following steps of: (1) mixing mixed rare earth concentrates and sodium hydroxide in the weight ratio of 1:0.5 to 1.5; (2) roasting the mixed rare earth ore at the roasting temperature of between 150 and 550 DEG C for 0.5 to 4 hours; (3) washing roasted ore water obtained by roasting until the water is neutral; (4) dissolving washed alkali cakes in hydrochloric acid, and controlling the pH value to be between 4 and 5 to prepare rare earth chloride solution; (5) after washing thorium enrichment dissolved by the hydrochloric acid, performing sealing pile-up or extracting thorium and rare earth through further dissolution. The mixed rare earth concentrates are processed by adopting the low-temperature roasting decomposition process, so that the continuous production of the alkali-decomposing mixed rare earth ore can be realized, no waste gas or ammonia nitrogen waste water is generated in the process, and the pollution-free production and comprehensive utilization of resources are realized.
Description
Technical field:
The present invention relates to a kind of liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, belong to the rare earth metallurgy field.
Background technology:
The rare earth resources in packet header is richly endowed by nature, accounts for 81% of national rare earth reserves, and Baotou rare earth ore concentrate accounts for China and smelts more than 60% of rare earth ore concentrate.The technology of extracting mishmetal from Baotou rare earth ore concentrate mainly is concentrated sulfuric acid roasting technology.But there is following some insoluble environmental protection defective in this technology: (1) roasting tail gas is the sour gas that contains a large amount of sulphur and fluorine, and the method that adopts the water spray to absorb is handled, but discharging tail gas is difficult to reach national relevant emission standards.Simultaneously, be difficult to recycle, can only adopt the lime neutralization method to handle because spray liquid is the mixing acid of sulfuric acid, silicofluoric acid and hydrofluoric acid, not only in and the quantity of slag big, and cause secondary pollution easily.(2) the thorium element combines in the leached mud, it is very big that this leaches the quantity of slag, account for more than 30% of rare earth ore concentrate amount, and radioactive intensity surpasses national low-activity slag standard, it is preserved and handles quite difficulty, and thorium is difficult to be recycled owing to generate thorium pyrophosphate in roasting process as a kind of resource.(3) this technology also produces in process of production and contains ammonia nitrogen class ammonium sulfate waste water, and this part waste water is because the low complicated component intractable of ammonia nitrogen concentration.
Another important decomposition technique of Baotou rare earth ore concentrate is the liquid caustic soda decomposition technique.This technology is at first used dissolving with hydrochloric acid deliming (rare earth loss 2-3%), washes excess acid then, decomposes with liquid caustic soda again, washes the soluble salt of excess base and generation then, the last excellent molten re chloride that obtains of hydrochloric acid.Fluorine, phosphorus enter in the solution and are reclaimed in this technology, thorium reclaims with the form of the thorium enriched thing of iron or can further separate purification, do not produce acid waste gas, the waste water that contains ammonia nitrogen and emissive industrial waste residue in the technological process, clean the technical process of decomposing than being one with acid technological process.But this technology has following major defect: operational process of craft is discontinuous, be the batch operation that in reactor, carries out, two step solid-liquid reaction and follow-up washings, the solid-liquid separation difficulty also consumes big water gaging, water resource waste is big, therefore is unfavorable for scale operation and application.A major cause that causes above-mentioned defective is many technological processs in a step " pickling deliming " in technological process.Calcium contents is generally at 6-12% in the Baotou rare earth ore concentrate, and present processing requirement deliming operation makes calcium contents be less than 1%, otherwise can influence the decomposition and the leaching of rare earth, reduces the rate of recovery of rare earth.Chinese patent " the alkali hydrothermal method is decomposed the technology and the equipment of preparation rare earth chloride from rare earth ore concentrate " (CN1142542A) has been invented the technology of decomposing rare-earth mineral under a kind of high pressure, decomposition reaction need be carried out in the reactor under the pressure of 1.8～2.0Mpa, remains batch operation.If can overcome the shortcoming of above-mentioned batch operation, cancellation pickling deliming operation realizes continuous reaction, and this technology will be the smelting technology of real efficient a, cleaning, comprehensive utilization of resources.
Summary of the invention:
The objective of the invention is for solve existing rare earth ore concentrate alkali decomposition course need the pickling deliming, can not the quantity-produced problem, and the recovery that realizes resources such as valuable element rare earth, thorium, fluorine provides a kind of liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, and the present invention can make alkali decomposition process realize the serialization industrial production.
For realizing purpose of the present invention, liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates provided by the invention comprises following process:
[1] mixed rare earth concentrates and sodium hydroxide solution are pressed the mixed of the weight ratio 1: 0.5～1.5 of mixed rare earth concentrates and sodium hydroxide;
[2] the mixture roasting of step (1) 0.5～4 hour, 150 ℃～550 ℃ of maturing temperatures;
[3] roasted ore that obtains of roasting to neutral, forms alkali cake and washings with hot wash; Washings reclaims fluorine, phosphorus and excess base.
[4] with tervalent rare earth optimum solvation, control pH value of solution=4～5 obtain re chloride to the alkali cake after the washing with hydrochloric acid;
Directly store up after the excellent thorium enriched thing washing after molten of hydrochloric acid or further extract thorium.
In the above-mentioned steps (1), the concentration of sodium hydroxide solution is 50%～90wt%, and preferred 65%～70wt% improves concentration of sodium hydroxide solution and can improve decomposition temperature, reduces roasting time, obtains high rate of decomposition.The ratio of mishmetal ore deposit and sodium hydroxide preferred 1: 0.8～1.0.
In the above-mentioned steps (1), rare earth ore concentrate REO content range is 30%～60wt%, has solved stoste alkaline process decomposition technique and can not use the problem of low-grade rare earth ore concentrate, can reduce the liquid caustic soda consumption but improve the rare earth ore concentrate grade, improve the concentrate rate of decomposition, reduce production costs.Preferred 50%～the 60wt% of REO content of rare earth ore concentrate.
In the above-mentioned steps (2), preferred 1.0～2.0 hours of roasting time, preferred 250 ℃～350 ℃ of maturing temperature; Described roasting is to carry out in Industrial Stoves such as rotary kiln of working continuously or tunnel furnace.Type of heating can be external-heat or internal heat type.
Adopt technology of the present invention, can reach following effect:
(1) saves pickling deliming operation in traditional alkali decomposition process, saved hydrochloric acid and bath water that this operation consumes, saved equipment such as pickling tank.Can realize continuous roasting decomposition after removing this operation.
(2) the alkali decomposition reaction has realized the continuous baked for producing of alkali decomposition process from the solid-liquid reaction to the solid-solid reaction.The excellent molten leaching yield of the hydrochloric acid of rare earth can reach more than 93%.The rare earth total recovery is more than 95%.Rare earth in the rare-earth mineral, thorium, fluorine and phosphorus all obtain reclaiming.
(3) only contain carbonic acid gas, water vapour in the tail gas of this technological process and drift along, no harmful exhaust produces, and meets discharging standards.
(4) this technological process can be grasped flexibly to the recovery of thorium, and thorium can thorium enriched thing form be deposited, and also can further purify obtains the thorium product.When thorium is not widely applied, can store up as raw material thorium with the sealing of enriched substance form, be recycled when to be needed.Thorium enriched thing amount only is 5～15% of a rare earth ore concentrate amount in this technology, lacks more than 60% than acid technological process, has significantly reduced volume of cargo in storage.Simultaneously, the thorium in the thorium enriched thing can obtain reclaiming with sulfuric acid or nitric acid dissolve, has solved in the acid technological process thorium and " burnt " to death the problem that can not continue to reclaim in slag, and therefore, this technology has very big handiness.
(5) water lotion is a high alkali liquid in this technological process, and wherein sodium hydrate content is more than 30%, and directly " causticization " filtered the concentrated additional new alkali in back and recycled cooling water circulation utilization.The causticization slag is Calcium Fluoride (Fluorspan), lime carbonate and calcium phosphate etc., gets final product further comprehensive reutilization fluorine and phosphorus, also can directly discharge.
Technical scheme provided by the invention has fundamentally solved the deficiency of present mixed rare earth concentrates decomposition technique (acid system and alkaline process), avoided the generation of sulfur-bearing, waste gas containing fluoride and nitrogen-containing wastewater, improved the utilization ratio of thorium, fluorine, phosphor resource, realized the serialization production of alkali decomposition process, solved the rare-earth smelting process " three wastes " from the source pollution of environment has been realized cleaning production.
Description of drawings:
Fig. 1 is a process flow diagram of the present invention.
Embodiment:
Explain technical scheme provided by the present invention in detail below in conjunction with embodiment, but not as the restriction to claim protection domain of the present invention.
Embodiment 1:
Get 500g sodium hydroxide and be made into 70wt% solution, add 500g mixed rare earth concentrates (REO 58.2wt%, CaO 5.65wt%), mix the back and in rotary kiln, is back to back, kiln residence time 1.5～2.0 hours, 180 ℃ of rotary kiln inlet temperatures, 190 ℃ of kiln temperatures, 230 ℃ of temperature outs.Roasted ore after the roasting enters in the aggregate bin of rotary kiln outlet automatically.Be washed to neutrality, hydrochloric acid optimum solvation then, control pH value of solution=4～5 obtain re chloride and thorium enriched thing.Analyze the rare earth in re chloride and the thorium enriched thing, the content of thorium.Rare-earth salts acid leaching yield 93.8%, rare earth total recovery 96.2%, thorium content is less than 0.01% in the re chloride.
Embodiment 2:
Get 500g sodium hydroxide and be made into 70wt% solution, add 500g mixed rare earth concentrates (REO 56.5wt%, CaO 5.74wt%), mix the back and in rotary kiln, is back to back, kiln residence time 1.5～2.0 hours, 180 ℃ of rotary kiln inlet temperatures, 190 ℃ of kiln temperatures, 230 ℃ of temperature outs.Roasted ore after the roasting enters in the aggregate bin of rotary kiln outlet automatically.Be washed to neutrality, hydrochloric acid optimum solvation then, control pH value of solution=4～5 obtain re chloride and thorium enriched thing.Analyze the rare earth in re chloride and the thorium enriched thing, the content of thorium.Rare-earth salts acid leaching yield 97.1%, rare earth total recovery 99%, thorium content is less than 0.01% in the re chloride.
Embodiment 3:
Get 500g sodium hydroxide and be made into 70wt% solution, add 500g mishmetal ore deposit (REO 56.5wt%, CaO 5.74wt%), mix the back and in rotary kiln, is back to back, kiln residence time 1.5～2.0 hours, 210 ℃ of rotary kiln inlet temperatures, 350 ℃ of kiln temperatures, 340 ℃ of temperature outs.Roasted ore after the roasting enters in the aggregate bin of rotary kiln outlet automatically.Be washed to neutrality, hydrochloric acid optimum solvation then, control pH value of solution=4.5～5 obtain re chloride and thorium enriched thing.Analyze the rare earth in rare earth chloride and the thorium enriched thing, the content of thorium.Rare-earth salts acid leaching yield 98.4%, rare earth total recovery 99%, thorium content is less than 0.01% in the re chloride.
Embodiment 4:
Get 400g sodium hydroxide and be made into 70wt% solution, add 500g mishmetal ore deposit (REO 56.5wt%, CaO 5.74wt%), mix the back and in rotary kiln, is back to back, kiln residence time 1.5～2.0 hours, 210 ℃ of rotary kiln inlet temperatures, 350 ℃ of kiln temperatures, 340 ℃ of temperature outs.Roasted ore after the roasting enters in the aggregate bin of rotary kiln outlet automatically.Be washed to neutrality, hydrochloric acid optimum solvation then, control pH value of solution=4.5～5 obtain re chloride and thorium enriched thing.Analyze the rare earth in rare earth chloride and the thorium enriched thing, the content of thorium.Rare-earth salts acid leaching yield 96.2%, rare earth total recovery 98.7%, thorium content is less than 0.01% in the re chloride.
Embodiment 5:
Get 500g sodium hydroxide and be made into 70wt% solution, add 500g mishmetal ore deposit (REO 50.6wt%, CaO 9.79wt%), mix the back and in rotary kiln, is back to back, kiln residence time 1.5～2.0 hours, 210 ℃ of rotary kiln inlet temperatures, 350 ℃ of kiln temperatures, 340 ℃ of temperature outs.Roasted ore after the roasting enters in the aggregate bin of rotary kiln outlet automatically.Be washed to neutrality, hydrochloric acid optimum solvation then, control pH value of solution=4.5～5 obtain re chloride and thorium enriched thing.Analyze the rare earth in rare earth chloride and the thorium enriched thing, the content of thorium.Rare-earth salts acid leaching yield 92.8%, rare earth total recovery 95.6%, thorium content is less than 0.01% in the re chloride.
Claims (8)
1. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, it is characterized in that: liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates comprises following process:
[1] mixed rare earth concentrates and sodium hydroxide solution are pressed the mixed of the weight ratio 1: 0.5～1.5 of mixed rare earth concentrates and sodium hydroxide;
[2] the mixture roasting of step (1) 0.5～4 hour, 150 ℃～550 ℃ of maturing temperatures;
[3] roasted ore that obtains of roasting to neutral, forms alkali cake and washings with hot wash; Washings reclaims fluorine, phosphorus and excess base.
[4] with tervalent rare earth optimum solvation, control pH value of solution=4～5 obtain re chloride to the alkali cake after the washing with hydrochloric acid.
2. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: in the step (1), the weight ratio of mixed rare earth concentrates and sodium hydroxide is 1: 0.8～1.0.
3. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: the scope of REO content is 30%～60wt% in the mixed rare earth concentrates.
4. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: the scope of REO content is 55%～60wt% in the mixed rare earth concentrates.
5. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: the concentration of sodium hydroxide solution is 50%～90wt%.
6. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: the concentration of sodium hydroxide solution is 65%～70wt%.
7. liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates according to claim 1 is characterized in that: in step (2), and 250 ℃～350 ℃ of maturing temperatures, roasting time 1～2 hour.
8. according to claim 1,2,3,4,5,6 or 7 described liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, it is characterized in that: described roasting is to carry out in quantity-produced rotary kiln or tunnel furnace, and type of heating is external-heat or internal heat type.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212674A (en) * | 2011-05-12 | 2011-10-12 | 包头稀土研究院 | Process for comprehensively recovering liquid alkali roasting resource of mixed rare earth concentrate |
| CN103103350A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing rare earth ore concentrate at low temperature through alkaline process |
| CN105369042A (en) * | 2015-12-11 | 2016-03-02 | 江西理工大学 | Method for efficiently extracting rare earths from fluoride system rare earth molten salt electrolysis slag |
| CN106145176A (en) * | 2015-04-21 | 2016-11-23 | 永州市湘江稀土有限责任公司 | The technique that a kind of alkaline process processes monazite |
| CN106591607A (en) * | 2016-12-10 | 2017-04-26 | 包头稀土研究院 | Liquid alkali decomposition method of high-grade mixed rare earth ore concentrate |
| 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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| CN1405337A (en) * | 2002-09-25 | 2003-03-26 | 包头稀土研究院 | Low-temperature roasting and decomposing process of rare earth heading concentrated sucfuric acid |
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- 2010-03-12 CN CN 201010145796 patent/CN101824531A/en active Pending
Patent Citations (1)
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| CN1405337A (en) * | 2002-09-25 | 2003-03-26 | 包头稀土研究院 | Low-temperature roasting and decomposing process of rare earth heading concentrated sucfuric acid |
Non-Patent Citations (1)
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| 《稀土》 19850630 韩学印等 浓NaOH溶液分解稀土矿物的研究 1-8 , 第3期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212674A (en) * | 2011-05-12 | 2011-10-12 | 包头稀土研究院 | Process for comprehensively recovering liquid alkali roasting resource of mixed rare earth concentrate |
| CN103103350A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing rare earth ore concentrate at low temperature through alkaline process |
| CN106145176A (en) * | 2015-04-21 | 2016-11-23 | 永州市湘江稀土有限责任公司 | The technique that a kind of alkaline process processes monazite |
| CN106145176B (en) * | 2015-04-21 | 2019-07-16 | 永州市湘江稀土有限责任公司 | A kind of technique of alkaline process processing monazite |
| CN105369042A (en) * | 2015-12-11 | 2016-03-02 | 江西理工大学 | Method for efficiently extracting rare earths from fluoride system rare earth molten salt electrolysis slag |
| CN106591607A (en) * | 2016-12-10 | 2017-04-26 | 包头稀土研究院 | Liquid alkali decomposition method of high-grade mixed rare earth ore concentrate |
| 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 |
| CN106586992B (en) * | 2016-12-10 | 2019-01-15 | 包头稀土研究院 | A kind of technique of the recycling of mixed rare earth concentrates liquid alkaline Decomposition-Synthesis fluorine and phosphorus |
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Application publication date: 20100908 |