CN101979335A - Process for recycling trace rare earth produced by treatment of waste residues and waste water of rare earth mine - Google Patents
Process for recycling trace rare earth produced by treatment of waste residues and waste water of rare earth mine Download PDFInfo
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- CN101979335A CN101979335A CN201010570069XA CN201010570069A CN101979335A CN 101979335 A CN101979335 A CN 101979335A CN 201010570069X A CN201010570069X A CN 201010570069XA CN 201010570069 A CN201010570069 A CN 201010570069A CN 101979335 A CN101979335 A CN 101979335A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a process for recycling trace rare earth produced by the treatment of waste residues and waste water of rare earth mine. The process comprises the following steps of: adjusting the pH value of the waste water to 7.0 by taking cheap lime as a precipitant; separating rare earth ions and hydroxide precipitates from the waste water, precipitating a plurality of non-rare earth impurities such as iron, aluminum, manganese and the like in the waste residues and the waste water synchronously, dissolving all hydroxides with hydrochloric acid and controlling the acid dissolving pH value to be between 4.2 and 5.5; dissolving rare earth after aluminum, iron and the like are dissolved preferably; and adjusting the pH value of dissolved solution to be between 6.0 and 6.4 by using lime milk, precipitating a small number of impurities such as iron, aluminum and the like in the solution by using the hydroxides, removing the precipitates, standing the solution for clarification, siphoning clarified solution into a precipitation tank, adjusting the pH value to 7.0 by using the lime milk, precipitating and separating the rare earth ions out by using the hydroxides, washing the precipitates with water by using a filter press and performing filter pressing so as to obtain rare earth chloride solution of which the acid solution meets the purchasing requirement of a rare earth separation plant.
Description
Technical field
The present invention relates to a kind of industrial residue recycling field, especially rare earth mine slag and effluent and administer emblem amount rare earth recovery technology.
Background technology
Along with China's rare earth mining technique constantly improves, from the primary dump leaching.Be extracted to present original place and soak in the ore deposit, improved many really.But still have a lot of problems: for example in the old mine after mining and receiving the ore deposit, having passed through the time of the more than ten years that had in several years has just abandoned it, that have even exceed and forgotten, it still produces remaining residue that gets off in back and acid group in addition, after rainwater is seen through, down spill in the river, irritate indignant crops again, caused certain harm like this.
Summary of the invention
The purpose of this invention is to provide rare earth mine slag and effluent and administer emblem amount rare earth recovery technology, to reach the trace rare-earth that reclaims safely and effectively in the slag and effluent of rare earth mine.
The present invention is achieved through the following technical solutions:
Rare earth mine slag and effluent is administered emblem amount rare earth and is reclaimed technology, wherein:
The first step, with low concentration of rare earth vitriol in the waste water, use milk of lime, regulate pH value and be 7.0 through multistage natural reaction clarification, rare earth sulfate is converted into the rare-earth hydroxide throw out fully.
Second the step, with the throw out of rare-earth hydroxide, pump into wash trough with sump pump, add a large amount of clear water again and wash, make remaining Ca (OH)
2Remove, in order to avoid cause the acid consumption.
The 3rd step, the rare earth hydrate after washing dissolve with concentrated hydrochloric acid, and beginning dissolved pH value is controlled between the 4.5-4.8, treat that dissolving tank slowly reduces the add-on of hydrochloric acid when expiring soon, be controlled between the 4.5-4.8 pH value.
The 4th step, ageing: the solution that the dissolving of solution pool the inside is good, pump into the ageing pond with pump, ageing 12-24 hour, pH value was about between the 4.5-5.0 therebetween.
The 5th step, pre-treatment: remove aluminium, iron, impurity and sulfate radical, use milk of lime, having air pump to stir under the companion, slowly add.Use bailer at last, add bit by bit, pH value is transferred to till the 6.3-6.5, then add the bariumchloride sulfate radical, the add-on of bariumchloride, every cube of rare earth mother solution water adds 3-4L approximately, makes saturated barium chloride solution.
The 6th step, precipitating rare earth: after pre-treatment, clarifying rare earth mother solution water, settling tank with the synchronous adding garden of the stone breast shape after the choosing of 100 mesh sieves precipitates, the precipitation pH value is treated precipitation clarification back venting supernatant 7.0 all the time, rare earth hydrate is entered, ageing is carried out in the ageing pond that the throw out crystal increases again.
The 7th step, press filtration: the rare earth hydrate that the ageing post crystallization is good carries out press filtration with plate-and-frame filter press, dehydration.
The 8th step, washing: the filter cake example after will dewatering is gone into wash trough and added clear water, and is fixing: liquor ratio: 1:6, and unlatching is stirred the companion and is stirred into the water slurry shape, and stirring companion's time is 0.5-1 hour.
The 9th step, secondary filter-press dehydration.
The tenth step, sour molten: the filter cake behind the second dehydration is dissolved with concentrated hydrochloric acid, and the dissolving pH value is 1.2-1.5.And add 15 liters of hydrogen peroxide in every cube of feed liquid.
The 11 step, feed clarification: press filtration, the feed liquid that dissolving is good pumps in the settling pond, and clarifying feed liquid is exactly a rare-earth products.The clear slag filter press of gained, filtrate is again rare-earth products, the waste residue that leaches returns in the waste residue pond for recovering again and reclaims rare earth.
Advantage of the present invention: by ageing, precipitating rare earth, press filtration, washing, acid is molten and series of steps such as feed clarification can reclaim from the slag and effluent of rare earth mine and obtains the emblem and measure rare earth.
Embodiment:
Embodiment 1, rare earth mine slag and effluent are administered emblem amount rare earth and are reclaimed technology, wherein:
The first step, with low concentration of rare earth vitriol in the waste water, use milk of lime, regulate pH value and be 7.0 through multistage natural reaction clarification, rare earth sulfate is converted into the rare-earth hydroxide throw out fully.
Second the step, with the throw out of rare-earth hydroxide, pump into wash trough with sump pump, add a large amount of clear water again and wash, make remaining Ca (OH)
2Remove, in order to avoid cause the acid consumption.
The 3rd step, the rare earth hydrate after washing dissolve with concentrated hydrochloric acid, and beginning dissolved pH value is controlled between the 4.5-4.8, treat that dissolving tank slowly reduces the add-on of hydrochloric acid when expiring soon, be controlled between the 4.5-4.8 pH value.
The 4th step, ageing: the solution that the dissolving of solution pool the inside is good, pump into the ageing pond with pump, ageing 12-24 hour, pH value was about between the 4.5-5.0 therebetween.
The 5th step, pre-treatment: remove aluminium, iron, impurity and sulfate radical, use milk of lime, having air pump to stir under the companion, slowly add.Use bailer at last, add bit by bit, pH value is transferred to till the 6.3-6.5, then add the bariumchloride sulfate radical, the add-on of bariumchloride, every cube of rare earth mother solution water adds 3-4L approximately, makes saturated barium chloride solution.
The 6th step, precipitating rare earth: after pre-treatment, clarifying rare earth mother solution water, settling tank with the synchronous adding garden of the stone breast shape after the choosing of 100 mesh sieves precipitates, the precipitation pH value is treated precipitation clarification back venting supernatant 7.0 all the time, rare earth hydrate is entered, ageing is carried out in the ageing pond that the throw out crystal increases again.
The 7th step, press filtration: the rare earth hydrate that the ageing post crystallization is good carries out press filtration with plate-and-frame filter press, dehydration.
The 8th step, washing: the filter cake example after will dewatering is gone into wash trough and added clear water, and is fixing: liquor ratio: 1:6, and unlatching is stirred the companion and is stirred into the water slurry shape, and stirring companion's time is 0.5-1 hour.
The 9th step, secondary filter-press dehydration.
The tenth step, sour molten: the filter cake behind the second dehydration is dissolved with concentrated hydrochloric acid, and the dissolving pH value is 1.2-1.5.And add 15 liters of hydrogen peroxide in every cube of feed liquid.
The 11 step, feed clarification: press filtration, the feed liquid that dissolving is good pumps in the settling pond, and clarifying feed liquid is exactly a rare-earth products.The clear slag filter press of gained, filtrate is again rare-earth products, the waste residue that leaches returns in the waste residue pond for recovering again and reclaims rare earth.
Principle:
Utilize cheap lime to make precipitation agent, the waste water pH value is transferred to 7.0.Make rare earth from separating with waste water with precipitation of hydroxide, because of there are many non-rare earth impurities the slag and effluent the inside: get off as iron, aluminium, manganese etc. also synchronous precipitation, then all oxyhydroxide is dissolved with hydrochloric acid, sour dissolved pH value is controlled between the 4.2-5.5.Rare earth meeting optimum solvation aluminium, back dissolving such as iron; Lysate is carried out pH value with milk of lime to transfer between the 6.0-6.4, make a spot of iron in the solution, foreign material such as aluminium are removed with precipitation of hydroxide, treat solution clarification after, siphon is to settling tank, adjust to pH value 7.0 with milk of lime, rare earth ion is separated out with precipitation of hydroxide, and throw out is washed through pressure filter, press filtration, acid solution reach the rare earth chloride solution that the purchase of Rare Earth Separation factory requires.
Claims (1)
1. rare earth mine slag and effluent is administered emblem amount rare earth and is reclaimed technology, it is characterized in that:
The first step, with low concentration of rare earth vitriol in the waste water, use milk of lime, regulate pH value and be 7.0 through multistage natural reaction clarification, rare earth sulfate is converted into the rare-earth hydroxide throw out fully;
Second the step, with the throw out of rare-earth hydroxide, pump into wash trough with sump pump, add a large amount of clear water again and wash, make remaining Ca (OH)
2Remove, in order to avoid cause the acid consumption;
The 3rd step, the rare earth hydrate after washing dissolve with concentrated hydrochloric acid, and beginning dissolved pH value is controlled between the 4.5-4.8, treat that dissolving tank slowly reduces the add-on of hydrochloric acid when expiring soon, be controlled between the 4.5-4.8 pH value;
The 4th step, ageing: the solution that the dissolving of solution pool the inside is good, pump into the ageing pond with pump, ageing 12-24 hour, pH value was about between the 4.5-5.0 therebetween;
The 5th step, pre-treatment: remove aluminium, iron, impurity and sulfate radical, use milk of lime, having air pump to stir under the companion, slowly add; Use bailer at last, add bit by bit, pH value is transferred to till the 6.3-6.5, then add the bariumchloride sulfate radical, the add-on of bariumchloride, every cube of rare earth mother solution water adds 3-4L approximately, makes saturated barium chloride solution;
The 6th step, precipitating rare earth: after pre-treatment, clarifying rare earth mother solution water, settling tank with the synchronous adding garden of the stone breast shape after the choosing of 100 mesh sieves precipitates, the precipitation pH value is treated precipitation clarification back venting supernatant 7.0 all the time, rare earth hydrate is entered, ageing is carried out in the ageing pond that the throw out crystal increases again;
The 7th step, press filtration: the rare earth hydrate that the ageing post crystallization is good carries out press filtration with plate-and-frame filter press, dehydration;
The 8th step, washing: the filter cake example after will dewatering is gone into wash trough and added clear water, and is fixing: liquor ratio: 1:6, and unlatching is stirred the companion and is stirred into the water slurry shape, and stirring companion's time is 0.5-1 hour;
The 9th step, secondary filter-press dehydration;
The tenth step, sour molten: the filter cake behind the second dehydration is dissolved with concentrated hydrochloric acid, and the dissolving pH value is 1.2-1.5, and adds 15 liters of hydrogen peroxide in every cube of feed liquid;
The 11 step, feed clarification: press filtration, the feed liquid that dissolving is good pumps in the settling pond, and clarifying feed liquid is exactly a rare-earth products; The clear slag filter press of gained, filtrate is again rare-earth products, the waste residue that leaches returns in the waste residue pond for recovering again and reclaims rare earth.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127646A (en) * | 2011-03-07 | 2011-07-20 | 福建省长汀金龙稀土有限公司 | Method for reprocessing rare earth slag by acid composition |
| CN103466738A (en) * | 2013-08-15 | 2013-12-25 | 南昌大学 | Method for removing ammonia nitrogen and recovering rare earth from low-concentration solution containing ammonium and rare earth |
| CN104313326A (en) * | 2014-10-17 | 2015-01-28 | 金川集团股份有限公司 | Method for reducing amount of barium chloride in eliminating sulfate radical in nickel chloride solution with high content of sulfate radical |
| CN104609589A (en) * | 2013-11-04 | 2015-05-13 | 南京源泉环保科技股份有限公司 | Solid-liquid separation method of electroplating wastewater |
| CN105506287A (en) * | 2016-01-13 | 2016-04-20 | 龙南县锦易矿业有限公司 | Process for recycling rare earth from Southern rare earth ore through leached mother liquor precipitation method |
| CN105779792A (en) * | 2016-03-29 | 2016-07-20 | 江西理工大学 | Method for preparing low-impurity-content rare earth hydrate |
| CN105907959A (en) * | 2016-05-16 | 2016-08-31 | 龙南县锦易矿业有限公司 | Ammonia-free mining method for rare earth ore in south China |
| CN106367621A (en) * | 2016-09-13 | 2017-02-01 | 南昌大学 | Method for recovering and recycling valuable elements from low-content rare earth solution and precipitation sludge |
| CN107604183A (en) * | 2017-09-27 | 2018-01-19 | 江西理工大学 | A kind of agent of low concentration ion type rareearth biogenic sediment and its preparation |
| CN108815916A (en) * | 2018-05-21 | 2018-11-16 | 陈键锋 | A kind of stone pulp-water processing technique and processing equipment |
| CN111876599A (en) * | 2020-07-24 | 2020-11-03 | 乐山盛和稀土股份有限公司 | A process for adjusting the value of rare earth material and liquid |
| CN112088224A (en) * | 2018-05-03 | 2020-12-15 | 阿拉弗拉资源有限公司 | Method for recovering rare earth |
| CN114990340A (en) * | 2022-06-10 | 2022-09-02 | 贵州大学 | A method for separating and recovering rare earth elements from acid mine wastewater |
| CN111876599B (en) * | 2020-07-24 | 2025-04-15 | 乐山盛和稀土有限公司 | A rare earth liquid value adjustment process |
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| JPH01230732A (en) * | 1988-03-09 | 1989-09-14 | Sumitomo Light Metal Ind Ltd | Recovering method for rare earth metal |
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| CN101451200A (en) * | 2007-11-29 | 2009-06-10 | 北京有色金属研究总院 | Rare-earth enrichment recovery method from phosphorite |
| CN101476033A (en) * | 2008-10-28 | 2009-07-08 | 黄日平 | Novel method for leaching, impurity removing and precipitating ion type rare earth ore |
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2010
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01230732A (en) * | 1988-03-09 | 1989-09-14 | Sumitomo Light Metal Ind Ltd | Recovering method for rare earth metal |
| RU2246773C2 (en) * | 2003-04-28 | 2005-02-20 | ООО Научно-производственная экологическая фирма "ЭКО-технология" | Method for recovering less-common and rare-earth metal production wastes |
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| CN101451200A (en) * | 2007-11-29 | 2009-06-10 | 北京有色金属研究总院 | Rare-earth enrichment recovery method from phosphorite |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127646B (en) * | 2011-03-07 | 2012-09-12 | 福建省长汀金龙稀土有限公司 | Method for reprocessing rare earth slag by acid composition |
| CN102127646A (en) * | 2011-03-07 | 2011-07-20 | 福建省长汀金龙稀土有限公司 | Method for reprocessing rare earth slag by acid composition |
| CN103466738A (en) * | 2013-08-15 | 2013-12-25 | 南昌大学 | Method for removing ammonia nitrogen and recovering rare earth from low-concentration solution containing ammonium and rare earth |
| CN104609589A (en) * | 2013-11-04 | 2015-05-13 | 南京源泉环保科技股份有限公司 | Solid-liquid separation method of electroplating wastewater |
| CN104313326A (en) * | 2014-10-17 | 2015-01-28 | 金川集团股份有限公司 | Method for reducing amount of barium chloride in eliminating sulfate radical in nickel chloride solution with high content of sulfate radical |
| CN105506287B (en) * | 2016-01-13 | 2017-09-19 | 赣州稀土开采技术服务有限公司 | The technique that southern RE ore leaches mother liquor precipitation method recovering rare earth |
| CN105506287A (en) * | 2016-01-13 | 2016-04-20 | 龙南县锦易矿业有限公司 | Process for recycling rare earth from Southern rare earth ore through leached mother liquor precipitation method |
| CN105779792A (en) * | 2016-03-29 | 2016-07-20 | 江西理工大学 | Method for preparing low-impurity-content rare earth hydrate |
| CN105907959A (en) * | 2016-05-16 | 2016-08-31 | 龙南县锦易矿业有限公司 | Ammonia-free mining method for rare earth ore in south China |
| CN106367621A (en) * | 2016-09-13 | 2017-02-01 | 南昌大学 | Method for recovering and recycling valuable elements from low-content rare earth solution and precipitation sludge |
| CN107604183A (en) * | 2017-09-27 | 2018-01-19 | 江西理工大学 | A kind of agent of low concentration ion type rareearth biogenic sediment and its preparation |
| CN107604183B (en) * | 2017-09-27 | 2019-03-26 | 江西理工大学 | A kind of low concentration ion type rareearth biogenic sediment agent and its preparation |
| CN112088224A (en) * | 2018-05-03 | 2020-12-15 | 阿拉弗拉资源有限公司 | Method for recovering rare earth |
| CN108815916A (en) * | 2018-05-21 | 2018-11-16 | 陈键锋 | A kind of stone pulp-water processing technique and processing equipment |
| CN111876599A (en) * | 2020-07-24 | 2020-11-03 | 乐山盛和稀土股份有限公司 | A process for adjusting the value of rare earth material and liquid |
| CN111876599B (en) * | 2020-07-24 | 2025-04-15 | 乐山盛和稀土有限公司 | A rare earth liquid value adjustment process |
| CN114990340A (en) * | 2022-06-10 | 2022-09-02 | 贵州大学 | A method for separating and recovering rare earth elements from acid mine wastewater |
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