CN1055033C - Beneficiation method for recovering wolframite and scheelite from complex polymetallic ores - Google Patents
Beneficiation method for recovering wolframite and scheelite from complex polymetallic ores Download PDFInfo
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- CN1055033C CN1055033C CN95117062A CN95117062A CN1055033C CN 1055033 C CN1055033 C CN 1055033C CN 95117062 A CN95117062 A CN 95117062A CN 95117062 A CN95117062 A CN 95117062A CN 1055033 C CN1055033 C CN 1055033C
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Abstract
The invention relates to a beneficiation method for recovering black and white tungsten from complex polymetallic ores. The present invention features that during the flotation of bismuth molybdenum sulfide mineral in tungsten ore, nitrosophenylhydroxylamine ammonium salt and emulsified oleic acid are added to make the flotation process in natural pH value for separation.
Description
The present invention is a kind of beneficiation method that reclaims black and white tungsten from the complex multi-metal ore deposit.Be particularly related to the floatation process of black and white tungsten, be applicable to sorting of black and white tungsten ore.
From sulphide ore, black tungsten, white tungsten, fluorite, flotation black and white tungsten ore in the complex multi-metal ore deposit of calcite symbiosis, this class separation by ore floatation is difficulty relatively, all be to adopt in strongly basic medium, to suppress fluorite at present both at home and abroad, calcite, method with fatty acid collecting agent (oxidation paraffin wax soap or oleic acid) flotation scheelite, be about to floatingly select sulphide ore earlier after the granularity that ore is ground to requirement, sulfide flotation mine tailing flotation black and white again tungsten (or the white tungsten of flotation), the method of this flotation tungsten ore has two kinds, a kind of soda processes of crying, promptly in ore pulp, add more than caustic soda (or soda ash) 1000 gram/tons, add waterglass and suppress fluorite, calcite and other gangue minerals, use oxidation paraffin wax soap or oleic acid to do collecting agent flotation black and white tungsten (or the white tungsten of flotation), another kind method is lime method, promptly in ore pulp, add more than the lime 1000 gram/tons, add waterglass and suppress fluorite, calcite and other gangue minerals, use oxidation paraffin wax soap or oleic acid to do collecting agent flotation black and white tungsten (or the white tungsten of flotation), the pH value of these two kinds of method flotation pulps is all more than 11.
Tungsten ore dressing plant, Korea S mulberry east, raw ore trioxygen-containing tungsten 0.7%.The major metal mineral have scheelite, wolframite, molybdenite, bismuthine, pyrite and a spot of cassiterite and gold, and gangue mineral has quartz, diopside, hornblend, fluorite, calcite and carbamate additives for low phosphorus lime stone.Raw ore carries out sulfide flotation earlier, reclaims molybdenum and bismuth, and the sulfide flotation mine tailing carries out Scheelite Flotation, and the medicament that white tungsten flotation is used is sodium carbonate, waterglass, oleic acid, and slurry pH is more than 10.
China's Hunan persimmon bamboo plantation polymetallic ore is the complex multi-metal ore deposit of a large-scale tungsten, molybdenum, bismuth, fluorite symbiosis.The major metal mineral have scheelite, wolframite, bismuthine, molybdenite, magnetic iron ore, pyrite etc., and main gangue mineral is garnet, quartz, fluorite, calcite, pyroxene, hornblend etc.Raw ore trioxygen-containing tungsten 0.56%, wherein 2/3 is scheelite, 1/3 is wolframite.Raw ore contains molybdenum 0.09%, bismuth-containing 0.18%, fluorinated calcium 18-20%.Present mineral processing circuit is: after raw ore was milled to-200 orders and accounts for 85% fineness, first flotation sulphide ore obtained molybdenum concntrate, bismuth concentrate and sulphur concentrate respectively.The sulfide flotation mine tailing adopts soda processes to carry out the tungsten flotation, the floating agent that uses is: caustic soda, waterglass, oxidation paraffin wax soap, flotation pulp pH value is 11-12, and the tungsten flotation tailing is used fatty acid collecting agent flotation fluorite after with sulfuric acid slurry pH being transferred to about 9 again.Existing floatation major defect is: the flotation recovering effect of black and white tungsten ore is relatively poor, generally also will add reselection operation (spiral concentrator and shaking table) and reclaim wolframite before or after the tungsten flotation operation.Make the technological process complexity, when fluorite is reclaimed in flotation after the tungsten flotation simultaneously, also need the sulfuric acid of reagent removal or interpolation 600-1000 gram/ton that slurry pH is transferred to about 9, not only increase medicament expense usefulness, and the floatation indicators of fluorite is also relatively poor.
The objective of the invention is to improve the recovery rate in ore-dressing and the concentrate grade of black and white tungsten ore, seek a kind of method of under natural pH value condition, carrying out flotation, simplifying technology, reducing reagent consumption, reduce cost.
The present invention reclaims the beneficiation method of black and white tungsten ore from the complex multi-metal ore deposit, its principle technology is raw ore to be ground to size mixing carry out flotation bismuth molybdenum sulphide ore earlier, get sulphide concentrate, the sulfide flotation mine tailing carries out the flotation of black and white tungsten concentrate, earlier must roughly select froth pulp through bulk flotation, it gets black and white tungsten rough concentrate through recleaning again, rougher tailings is after secondary is scanned, mine tailing enters the fluorite operation, black and white tungsten rough concentrate carries out tungsten selected the white tungsten fine ore of heating, and the cleaner tailings of heating adopts magnetic-weight-float flow processing can obtain wolframite.Flotation (tungsten flotation) method that the invention is characterized in black and white tungsten adopts: a. adds sodium metasilicate 250-500 gram/ton, carboxymethyl cellulose 20-40 gram/ton, stirs 2-5 minute; B. add plumbi nitras 800-1200 gram/ton, add nitrosophenyl hydroxylamine amine ammonium salt 500-800 gram/ton, stirred 6-10 minute; C. add emulsification oleic acid 2-12 gram/ton, stirred 2-5 minute; D. through roughly select for 1 time, 2 times selected, scan for 2 times, the tungsten rough concentrate.
Method of the present invention is that the complex multi-metal raw ore with tungstenic (tungstic acid) 0.55%, molybdenum (Mo) 0.11%, bismuth (Bi) 0.18%, fluorite (calcirm-fluoride) 18% carries out fragmentation, wet grinding, be milled to fineness-0.074mm and account for 85-90%, the control pulp density is 40%, enter surge tank, add medicament in the groove: waterglass 200 gram/tons, kerosene and diesel oil are by the miscella 30 gram/tons, 2 that mix at 1: 1
#Oil 20 gram/tons stir beginning flotation molybdenum, bismuth mineral after 6 minutes.Flotation froth enters the operation of molybdenum bismuth separating flotation through 3 times after selected, adds active carbon, vulcanized sodium size mixing back FLOTATION SEPARATION molybdenum, bismuth, obtains molybdenum concntrate, bismuth concentrate respectively.After molybdenum, bismuth flotation tailing are scanned through 2 times, diesel oil=1: 1) and 2 add sulphur nitrogen in the mine tailing ore pulp No. 9, miscella (kerosene:
#Oil carries out the flotation of bismuth sulphur, and flotation froth enters bismuth sulphur content from flotation operation through 2 times after selected, adds bleaching powder, sulphur nitrogen in the ore pulp No. 9 and 2
#Oil, through 2 times selected and scan for 3 times, obtain the mine tailing after bismuth concentrate, sulphur concentrate and the flotation of bismuth sulphur respectively.
The mine tailing of bismuth sulphur flotation is added surge tank, the certain density ore pulp of furnishing, carry out the tungsten flotation operation, in surge tank, successively add: sodium metasilicate 250-500 gram/ton, carboxymethyl cellulose 20-40 gram/ton, stirred 3 minutes, add again: plumbi nitras 800-1200 gram/ton, nitrosophenyl hydroxylamine amine ammonium salt (being called for short CF) 500-800 gram/ton, stirred 6 minutes, and then add: emulsification oleic acid (being called for short OS-2) 2-12 gram/ton, stirred 3 minutes, ore pulp is fed flotation device carries out the tungsten flotation, roughly select for 1 time, 2 times selected, scan for 2 times.Each selected sodium metasilicate 50 gram/tons of adding are scanned at every turn and are added CF 25-50 gram/ton, OS-2 1-2 gram/ton.Whole floatation process slurry pH is 8-9.Obtain the tungsten rough concentrate after selected, trioxygen-containing tungsten 5-10%.
The at first thickening of tungsten rough concentrate ore pulp makes pulp density reach 50-60%, adds NaOH 50 gram/tons, oxidation paraffin wax soap (being called for short 731) 200 gram/tons then, stirs 8 minutes.Add sodium metasilicate 2000 gram/tons again, ore pulp is heated to stirring 45 minutes more than 95 ℃.After finishing, stirring in ore pulp, adds raw ore slurry volume 3-4 clear water dilution doubly, sedimentation clarification dehydration, the control pulp density reaches 30-35% and sends into flotation device and carry out selected, through 4 times selected, scan for 2 times, add hydrochloric acid 2000 gram/tons in the selected concentrate pulp, stirred 60 minutes, dewatering and filtering obtains white tungsten fine ore, mine tailing is through high-gradient magnetic separation, and magnetic product obtains wolframite through table concentration, and the non-magnetic product of high-gradient magnetic separation is mine tailing and abandons.The mine tailing of shaking table reaches about 30% pulp density through thickening, adds plumbi nitras, sodium carbonate, bigcatkin willow hydroximic acid, tributyl phosphate, 2
#Wet goods is deceived the tungsten flotation, obtains tungsten ore, trioxygen-containing tungsten about 15%.Flotation tailing abandons as mine tailing.
Adopt this method flotation tungsten ore except that the tungsten rough concentrate that obtains trioxygen-containing tungsten 5-10%, its mine tailing enters the fluorite operation.At first tungsten flotation tailing ore pulp is sent into tank diameter, the interpolation medicament is sodium metasilicate 200-500 gram/ton, oxidation paraffin wax soap 100 gram/tons, stir and send into flotation device flotation fluorite after 5 minutes, the rough concentrate of flotation is gone into the ball mill fine grinding through thickening is laggard, and mog reaches-and 0.074mm accounts for more than 92%.It is selected through 8 times that ore pulp after the fine grinding is sent into flotation device, each selected acidified sodium silicate (sodium metasilicate: sulfuric acid=1: 1) that adds respectively, the 6th time selected after, small amount of fluorine sodium metasilicate and carboxymethyl cellulose are added in selected operation again, the 8th selected flotation concentrate that obtains selected the mineral that a part of garnet, hornblend, diopside etc. and fluorite are intergrowth with the method for high-gradient magnetic separation, turn back to the fine grinding operation, the non-magnetic product of high-gradient magnetic separation is final fluorite concentrate, and all the other products of this operation all abandon as mine tailing.
The method that reclaims the black and white tungsten ore from the complex multi-metal ore deposit of the present invention has technological process and simplifies, the rate of recovery height of tungsten, whole process is not owing to use slurry pH such as caustic soda, sulfuric acid to adjust agent, flotation tailing water has reached emission request, saved medicament expense usefulness, owing to realized flotation operation under the natural pH value, help improving advantages such as fluorite index simultaneously, can be widely used in sorting of tungsten ore.
Fig. 1 is the beneficiation method principle flow chart that reclaims the black and white tungsten ore from the complex multi-metal ore deposit of the present invention.
Embodiment 1:
Adopt method of the present invention to reclaim the black and white tungsten ore from the polymetallic ore of complexity, its regime of agent of tungsten flotation operation that carries out is: sodium metasilicate 400 gram/tons, plumbi nitras 1000 gram/tons, nitrosophenyl hydroxylamine amine ammonium salt 700 gram/tons, emulsification oleic acid 8 gram/tons.Roughly select operation concentrate grade tungstic acid 2.74%, the rate of recovery 87.89%.Carried out contrast test with soda processes and lime method, soda processes concentrate grade tungstic acid 2.67%, the rate of recovery 76.92% under the optimum condition.And the lime method concentrate grade is 2.50%, and the rate of recovery also can only reach 80.15%.Result of the test is shown in Table 1.
Embodiment 2:
Adopt method of the present invention to reclaim black and white tungsten from the complex multi-metal ore deposit, carry out the tungsten flotation operation, its regime of agent is: sodium metasilicate 400 gram/tons, carboxymethyl cellulose 40 gram/tons, plumbi nitras 800 gram/tons, nitrosophenyl hydroxylamine amine ammonium salt 600 gram/tons, emulsification oleic acid 4 gram/tons.Ore deposit grade tungstic acid 0.44%, tungsten rough concentrate grade tungstic acid 3.30%, the rate of recovery 87.85% are given in flotation.
Table 1
| Method | Name of product | Productive rate % | Grade % | Rate of recovery % |
| Soda processes | Concentrate mine tailing sulfide ore tailings | 15.77 84.23 100.00 | 2.67 0.15 0.547 | 76.92 23.08 100.00 |
| Lime method | Concentrate mine tailing sulfide ore tailings | 17.35 82.65 100.00 | 2.50 0.13 0.541 | 80.15 19.85 100.00 |
| The CF method | Concentrate mine tailing sulfide ore tailings | 17.67 82.23 100.00 | 2.74 0.081 0.551 | 87.89 12.11 100.00 |
Claims (1)
- One kind from the complex multi-metal ore deposit first flotation sulphide ore reclaim the beneficiation method of black and white tungsten again, it is characterized in that the step of flotation tungsten from the mine tailing behind the flotation sulphide ore is:A. add sodium metasilicate 250-500 gram/ton, carboxymethyl cellulose 20-40 gram/ton, stirred 2-5 minute;B. add plumbi nitras 800-1200 gram/ton, add nitrosophenyl hydroxylamine amine ammonium salt 500-800 gram/ton, stirred 6-10 minute;C. add emulsification oleic acid 2-12 gram/ton, stirred 2-5 minute;D. through roughly select for 1 time, 2 times selected, scan for 2 times, the tungsten rough concentrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117062A CN1055033C (en) | 1995-10-23 | 1995-10-23 | Beneficiation method for recovering wolframite and scheelite from complex polymetallic ores |
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| Application Number | Priority Date | Filing Date | Title |
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| CN95117062A CN1055033C (en) | 1995-10-23 | 1995-10-23 | Beneficiation method for recovering wolframite and scheelite from complex polymetallic ores |
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| Publication Number | Publication Date |
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| CN1133265A CN1133265A (en) | 1996-10-16 |
| CN1055033C true CN1055033C (en) | 2000-08-02 |
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| CN95117062A Expired - Fee Related CN1055033C (en) | 1995-10-23 | 1995-10-23 | Beneficiation method for recovering wolframite and scheelite from complex polymetallic ores |
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| CN101224441B (en) * | 2007-01-18 | 2012-03-28 | 中国地质科学院郑州矿产综合利用研究所 | Molybdenum-tungsten oxide ore dressing process |
| CN101451187B (en) * | 2007-12-04 | 2010-09-01 | 灵宝市金源矿业有限责任公司 | Comprehensive recovery method of gold ore resource containing molybdenum multi-metal |
| CN101269352B (en) * | 2008-05-05 | 2012-05-30 | 广州有色金属研究院 | Beneficiation method for black and white tungsten fine deposit |
| CN101612606B (en) * | 2008-06-25 | 2012-10-03 | 灵宝金源矿业股份有限公司 | Method for comprehensively reclaming quartz vein polymetallic oxidized ore resources |
| CN101648157B (en) * | 2009-08-25 | 2013-05-01 | 广州有色金属研究院 | Beneficiation method of black and white tungsten mineral |
| CN101979145A (en) * | 2010-10-25 | 2011-02-23 | 云南锡业集团（控股）有限责任公司 | Method for separating scheelite from fluorite |
| CN102211053B (en) * | 2011-05-27 | 2013-06-19 | 广州有色金属研究院 | Method for separating black and white tungsten bulk flotation rough concentrates |
| CN102631976B (en) * | 2012-03-30 | 2013-10-09 | 洛阳栾川钼业集团股份有限公司 | Method for replacing lime by sodium hydroxide in scheelite heating concentration |
| CN103406209A (en) * | 2013-07-19 | 2013-11-27 | 广州有色金属研究院 | Beneficiation method for recycling bismuth from molybdenum selecting tailings |
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| CN104084315B (en) * | 2014-07-10 | 2015-04-22 | 湖南柿竹园有色金属有限责任公司 | Beneficiation method for separating fluorite and tungsten through flotation |
| CN105312159A (en) * | 2014-07-18 | 2016-02-10 | 沈阳有色金属研究院 | Flotation reagent system for fine wolframite in gravity concentration tailings |
| CN105498978A (en) * | 2015-11-24 | 2016-04-20 | 韦立坚 | Beneficiation method for scheelite |
| CN105327784B (en) * | 2015-12-04 | 2017-11-21 | 云南锡业股份有限公司卡房分公司 | It is a kind of to select separation method of the association rich in fluorite and low-grade cassiterite in Tungsten tailing |
| CN107433230A (en) * | 2017-08-23 | 2017-12-05 | 洛阳市奇航化工有限公司 | A kind of Scheelite Flotation inhibitor and its preparation technology |
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| CN110302905A (en) * | 2019-07-31 | 2019-10-08 | 湖南柿竹园有色金属有限责任公司 | A kind of beneficiation method of wolframite |
| CN112588453A (en) * | 2020-11-27 | 2021-04-02 | 湖南柿竹园有色金属有限责任公司 | Mineral separation process for black and white tungsten ores |
| CN113428902B (en) * | 2021-07-09 | 2023-03-24 | 崇义章源钨业股份有限公司 | Method for preparing ammonium paratungstate |
| CN117960390B (en) * | 2024-04-01 | 2024-05-31 | 中国矿业大学(北京) | Method for recycling sulfur in tin polymetallic ore |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1645024A1 (en) * | 1989-05-31 | 1991-04-30 | Казахский государственный университет им.С.М.Кирова | Flotation of rare metal and tin ores |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1645024A1 (en) * | 1989-05-31 | 1991-04-30 | Казахский государственный университет им.С.М.Кирова | Flotation of rare metal and tin ores |
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