CN103232106B - Method for neutralizing copper-sulfur mine acidic wastewater - Google Patents
Method for neutralizing copper-sulfur mine acidic wastewater Download PDFInfo
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- CN103232106B CN103232106B CN201210265957.XA CN201210265957A CN103232106B CN 103232106 B CN103232106 B CN 103232106B CN 201210265957 A CN201210265957 A CN 201210265957A CN 103232106 B CN103232106 B CN 103232106B
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Abstract
The invention relates to a method for neutralizing copper-sulfur mine acidic wastewater. First, lime or sodium hydroxide is added into a grinding machine, and grinding is carried out with crude ore; copper selection is carried out by sequentially adding water glass, aniline aerofloat, and ethionine ester; primary neutralization reaction is carried out with the acidic wastewater and copper tailing slurry; butyl xanthate and terpenic oil are added for selecting sulfur; lime or sodium hydroxide is added into sulfur tailing slurry, and a neutralization reaction is carried out again. The method is fast and convenient, and has the advantages of high adaptability and good effect. With the method, acidic wastewater can be effectively treated during a floatation process, and can reach a discharge standard. The method has important significance in ensuring mineral resource development sustainable development and avoiding environment pollution.
Description
One. technical field
The present invention relates to technical field of waste water processing, particularly a kind of in and the method for copper sulphur acid wastewater in mine.
Two. background technology
Mine wastewater is one of primary pollution source of mine environment, and wherein, what pollution range was the widest, hazard rating is maximum is acid wastewater in mine.Due to nonferrous mine acid waste water acidity high (general pH=1.5～2.5), contain the heavy metal ion that kind is many, concentration is high (generally containing cu, Pb, zn, cd, As and Mn etc.), discharge of wastewater will cause severe contamination to ecotope.Neutralisation is to administer the most frequently used method of acid waste water.So-called neutralisation refers to neutralizing agent eliminates excessive acid or alkali in waste water, makes pH value for neutral.But all there is drawback in currently used several neutralization method in various degree.As the neutralisation improvement acid waste water of offeing medicine, neutralizing agent is generally used caustic soda.Its disadvantage is: one, caustic soda price is very expensive, and many producers are reluctant to use, and cause a large amount of acid waste water not do any processing with regard to outer row; Two, the dosage of caustic soda is not easy to grasp, and adds excessive meeting to make water be alkalescence, still polluted-water; Three, the wastewater treatment larger to variation water quality, dispensing neutralisation is more aobvious ineffective.Though can save caustic soda and make neutralizing agent with unslaked lime, but still have above-mentioned two, three shortcomings, and labour intensity is large, operating environment is poor, lime-ash is more in addition, and sediment is bulky, dehydration trouble.In addition, after lime neutralizing treatment waste water, heavy metal hydroxide-alumen ustum proportion of generation is little, is easily broken into again small-particle, so its settling velocity is slow when strong mixing or conveying.Tend in settlement separate process excessively with current, make again the turbidity of wastewater after processing raise.Neutralization of lime milk is easy to operate, and cost is lower, strong adaptability, shortcoming be in reaction tank, easily form larger particles and be deposited in pond at the bottom of, reduce the utilization ratio of lime, body refuse amount is large.In Wingdale and drum process because producing precipitation at inner wall of rotary drum water outlet in a large number, easily cause cylinder internal diameter effective dimensions to reduce, stop up water outlet, therefore need often to clean, reduce plant factor, and equipment is huge, complex structure, greatly, during running, noise is large in investment.Flow lifting type becomes filtering velocity expansion neutralisation because containing a large amount of suspended substances in sour water, easily cause the obstruction of Up-Flow Expansion Filter, therefore particle diameter of filter medium requires strict, simultaneously, restricted containing acid concentration for waste water, after processing, pH value is lower, needs to supplement to process and could discharge, and treatment facility can not overload operation.
Visible, according to the water quality characteristic of acid wastewater in mine, seek in a kind of quick and convenient, strong adaptability, effective flotation and regime of agent, acid waste water is effectively addressed and qualified discharge in flotation flowsheet, guarantees exploitation of mineral resources Sustainable development and avoid environmental pollution significant.
Three. summary of the invention
The object of this research be to develop a kind of quick and convenient, strong adaptability, effect significant in and the method for copper sulphur acid wastewater in mine.
In order to reach above object, the technical solution used in the present invention: be first to throw in unslaked lime or sodium hydroxide and raw ore while ore grinding in grinding machine, add successively again water glass, aniline black powder, ethyl ammonia sulfate preferentially to select copper, acid waste water and copper Tailings Slurry carry out neutralization reaction first, then add successively butyl xanthate, pine camphor grease separation sulphur, finally in sulphur Tailings Slurry, add unslaked lime or sodium hydroxide to carry out neutralization reaction again.
The inventive method specifically comprises the following steps:
(1) use clear water and the raw ore ratio ore grinding of 1:1 in mass ratio, in ore mill, add 80～100g unslaked lime/L acid waste water or 20～30g sodium hydroxide/L acid waste water simultaneously;
(2) in the ore grinding product of high alkalinity, add successively water glass 400～500g/ ton raw ore, aniline black powder 40～50g/ ton raw ore, ethyl ammonia sulfate 40～50g/ ton raw ore carries out copper and roughly selects, add again aniline black powder 10～20g/ ton raw ore, ethyl ammonia sulfate 10～20g/ ton raw ore carries out copper to be scanned, and does not add any medicament to carry out twice bronze medal selected, obtains copper ore concentrates;
(3) copper Tailings Slurry concentration is controlled to 33%, adds acid waste water to make this copper Tailings Slurry be diluted to 20% concentration by 33%, carry out neutralization reaction first;
(4) in the copper Tailings Slurry after the neutralization first of 20% concentration, add 0～20g unslaked lime/L acid waste water or 0～10g sodium hydroxide/L acid waste water, make pH remain on 6～7, add successively butyl xanthate 80～100g/ ton raw ore, pine camphor oil 30～40g/ ton raw ore carries out sulphur and roughly selects, add again butyl xanthate 10～20g/ ton raw ore, pine camphor oil 10～20g/ ton raw ore carries out sulphur to be scanned, and does not add any medicament to carry out twice sulphur selected, obtains sulphur concentrate;
(5) in sulphur Tailings Slurry, add 0～20g unslaked lime/L acid waste water or 0～10g sodium hydroxide/L acid waste water, again carry out neutralization reaction, control true tailings slurry pH value 7～8.
3, effect: use this regime of agent can realize the flotation neutralizing treatment to acid waste water, do not affect production, acid waste water treatment capacity can reach 2m3/ ton raw ore, the tail washings water quality after processing can up to standardly directly be discharged into Tailings Dam, and in and tailing slurry settlement functional.
Four. accompanying drawing explanation
Fig. 1 be the present invention a kind of in and the process flow sheet of the method for copper sulphur acid wastewater in mine;
Fig. 2 be of the present invention final in and tailing slurry settlement curve.
In figure, identify:
A raw ore; B acid waste water; C copper ore concentrates; D sulphur concentrate; E true tailings slurry;
A unslaked lime; B sodium hydroxide; C water glass; D aniline black powder; E ethyl ammonia sulfate;
F butyl xanthate; G pine camphor oil.
Five. embodiment
Below in conjunction with accompanying drawing 1 and embodiment, the present invention is described in further detail.
Below in conjunction with specific embodiment, the specific embodiment of the invention is further illustrated.The super-huge copper mine of Min Xi produces a large amount of copper-containing acid waste waters in exploitation and production process, and the copper-containing acid waste water that particularly copper dump leaching factory discharges, does a lot of damage to peripheral region ecotope, not yet has at present good improvement method.The acid waste water that embodiment adopts is this mine biological dump leaching process spray pond sour water, and this acid waste water is strongly-acid cupric liquid, and its essentially consist is in Table l.Flotation adopts this Mine Cu to select factory to be selected in raw ore, and metalliferous mineral be take pyrite as main, and copper mineral be take alpha chalcocite, enargite and covellite as main, and the multinomial analytical results of raw ore is in Table 2.
Table 1 acid waste water essentially consist
| pH | H 2SO 4/g·L -1 | Cu/g·L -1 | Fe/g·L -1 | Fe 2+/g/L | Fe 3+/g/L |
| 2～3 | 4.18 | 0.74 | 12.55 | 5.88 | 6.67 |
Multinomial analytical results/the % of table 2 Copper Ores chemistry
| Element | Cu | S | Al 2O 3 | As | Fe 2O 3 | SiO 2 |
| Content | 0.34 | 4.36 | 11.38 | 0.015 | 6.06 | 67.6 |
| Element | K 2O | TiO 2 | MgO | Ag | Ga | Bi |
| Content | 1.32 | 0.16 | 0.015 | 4.9g/t | 30.6*10 -6 | 0.01 |
Embodiment 1: use clear water and the raw ore ratio ore grinding of 1:1 in mass ratio, add 90g unslaked lime/L acid waste water simultaneously in ball ore mill; In ore milling product, add successively water glass 450g/ ton raw ore, aniline black powder 45g/ ton raw ore, ethyl ammonia sulfate 45g/ ton raw ore carries out copper and roughly selects, add aniline black powder 15g/ ton raw ore, ethyl ammonia sulfate 15g/ ton raw ore carries out copper to be scanned, and does not add any medicament to carry out twice bronze medal selected, obtains copper ore concentrates; Copper Tailings Slurry concentration is controlled to 33%, adds acid waste water to make this copper Tailings Slurry be diluted to 20% concentration by 33%, carry out neutralization reaction first; In copper Tailings Slurry after the neutralization first of 20% concentration, add 10g unslaked lime/L acid waste water, make pH remain on 6～7, add successively butyl xanthate 90g/ ton raw ore, pine camphor oil 35g/ ton raw ore carries out sulphur and roughly selects, add again butyl xanthate 15g/ ton raw ore, pine camphor oil 15g/ ton raw ore carries out sulphur to be scanned, and does not add any medicament to carry out twice sulphur selected, obtains sulphur concentrate; In sulphur Tailings Slurry, add 10g unslaked lime/L acid waste water, carry out neutralization reaction again, after neutralization, true tailings slurry pH value is 7～8.
Embodiment 2: use clear water and the raw ore ratio ore grinding of 1:1 in mass ratio, add 25g sodium hydroxide/L acid waste water simultaneously in ball ore mill; In ore milling product, add successively water glass 450g/ ton raw ore, aniline black powder 45g/ ton raw ore, ethyl ammonia sulfate 45g/ ton raw ore carries out copper and roughly selects, add again aniline black powder 15g/ ton raw ore, ethyl ammonia sulfate 15g/ ton raw ore carries out copper and scans, do not add any medicament to carry out twice bronze medal selected, obtain copper ore concentrates; Copper Tailings Slurry concentration is controlled to 33%, adds acid waste water to make this copper Tailings Slurry be diluted to 20% concentration by 33%, carry out neutralization reaction first; In copper Tailings Slurry after the neutralization first of 20% concentration, add 5g sodium hydroxide/L acid waste water, make pH remain on 6～7, add successively butyl xanthate 90g/ ton raw ore, pine camphor oil 35g/ ton raw ore carries out sulphur and roughly selects, add again butyl xanthate 15g/ ton raw ore, pine camphor oil 15g/ ton raw ore carries out sulphur to be scanned, and does not add any medicament to carry out twice sulphur selected, obtains sulphur concentrate; In sulphur Tailings Slurry, add 5g sodium hydroxide/L acid waste water, carry out neutralization reaction again, after neutralization, true tailings slurry pH value is 7～8.The concrete technic index of the embodiment of the present invention 1, embodiment 2 is in Table 3, and true tailings slurry settling property curve is shown in Fig. 2.
Table 3 embodiment of the present invention technic index
By embodiment table 3 and Fig. 2 result, further verified, regime of agent of the present invention not only neutralizing acid wastewater fast and flexible, strong adaptability, treatment capacity is large, can obtain copper ore concentrates, the sulphur concentrate of higher-grade and high-recovery simultaneously, after tail washings water quality reaching standard after processing, can directly be discharged into Tailings Dam, and in and tailing slurry settlement functional.
Claims (1)
1. a method that neutralizes copper sulphur acid wastewater in mine, is characterized in that: specifically comprise the following steps:
(1) use clear water and the raw ore ratio ore grinding of 1:1 in mass ratio, in ore mill, add 80～100g unslaked lime/L acid waste water or 20～30g sodium hydroxide/L acid waste water simultaneously;
(2) in the ore grinding product of high alkalinity, add successively water glass 400～500g/ ton raw ore, aniline black powder 40～50g/ ton raw ore, ethyl ammonia sulfate 40～50g/ ton raw ore carries out copper and roughly selects, add again aniline black powder 10～20g/ ton raw ore, ethyl ammonia sulfate 10～20g/ ton raw ore carries out copper to be scanned, and does not add any medicament to carry out twice bronze medal selected, obtains copper ore concentrates;
(3) copper Tailings Slurry concentration is controlled to 33%, adds acid waste water to make this copper Tailings Slurry be diluted to 20% concentration by 33%, carry out neutralization reaction first;
(4) in the copper Tailings Slurry after the neutralization first of 20% concentration, add 0～20g unslaked lime/L acid waste water or 0～10g sodium hydroxide/L acid waste water, make pH remain on 6～7, add successively butyl xanthate 80～100g/ ton raw ore, pine camphor oil 30～40g/ ton raw ore carries out sulphur and roughly selects, add again butyl xanthate 10～20g/ ton raw ore, pine camphor oil 10～20g/ ton raw ore carries out sulphur to be scanned, and does not add any medicament to carry out twice sulphur selected, obtains sulphur concentrate;
(5) in sulphur Tailings Slurry, add 0～20g unslaked lime/L acid waste water or 0～10g sodium hydroxide/L acid waste water, again carry out neutralization reaction, control true tailings slurry pH value 7～8.
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| CN103706461A (en) * | 2013-12-13 | 2014-04-09 | 北京华夏建龙矿业科技有限公司 | Unrestraint mineral processing process for arsenious copper sulphide ores |
| CN104211205B (en) * | 2014-08-14 | 2016-05-04 | 紫金矿业集团股份有限公司 | Mine low concentration acid waste water method for innocent treatment |
| CN104772220A (en) * | 2015-03-11 | 2015-07-15 | 铜陵鑫腾矿业科技有限公司 | Copper oxide ore flotation agent |
| CN104726700B (en) * | 2015-04-09 | 2016-10-19 | 紫金矿业集团股份有限公司 | The method producing copper concentrate with copper-contained sludge |
| CN104944560A (en) * | 2015-06-07 | 2015-09-30 | 长春黄金研究院 | Quick non-ferrous metal mine acid wastewater treatment method |
| CN107790291B (en) * | 2017-09-30 | 2019-08-27 | 紫金矿业集团股份有限公司 | The floatation process of comprehensive recovery of gold sulphur from copper tailing |
| CN115259815B (en) * | 2021-04-30 | 2023-07-28 | 广东清大同科环保技术有限公司 | Preparation method of metal tailing artificial aggregate |
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