CN101628773B - Treatment process of copper-iron-contained high-concentration acidic mine wastewater - Google Patents
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Abstract
The invention relates to a treatment process of copper-iron-contained high-concentration acidic mine wastewater. The treatment process comprises the following sequential process steps: (1) neutralization to remove iron; (2) solid-liquid separation; (3) biological sulfuration; (4) solid-liquid separation; and (5) biological purification for recovering valuable constituents in the wastewater and enabling yielding water to achieve an emission standard. The invention has the advantages of high removal rate of copper, iron and sulfate radicals, strong suitability, low treatment cost, environmentalprotection, good comprehensive recovery utilization effect, and the like and is particularly suitable for treating the copper-iron-contained high-concentration acidic mine wastewater generated in thecopper-extracting production process by a biological wet method and in the mining process of copper sulphide.
Description
One. technical field
The present invention relates to a kind of waste water treatment process, especially a kind of treatment process of copper-iron-contained high-concentration acidic mine wastewater is suitable for copper-sulphide ores mining and biological wet method and proposes the copper-iron-contained high-concentration acid wastewater in mine processing that produces in the copper production process.
Two. background technology
Carry in the copper production process in copper-sulphide ores mining and biological wet method, the acid wastewater in mine principal feature that is produced is that the pH value is low, species of metal ion is many, copper, iron and sulfate radical plasma concentration are higher, and its pH value is about 2.0, iron ion content is higher than 7g/L, sulfate concentration reaches 20g/L, content of copper ion is 300-500mg/L.If acidic mine waste water is entered near farmland, can make the farm crop jaundice, salting of soil; Enter near water body, can endanger fish and other hydrobiont, and by the food chain harmful to human.
At present in the industry following three kinds of methods are mainly adopted in the processing of acid wastewater in mine:
(1) be the chemical precipitation method of representative with neutralization precipitation and sulfide precipitation.It mainly is by adding neutralizing agent or vulcanizing agent that chemical precipitation method is handled the high density acid wastewater in mine, increase waste water ph and generate oxyhydroxide or sulfide precipitation with metal ion in the waste water, by solid-liquid separation throw out is removed discharged wastewater met the national standard at last.Though chemical precipitation method is through constantly development and improvement are ripe day by day, because its treating processes exists the precipitation additive amount of medicament big, the processing cost height, handle not thorough, produce secondary pollution, valuable constituent such as can't reclaim at deficiency, restricts further applying of this method.Chinese patent CN1418831 disclosed " a kind of method of handling non-ferrous metal acid waste water " for example, this method is to adopt one section lime neutralization to add two steps of two sections bodied ferric sulfate precipitation process to handle non-ferrous metal acid waste water.Chinese patent CN1613796 disclosed " a kind of treatment process of acid waste water " for another example, this method directly is added in the barium slag in the waste water that contains a large amount of sulfate ions, barium ion in the barium slag and the reaction of the sulfate ion in the waste water generate barium sulfate precipitate, have purified acid waste water.In addition, Chinese patent CN1931729 discloses " method that a kind of acid waste water containing heavy metal is handled and utilized ", and this method comprises the following steps: that 1. contain the acid waste water of heavy metal respectively through two kinds of exotic materials filtration facility filtration, purifications; 2. the relieving haperacidity of purifying waste water; 3. the low cycling utilization of wastewater that contains acid concentration of facility exit after filtration.Also there are processing costs height, filter plant deficiencies such as dirt is stifled easily, working pressure is big, are unsuitable for high content acid wastewater and handle.
(2) membrane separation process.Membrane separation process is to be separating medium with the selective permeation film, when having impellent such as pressure difference, concentration difference, potential difference, temperature head when the film both sides, separates, purifies thereby the feed side component optionally sees through film.Must adopt additive method to reclaim valuable metal when the Mo partition method is used for acid waste water technology, the acid waste water pH qualified discharge of having purified with the neutralisation assurance perhaps recycles the acid waste water of having purified simultaneously.In addition, because there are deficiencies such as processing costs height, dirt is stifled easily, working pressure is big in membrane separation process, are unsuitable for high content acid wastewater and handle.Chinese patent CN1872742 disclosed " processing method of methd for treating mine wastewater by using membrane technology " for example, the technical process of this method is: mine wastewater → water reservoir → water transfer pump → mechanical filter → fiber ball filter → activated charcoal filter → accurate filter → reverse osmosis membrane group → water purification.Chinese patent CN1872742 disclosed " processing method of methd for treating mine wastewater by using membrane technology " for another example, the technical process of this method is: mine wastewater → water reservoir → water transfer pump → mechanical filter → fiber ball filter → activated charcoal filter → accurate filter → reverse osmosis membrane group → water purification.
(3) method such as biological process is handled.Microbial method is the fresh approach of at present domestic and international same for treating acidic mine wastewater, and this method is to utilize the biological reducing reaction of sulphate reducing bacteria by alienation vitriol, is H with sulfate reduction
2S or S
2-, and then with waste water in metal ion generate sulfide precipitation, reclaim metallic sulfide; Biological reducing reaction simultaneously will discharge basicity, improve wastewater pH.Utilize the microbial method same for treating acidic mine wastewater of sulphate reducing bacteria to have advantages such as expense is low, suitability strong, non-secondary pollution, recyclable valuable constituent, but since pure microbial method exist be subjected to the restriction of organism self-ability, treatable pH scope little, to deficiencies such as metal ion tolerance ability, processing efficiency are low, also be unsuitable for high content acid wastewater and handle, therefore fail to apply.Chinese patent CN101219844 disclosed " a kind of technology of biological treatment of mine acidic wastewater " for example, this technology is to utilize sewage plant sludge acid fermentation product to handle hydrosulphate waste water and reclaim elemental sulfur for the carbon source of sulphate reducing bacteria: sulphate reducing bacteria SRB is H with biological sulphate reduction in the anaerobic biological reactor
2S or S
2-, colorless sulfur bacteria is with H in the easy-to-keep biological membrane reactor
2S or S
2-Bio-oxidation is an elemental sulfur.
Along with the minimizing day by day of global Mineral resources amount, and the increasingly stringent of national environmental protection policy, seek that a kind of processing cost is low, suitability is strong, acid wastewater in mine treatment process environmentally friendly and that can reclaim valuable constituent in the waste water just seems particularly urgent.
Three. summary of the invention
The object of the present invention is to provide a kind of treatment process of copper-iron-contained high-concentration acidic mine wastewater, it can reclaim in the waste water valuable constituent and make treating water environmentally friendly, can reduce processing cost again and promote suitability.
For finishing this task, the present invention carries out in the following way:
A kind of treatment process of copper-iron-contained high-concentration acidic mine wastewater comprises following processing steps in sequence and condition:
The first step: in and deironing, add lime or Wingdale is regulated waste water ph to 2.5～3.5 to cupric iron mine acid waste water, make that ferric iron generates Fe (OH) in the waste water
3In and slag;
Second the step: solid-liquid separation, with in and deironing after clear liquid and in and slag carry out solid-liquid separation, isolated in and slag send the mine tailing storehouse;
The 3rd step: biological sulfuration, clear liquid behind the solid-liquid separation A and the 5th recirculation water of step after the biopurification are mixed, blending ratio is 1: 3～10, mix back pH value and be controlled at 4.0～7.0 scopes, make the sulfonium ion generation vulcanization reaction in copper, remainder fe ion and the biopurification recirculation water in the clear liquid, generate the sulfuration scum and the sulfuration clear liquid of sulfuration copper ashes, trace.
The 4th step: solid-liquid separation, the sulfuration copper ashes of biology sulfuration generation, the sulfuration scum and the sulfuration clear liquid of trace are carried out solid-liquid separation, the sulfuration scum of isolated sulfuration copper ashes, trace send the smeltery to reclaim copper;
The 5th step: biopurification, the sulfuration clear liquid behind solid-liquid separation B add microorganism sulphate reducing bacteria SRB, make SO in the waste water
4 2-Be reduced into HS
-And with metal remained ion generation sulfide or precipitation of hydroxide in the waste water, to vulcanize clear liquid pH value simultaneously and transfer to neutrality, after the reaction, sulfide or precipitation of hydroxide be Separation and Recovery in the UASB reactor, recirculation water after the biopurification partly turns back to biological vulcanisation step of the 3rd step, and all the other water outlets up to standard efflux.
Treatment process of copper-iron-contained high-concentration acidic mine wastewater of the present invention further comprises following processing condition:
The first step: in and deironing, regulate waste water ph to 2.7～2.9;
The 3rd step: biological sulfuration, the blending ratio of clear liquid and recirculation water is 1: 3～6, mixes back pH value and is controlled at 4.6～5.0 scopes.
Technology of the present invention, the i.e. ultimate principle of " in and deironing-biology sulfuration-biopurification " combined treatment process:
(1) in and deironing
Adopt and add lime or Wingdale adjusting waste water ph, ferric iron generates Fe (OH) in the waste water
3Throw out, small quantity of copper ion generates Cu (OH)
2Throw out, the main chemical reactions of generation is as follows:
OH
-+H
+＝H
2O
Ca
2++SO
4 2-＝CaSO
4↓
Fe
3++3OH
-＝Fe(OH)
3↓
Cu
2++2OH
-＝Cu(OH)
2↓
The purpose of handling with deironing during waste water carries out is to remove most of ferric iron in the waste water, the one, in follow-up sulfidizing, consume sulfonium ion in order to prevent ferric iron, the 2nd, remove the redox potential that ferric iron can reduce waste water, be beneficial to the growth and breeding of sulphate reducing bacteria in the biopurification processing.
(2) biological sulfuration
Solution and the 3rd in the lime and after the deironing is gone on foot the biopurification recirculation water mix, the sulfonium ion generation vulcanization reaction in the copper in the waste water, iron ion and the biopurification recirculation water, main chemical reactions is as follows:
Cu
2++S
2-＝CuS↓
2Fe
3++3S
2-＝2FeS↓+S↓
Fe
2++S
2-＝FeS↓
(3) biopurification is handled
Utilize microorganism sulphate reducing bacteria SRB with waste water SO
4 2-Be reduced into HS
-, and with waste water in the metal remained ion generate sulfide or precipitation of hydroxide is removed, the main chemical reactions of generation is as follows:
HS
-+M
2+＝MS↓+H
+
M
2++2OH
-＝M(OH)
2↓
Can be used as lime of the present invention or Wingdale and be the production domesticization raw material easily purchased in market and cheap, microorganism sulphate reducing bacteria SRB is common bacteria and is easy to cultivate.
Advantage of the present invention:
Since designed in and deironing-biology sulfuration-biopurification composite technology, made full use of the processing advantage of chemical method and biological process, so can make the iron clearance greater than 99%, the sulfate radical clearance is greater than 90%, water outlet reaches GB8978-96 " integrated wastewater discharge standard " primary standard, can be back to produce or directly discharging.
2. simultaneously because waste water carries out pre-treatment through " in and deironing " earlier, it is strong that waste water quality is changed adaptability; The biological reducing reaction discharges basicity, the neutralizing acid wastewater, in the saving and medicament and bioenergy be nutrition source with organic waste, the treatment of wastes with processes of wastes against one another is so Treatment of Copper iron high density acid wastewater in mine has advantages such as suitability is strong, processing cost is low, environmentally friendly.
3. in addition owing to use valuable constituent copper in " biological sulfuration " Separation and Recovery waste water, copper recovery can reach 85%, so this process synthesis recycling is profitable.
Four. description of drawings
The concrete grammar of invention is provided by the following drawings.
Fig. 1 is a kind of treatment process of copper-iron-contained high-concentration acidic mine wastewater schema that proposes according to the present invention.
The present invention is described in further detail below in conjunction with accompanying drawing.
Five. embodiment
As shown in Figure 1, a kind of treatment process of copper-iron-contained high-concentration acidic mine wastewater according to the present invention proposes comprises following processing steps in sequence and condition:
The first step: in and deironing, add lime or Wingdale is regulated waste water ph to 2.5～3.5 to cupric iron mine acid waste water, make that ferric iron generates Fe (OH) in the waste water
3In and slag;
Second the step: solid-liquid separation, with in and deironing after clear liquid and in and slag carry out solid-liquid separation, isolated in and slag send the mine tailing storehouse;
The 3rd step: biological sulfuration, clear liquid behind the solid-liquid separation A and the 5th recirculation water of step after the biopurification are mixed, blending ratio is 1: 3～10, mix back pH value and be controlled at 4.0～7.0 scopes, make the sulfonium ion generation vulcanization reaction in copper, remainder fe ion and the biopurification recirculation water in the clear liquid, generate the sulfuration scum and the sulfuration clear liquid of sulfuration copper ashes, trace.
The 4th step: solid-liquid separation, the sulfuration copper ashes of biology sulfuration generation, the sulfuration scum and the sulfuration clear liquid of trace are carried out solid-liquid separation, the sulfuration scum of isolated sulfuration copper ashes, trace send the smeltery to reclaim copper;
The 5th step: biopurification, the sulfuration clear liquid behind solid-liquid separation B add microorganism sulphate reducing bacteria SRB, make SO in the waste water
4 2-Be reduced into HS
-And with metal remained ion generation sulfide or precipitation of hydroxide in the waste water, to vulcanize clear liquid pH value simultaneously and transfer to neutrality, after the reaction, sulfide or precipitation of hydroxide be Separation and Recovery in the UASB reactor, recirculation water after the biopurification partly turns back to biological vulcanisation step of the 3rd step, and all the other water outlets up to standard efflux.
Treatment process of copper-iron-contained high-concentration acidic mine wastewater further comprises following processing condition:
The first step: in and deironing, regulate waste water ph to 2.7～2.9;
The 3rd step: biological sulfuration, the blending ratio of clear liquid and recirculation water is 1: 3～6, mixes back pH value and is controlled at 4.6～5.0 scopes.
Add the nutrition source Sodium.alpha.-hydroxypropionate in described biopurification step, control COD compares SO
4 2-In 1.0～1.5 scopes.
In described biopurification step with all the other water outlets reuse or efflux after the aeration oxide treatment.
The embodiment of the invention one and embodiment two are all by above-mentioned processing step and condition, promptly get a certain amount of copper-iron-contained high-concentration acid wastewater in mine, add lime and stirring, regulate waste water ph to 2.5～3.5 and 2.7～2.9 respectively, fully carry out solid-liquid separation after the reaction, gained clear liquid and biopurification reaction recirculation water fully stir by after 1: 3～10 and 1: 3～6 mixed, treat to carry out solid-liquid separation after vulcanization reaction is finished.The gained clear liquid carries out the SRB biological reducing and handles as the water inlet of 50L biopurification processing unit, the recirculation water partial reflux after the biopurification, and all the other water outlets up to standard efflux.
Adopt lime neutralisation Comparative Examples one, it is identical quantitatively and the copper-iron-contained high-concentration acid wastewater in mine of kind to get the foregoing description, adds lime and stirs, and regulates about waste water ph to 7.5, carries out solid-liquid separation after fully reacting.
Above-mentioned three examples adopt same test analysis method: Cu to adopt the GB/T7475-1987 atomic absorption spectroscopy determination, and Fe adopts the GB/T11911-1989 atomic absorption spectrophotometry to measure, and vitriol adopts GB 11899-89 gravimetric determination; Test materials is the accurate pH meter of pHS-3C, technical grade Sodium.alpha.-hydroxypropionate, lime.
With in technology of the present invention and the prior art lime and technology comparative test result such as table 1.
In table 1 the present invention and the lime and art breading cupric iron mine acid waste water effect (g/L)
From table 1, can find out, adopt the every index of water outlet of art breading copper-iron-contained high-concentration acid wastewater in mine of the present invention to be better than in the lime and technology, and handle waste water per ton and can increase income and economize on spending more than 19 yuan.
Claims (4)
1. treatment process of copper-iron-contained high-concentration acidic mine wastewater comprises following processing steps in sequence and condition:
The first step: in and deironing, add lime or Wingdale is regulated waste water ph to 2.5～3.5 to cupric iron mine acid waste water, make in the waste water ferric iron produce Fe (OH)
3In and slag;
Second the step: solid-liquid separation, with in and deironing after clear liquid and in and slag carry out solid-liquid separation, isolated in and slag send the mine tailing storehouse;
The 3rd step: biological sulfuration, the recirculation water that second clear liquid of step after the solid-liquid separation and the 5th gone on foot after the biopurification mixes, blending ratio is 1: 3～10, mix back pH value 4.0～7.0 scopes that are controlled at and make sulfonium ion generation vulcanization reaction in copper, remainder fe ion and the biopurification recirculation water in the clear liquid, generate sulfuration copper ashes, micro-sulfuration scum and vulcanize clear liquid;
The 4th step: solid-liquid separation, the sulfuration copper ashes of biology sulfuration generation, the sulfuration scum and the sulfuration clear liquid of trace are carried out solid-liquid separation, the sulfuration scum of isolated sulfuration copper ashes, trace send the smeltery to reclaim copper;
The 5th step: biopurification, the sulfuration clear liquid after the 4th step solid-liquid separation adds microorganism sulphate reducing bacteria SRB, makes SO in the waste water
4 2-Be reduced into HS
-And with metal remained ion generation sulfide or precipitation of hydroxide in the waste water, to vulcanize clear liquid pH value simultaneously and transfer to neutrality, after the reaction, sulfide or precipitation of hydroxide be Separation and Recovery in the UASB reactor, recirculation water after the biopurification partly turns back to biological vulcanisation step of the 3rd step, all the other water outlet dischargings up to standard.
2. treatment process of copper-iron-contained high-concentration acidic mine wastewater according to claim 1 further comprises following processing condition:
The first step: in and deironing, regulate waste water ph to 2.7～2.9;
The 3rd step: biological sulfuration, the blending ratio of clear liquid and recirculation water is 1: 3～6, mixes back pH value and is controlled at 4.0～5.0 scopes.
3. treatment process of copper-iron-contained high-concentration acidic mine wastewater according to claim 1 is characterized in that adding the nutrition source Sodium.alpha.-hydroxypropionate in described biopurification step, control COD compares SO
4 2-In 1.0～1.5 scopes.
4. according to claim 1 or 3 described treatment process of copper-iron-contained high-concentration acidic mine wastewater, it is characterized in that in described biopurification step, all the other water outlets being effluxed after the aeration oxide treatment.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285730A (en) * | 2011-05-26 | 2011-12-21 | 武汉海德天物新材料有限公司 | Treatment method and device for acid-base neutralization of mine wastewater |
| CN102241446B (en) * | 2011-05-26 | 2013-12-18 | 武汉海德天物新材料有限公司 | Mine wastewater treatment method and device |
| CN102311189B (en) * | 2011-08-12 | 2013-04-24 | 马前 | System for treatment of acid mine drainage and resource recovery of iron, aluminum, copper and zinc in drainage |
| CN102515389A (en) * | 2011-12-09 | 2012-06-27 | 紫金矿业集团股份有限公司 | Harmless treatment process for acidic copper-containing wastewater |
| CN103232106B (en) * | 2012-07-27 | 2014-07-16 | 紫金矿业集团股份有限公司 | Method for neutralizing copper-sulfur mine acidic wastewater |
| CN102839285B (en) * | 2012-09-10 | 2014-04-23 | 合肥工业大学 | Method for recovering copper from waste mine rocks |
| CN104211156B (en) * | 2014-08-14 | 2016-05-04 | 中国科学院沈阳应用生态研究所 | A kind of acid waste water Fe that removes3+The method of acidity |
| CN105439374B (en) * | 2014-12-12 | 2018-01-23 | 武汉森泰环保股份有限公司 | A kind of handling process and its device of acid high-sulfate organic wastewater |
| CN104944575B (en) * | 2015-05-29 | 2017-03-22 | 江汉大学 | Biological treatment method of acidic sulfate wastewater containing Fe3+ and Cu2+ |
| CN108164081A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of lead-zinc smelting waste acid purifying treatment method |
| CN107601779B (en) * | 2017-10-27 | 2020-07-21 | 紫金矿业集团股份有限公司 | Method and device for treating and recycling mine copper-containing acidic wastewater |
| CN111362419A (en) * | 2018-12-26 | 2020-07-03 | 有研工程技术研究院有限公司 | Biochemical treatment system for mine acidic wastewater |
| CN111252873B (en) * | 2020-02-20 | 2021-06-08 | 中国科学院过程工程研究所 | Source inhibition method for acid mine wastewater |
| CN112537838B (en) * | 2020-11-16 | 2023-04-07 | 武汉理工大学 | Treatment method and treatment device for copper ions in mine wastewater |
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| WO1997029055A1 (en) * | 1996-02-06 | 1997-08-14 | Thiopaq Sulfur Systems B.V. | Process for the treatment of water containing heavy metal ions |
| CN101186398A (en) * | 2007-09-12 | 2008-05-28 | 昆山华科生物高分子材料研究所有限公司 | Heavy metal waste water continuous treating method and treating device thereof |
| CN101219844A (en) * | 2008-01-23 | 2008-07-16 | 太原理工大学 | Technique for biological treatment of mine acidic wastewater |
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| WO1997029055A1 (en) * | 1996-02-06 | 1997-08-14 | Thiopaq Sulfur Systems B.V. | Process for the treatment of water containing heavy metal ions |
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| CN101219844A (en) * | 2008-01-23 | 2008-07-16 | 太原理工大学 | Technique for biological treatment of mine acidic wastewater |
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