CN103468975B - Method for extracting beryllium from aureobasite type beryllium concentrate with low beneficiation enrichment ratio - Google Patents
Method for extracting beryllium from aureobasite type beryllium concentrate with low beneficiation enrichment ratio Download PDFInfo
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Abstract
The invention discloses a method for extracting beryllium oxide from a aureoviride type beryllium concentrate with low beneficiation enrichment ratio, which aims to solve the problems that the impurity content in a leaching solution is high and the subsequent recovery of beryllium is not facilitated when the aureoviride type beryllium concentrate is directly subjected to acid leaching. The method comprises the working procedures of pretreatment, acidification roasting, water leaching, impurity removal, extraction and recovery of concentrate, and the specific process comprises the following steps: pretreating beryllium concentrate with 3-5mol/L hydrochloric acid solution, adding concentrated sulfuric acid into the pretreated material obtained in the step (1) according to the acid-mineral ratio of 1:0.8-1.2, and carrying out acidification roasting for 0.5-1.5 h; soaking in water for 20-40min at a liquid-solid ratio of 2-3: 1; removing impurities by coprecipitation; extracting; back extraction: and (3) carrying out back extraction on the loaded organic phase obtained in the step (5) by adopting a back extractant of 2-3mol/L, and salting out or heating and decomposing the obtained back extractant by using ammonia water to obtain a product. The method has simple and reliable process and easy realization of industrial production, has the product content of beryllium fluoride and beryllium oxide of more than 97 percent, good product quality and the recovery rate of beryllium of more than 73 percent, and is suitable for extracting beryllium from high-fluorine low-grade chrysoberyl type beryllium ores.
Description
Technical field
The present invention relates to a kind of from beneficiation enrichment than the method proposing beryllium oxide low chrysoberyl type beryllium concentrate, particularly low from beryllium content, the method for beryllium oxide is produced in the chrysoberyl type beryllium ore deposit that Oil repellent is high.
Background technology
Beryllium is a kind of rare elements, occupies an important position in national economy and national defense industry, particularly significant in fields such as nuclear industry, aerospace industry, electronic industries.From beryllium metallurgy is used for industrial production, industrial beryllium oxide all extracts from beryl lump ore.Because beryl resource can not meet the demand of industrial development, the 1969 assorted companies of Bradley of the Nian Qi U.S. start with bertrandite manufacture beryllium oxide.Crow Bhujerba beryllium smeltery of Kazakhstan also extracts industrial beryllium oxide by alkali solution attack process method from the eighties in last century from Russian phenakite.In recent years, it is increasingly short to be used for the green post lump ore of manufacture beryllium oxide, in order to meet beryllium produce market and war products to the needs of beryllium material, must find other beryllium ore resources of alternative beryl lump ore.Non-beryl beryllium ore stone mainly contains: helvite, ytterbite, Russian phenakite ore deposit, Canadian phenacite, chrysoberyl and hsianghualite and taaffeite etc.Chrysoberyl type beryllium ore resources reserves are large, and resource is unique, are the important reserved resources of beryllium resource.But because chrysoberyl type beryllium ore deposit ore grade is low, difficult floating and enriching; Ore decomposition difficulty is all again flotate from the raw ore containing a large amount of fluorite, so chrysoberyl type beryllium is fluorine-containing very high.Therefore how decomposing ore, leaches, and the fluorine removed in beryllium or eliminate fluorine to the impact of industrial beryllium oxide smelting process, and the treatment process of economic environmental protection is the difficult point of the type beryllium ore deposit manufacture beryllium oxide.
Containing mineral such as fluorite rhombspars in chrysoberyl type beryllium ore deposit, calcic is high, adds silicofluoric acid ammonia roasting conversion method process the type ore deposit as adopted, due in conversion process, a large amount of berylliums forms fluorine beryllium acid calcium indissoluble thing, is unfavorable for the recovery of beryllium, the rate of recovery of beryllium is significantly reduced.As direct acidleach, the foreign matter content in leach liquor is high, is unfavorable for the recovery of follow-up beryllium, adds consumption and cost.
Summary of the invention
The object of this invention is to provide a kind of from beneficiation enrichment than the method proposing beryllium oxide low chrysoberyl type beryllium concentrate, high to solve the foreign matter content existed in leach liquor the direct acidleach in chrysoberyl type beryllium ore deposit, be unfavorable for the problem of the recovery of follow-up beryllium.
Technical scheme of the present invention is: a kind of from beneficiation enrichment than the method extracting beryllium low chrysoberyl type beryllium concentrate, it is characterized in that: it comprises the pre-treatment of concentrate, acidizing fired, water logging, removal of impurities, extraction, recovery process, and detailed process is:
(1) pre-treatment: by the hydrochloric acid soln pre-treatment of beryllium concentrate 3-5mol/L, liquid-solid ratio is 2-3:1, carries out pre-treatment to concentrate;
(2) acidizing fired: by the sour ore deposit ratio of 1:0.8-1.2, in the pre-treatment material that the interpolation vitriol oil to step (1) obtains, at temperature is 400-500 DEG C, acidizing fired 0.5-1.5h;
(3) two sections of water loggings: be 2-3:1 by liquid-solid ratio, by the fired slags that step (2) obtains, add in boiling water and stir, water logging 20-40min, and filtered filtration residue leaches through two sections of boiling water again, and filter and hot wash, two sections of infusions are mixed into leach liquor; Two sections of water logging slags abandon through washing;
(4) co-precipitation removal of impurities: by the leach liquor heating and thermal insulation of step (3), temperature controls at 90-95 DEG C, by adjusting PH with base value between 3.0-4.0, reaction 4-5h, meanwhile, iron also hydrolytic precipitation is gone out; Filter, precipitation slag ammoniumsulphate soln pulping and washing, washing lotion returns step (3) two sections of water loggings;
(5) extract: the removal of impurities leach liquor organic extractant phase agent extraction that step (4) is obtained, organic extractant phase agent is volume ratio is two (the 2-ethylhexyl phosphoric acids) of 20-30:80-70 and the mixture of kerosene, extraction is in a ratio of 1:1, extraction time is 3-5min, carry out at least two-stage countercurrent extraction, be extracted load organic phases and raffinate;
(6) back extraction: adopt the load organic phases that the strippant stripping steps (5) of 2-3mol/L obtains, extraction is in a ratio of 1:1, adopts secondary countercurrent reextraction, obtains back extraction organic phase and strip liquor;
(7) reclaim: the strip liquor ammoniacal liquor that step (6) obtains to be saltoutd or thermal degradation obtains product.
Further, the alkali of adjust pH is the one in ammoniacal liquor or sodium hydroxide in described step (4).
Further, in described step (5) stripping process, strippant adopts the one in ammonium bifluoride or volatile salt, and when adopting ammonium bifluoride to carry out back extraction, the strip liquor ammoniacal liquor that step (6) obtains is saltoutd, and evaporative crystallization forms beryllium fluoride; During with volatile salt back extraction, volatile salt strip liquor, through heating, makes beryllium with the form Precipitation of basic carbonate beryllium, solid-liquor separation, precipitation pure water, and heating and calcining forms beryllium oxide.
Further, the acidizing fired middle fired slags ball milling of described step (2) is to 100-120 order.
The present invention compared with prior art has following features: 1. the present invention's hydrochloric acid soln carries out pre-treatment, reduces foreign matter content in follow-up leaching process; 2. roasted ore adopts acidizing fired, and flue gas can reclaim the fluorine in ore, reduces the content of fluorine in leach liquor, and leach and adopt water logging, leach liquor acidity is low, is conducive to subsequent disposal, and the leaching yield of beryllium is more than 93%; 3. the iron in leach liquor, aluminium, fluorine impurity adopt co-precipitation to go out, and reduce extraction deironing cost and wastewater flow rate, avoid extracting and emulsifying simultaneously, also make extraction process more stable, avoid fluorine on the impact of extraction efficiency, improve beryllium oxide quality; 4. back extraction adopt ammonium bifluoride, strip liquor saltout thermal degradation reclaim beryllium fluoride; Or use volatile salt back extraction, as long as strip liquor heating just can make beryllium with the form Precipitation of basic carbonate beryllium, reduce hydrolysis acid consumption and wastewater flow rate.Production operation simple possible of the present invention, wastewater flow rate is little, and environmental pollution is little, and cost is low, and quality product is high, and the beryllium rate of recovery can reach more than 73%.
Embodiment
Embodiment 1
Raw material: chrysoberyl type beryllium concentrate, BeO content is 1.31%, fluorine-containing 5.46%,
(1) pre-treatment: by the hydrochloric acid soln pre-treatment of beryllium concentrate 3mol/L, liquid-solid ratio is 2:1, carries out pre-treatment to concentrate, wash away most iron, the impurity such as magnesiumcarbonate, washing lotion is with after limestone vegetation process, solution reclaims calcium chloride, magnesium hydroxide etc., and beryllium rate of loss is 2%;
(2) acidizing fired: by the sour ore deposit ratio of 1:0.8, in the pre-treatment material that the interpolation vitriol oil to step (1) obtains, at temperature is 400 DEG C, acidizing fired 0.5h, baking flue gas is HF, SiF
4, H
2o, solid particulate matter etc., flue gas reclaims hydrofluoric acid etc. through removal of impurities process of gathering dust, and the fired slags ball milling obtained is to 100 orders, and loss by roasting rate is 5%;
(3) two sections of water loggings: be 2:1 by liquid-solid ratio, by the fired slags that step (2) obtains, add in boiling water and stir, water logging 20min, and filtered filtration residue leaches through two sections of boiling water again, and filter and hot wash, two sections of infusions are mixed into leach liquor; Leaching yield is that 93%, two sections of water logging slags abandon through washing;
(4) co-precipitation removal of impurities: by the leach liquor heating and thermal insulation of step (3), temperature controls at 90 DEG C, and with ammoniacal liquor adjust pH 3.0, reaction 4h, makes fluorine, aluminium form co-precipitation 16Al (OH, F) .6H
2o, meanwhile, iron also hydrolytic precipitation is gone out, and the reaction later stage adds a small amount of hydrogen peroxide, makes iron precipitate completely; Filter, precipitation slag ammoniumsulphate soln pulping and washing, washing lotion returns step (3) two sections of water loggings, and slag abandons, and beryllium rate of loss is 10%;
(5) extract: the removal of impurities leach liquor organic extractant phase agent extraction that step (4) is obtained, organic extractant phase agent is volume ratio is two (the 2-ethylhexyl phosphoric acids) of 20:80 and the mixture of kerosene, extraction is in a ratio of 1:1, extraction time is 3min, carry out two-stage countercurrent extraction, be extracted load organic phases and raffinate, percentage extraction is 99%;
(6) back extraction: the ammonium hydrogen fluoride solution adopting 2mol/L, the load organic phases that stripping steps (5) obtains, extraction is in a ratio of 1:1, adopt secondary countercurrent reextraction, obtain back extraction organic phase and strip liquor, back extraction ratio is 95%;
(7) reclaim: saltoutd by the strip liquor ammoniacal liquor that step (6) obtains and thermal degradation, ammonium bifluoride strip liquor evaporative crystallization forms beryllium fluoride, and the beryllium rate of recovery is 98%; Obtain the beryllium fluoride containing 97%, beryllium total yield is 73%.
Embodiment 2
Raw material: chrysoberyl type beryllium concentrate, BeO content is 1.53%, fluorine-containing 6.13%,
(1) pre-treatment: by the hydrochloric acid soln pre-treatment of beryllium concentrate 5mol/L, liquid-solid ratio is 3:1, carries out pre-treatment to concentrate, wash away most iron, the impurity such as magnesiumcarbonate, washing lotion is with after limestone vegetation process, solution reclaims calcium chloride, magnesium hydroxide etc., and beryllium rate of loss is 2%;
(2) acidizing fired: by the sour ore deposit ratio of 1:1.2, in the pre-treatment material that the interpolation vitriol oil to step (1) obtains, at temperature is 500 DEG C, acidizing fired 1.5h, baking flue gas is HF, SiF
4, H
2o, solid particulate matter etc., flue gas reclaims hydrofluoric acid etc. through removal of impurities process of gathering dust, and the fired slags ball milling obtained is to 120 orders, and loss by roasting rate is 5%;
(3) two sections of water loggings: be 3:1 by liquid-solid ratio, by the fired slags that step (2) obtains, add in boiling water and stir, water logging 40min, and filtered filtration residue leaches through two sections of boiling water again, and filter and hot wash, two sections of infusions are mixed into leach liquor; Leaching yield is that 95%, two sections of water logging slags abandon through washing;
(4) co-precipitation removal of impurities: by the leach liquor heating and thermal insulation of step (3), temperature controls at 95 DEG C, and with sodium hydroxide adjust pH 4.0, reaction 5h, makes fluorine, aluminium form co-precipitation 16Al (OH, F) .6H
2o, meanwhile, iron also hydrolytic precipitation is gone out, and the reaction later stage adds a small amount of hydrogen peroxide, makes iron precipitate completely; Filter, precipitation slag ammoniumsulphate soln pulping and washing, washing lotion returns step (3) two sections of water loggings, and slag abandons, and beryllium rate of loss is 10%;
(5) extract: the removal of impurities leach liquor organic extractant phase agent extraction that step (4) is obtained, organic extractant phase agent is volume ratio is two (the 2-ethylhexyl phosphoric acids) of 30:70 and the mixture of kerosene, be in a ratio of 1, extraction time is 5min, carry out three stage countercurrent extractions, be extracted load organic phases and raffinate, percentage extraction is 99%;
(6) back extraction: adopt the volatile salt of 3mol/L to carry out back extraction, the load organic phases that stripping steps (5) obtains, be in a ratio of 1, adopt secondary countercurrent reextraction, make beryllium with the form Precipitation of basic carbonate beryllium, solid-liquor separation, precipitation pure water, back extraction ratio is 94%;
(7) reclaim: the volatile salt strip liquor of precipitation forms beryllium oxide through heating and calcining, obtain the beryllium oxide containing 98%, calcining scaling loss is 1%; The beryllium rate of recovery is 74%.
Claims (4)
1. from beneficiation enrichment than the method extracting beryllium low chrysoberyl type beryllium concentrate, it is characterized in that: it comprises the pre-treatment of concentrate, acidizing fired, water logging, removal of impurities, extraction, recovery process, and detailed process is:
(1) pre-treatment: by the hydrochloric acid soln pre-treatment of beryllium concentrate 3-5mol/L, liquid-solid ratio is 2-3:1, carries out pre-treatment to concentrate;
(2) acidizing fired: by the sour ore deposit ratio of 1:0.8-1.2, in the pre-treatment material that the interpolation vitriol oil to step (1) obtains, at temperature is 400-500 DEG C, acidizing fired 0.5-1.5h;
(3) two sections of water loggings: be 2-3:1 by liquid-solid ratio, by the fired slags that step (2) obtains, add in boiling water and stir, water logging 20-40min, and filtered filtration residue leaches through two sections of boiling water again, and filter and hot wash, two sections of infusions are mixed into leach liquor; Two sections of water logging slags abandon through washing;
(4) co-precipitation removal of impurities: by the leach liquor heating and thermal insulation of step (3), temperature controls at 90-95 DEG C, by adjusting PH with base value between 3.0-4.0, reaction 4-5h, meanwhile, iron also hydrolytic precipitation is gone out; Filter, precipitation slag ammoniumsulphate soln pulping and washing, washing lotion returns step (3) two sections of water loggings;
(5) extract: the removal of impurities leach liquor organic extractant phase agent extraction that step (4) is obtained, organic extractant phase agent is volume ratio is two (the 2-ethylhexyl phosphoric acids) of 20-30:80-70 and the mixture of kerosene, extraction is in a ratio of 1:1, extraction time is 3-5min, carry out at least two-stage countercurrent extraction, be extracted load organic phases and raffinate;
(6) back extraction: adopt the load organic phases that the strippant stripping steps (5) of 2-3mol/L obtains, extraction is in a ratio of 1:1, adopts secondary countercurrent reextraction, obtains back extraction organic phase and strip liquor;
(7) reclaim: the strip liquor ammoniacal liquor that step (6) obtains to be saltoutd or thermal degradation obtains product.
2. according to claim 1 a kind of from beneficiation enrichment than the method extracting beryllium low chrysoberyl type beryllium concentrate, it is characterized in that: the alkali of adjust pH is the one in ammoniacal liquor or sodium hydroxide in described step (4).
3. according to claim 1 and 2 a kind of from beneficiation enrichment than the method extracting beryllium low chrysoberyl type beryllium concentrate, it is characterized in that: in described step (6) stripping process, strippant adopts the one in ammonium bifluoride or volatile salt, when adopting ammonium bifluoride to carry out back extraction, the strip liquor ammoniacal liquor that step (6) obtains is saltoutd, and evaporative crystallization forms beryllium fluoride; During with volatile salt back extraction, the volatile salt strip liquor that step (6) obtains, through heating, makes beryllium with the form Precipitation of basic carbonate beryllium, solid-liquor separation, precipitation pure water, and heating and calcining forms beryllium oxide.
4. according to claim 3 a kind of from beneficiation enrichment than the method extracting beryllium low chrysoberyl type beryllium concentrate, it is characterized in that: the acidizing fired middle fired slags ball milling of described step (2) is to 100-120 order.
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| CN103818937B (en) * | 2013-12-30 | 2016-01-13 | 新疆有色金属研究所 | From containing the method producing beryllium oxide or high-purity beryllium oxide beryllium solution |
| CN106925434A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | One kind ore dressing defluorination process from beryllium ore deposit |
| CN105671341B (en) * | 2016-01-27 | 2018-04-06 | 广东省资源综合利用研究所 | A kind of selecting smelting combination method from chrysoberyl beryllium extraction beryllium oxide |
| CN105734309B (en) * | 2016-03-17 | 2017-09-05 | 湘潭大学 | A kind of method that beryllium is extracted in the type beryllium from chrysoberyl |
| CN105907962B (en) * | 2016-04-26 | 2018-09-07 | 新疆有色金属研究所 | The preparation method of high-purity strip liquor containing beryllium and preparation method thereof, ammonium fluoberyllate, beryllium fluoride and metallic beryllium |
| CN107641712A (en) * | 2017-09-21 | 2018-01-30 | 湖南行者环保科技有限公司 | A kind of method that beryllium hydroxide is prepared from extraction in ore deposit containing beryllium |
| CN110589858B (en) * | 2019-10-08 | 2022-06-17 | 昆明先导新材料科技有限责任公司 | Method for preparing beryllium fluoride from industrial-grade beryllium |
| CN115786742B (en) * | 2022-11-04 | 2024-02-09 | 核工业北京化工冶金研究院 | Comprehensive recycling method for uranium beryllium ore |
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| CN102168184B (en) * | 2011-05-27 | 2012-10-24 | 广州有色金属研究院 | Method for extracting beryllium oxide from low-grade beryllium ore |
| CN102851502B (en) * | 2012-04-26 | 2013-10-30 | 广州有色金属研究院 | Method for extracting and separating beryllium |
| CN103088206B (en) * | 2012-12-25 | 2014-04-23 | 戴元宁 | Chemical metallurgy method for extracting beryllium oxide from chrysoberyl |
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