CN102826724A - Acidic coal mine wastewater treatment device and method - Google Patents
Acidic coal mine wastewater treatment device and method Download PDFInfo
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- CN102826724A CN102826724A CN2012103493868A CN201210349386A CN102826724A CN 102826724 A CN102826724 A CN 102826724A CN 2012103493868 A CN2012103493868 A CN 2012103493868A CN 201210349386 A CN201210349386 A CN 201210349386A CN 102826724 A CN102826724 A CN 102826724A
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Abstract
The invention provides an acidic coal mine wastewater treatment device and method. The acidic coal mine wastewater treatment device comprises a coagulation tank, a precipitation tank, a filter unit and a bioreactor, wherein a stirrer is arranged in the coagulation tank, and the rotation speed of the stirrer is adjustable. The coagulant is prepared by the following steps: preparing diesel caustic sludge with the oil content of lower than 5% and water into 20-40% caustic sludge slurry, preparing PAM (polyacrylamide) into a 0.06-0.1% water solution, and mixing the PAM solution and the caustic sludge slurry in a volume ratio o 1:2-1:5. The filter unit is a filter column which is 1.5-1.8 meters long, the internal diameter of the column is 30 millimeters, and the filter material used in the filter column is manganese sand soaked with a potassium permanganate solution. A biomembrane carrier is added into the bioreactor; and the carrier is a suspended biological carrier prepared from cocoanut shells.
Description
Technical field
The present invention relates to the apparatus and method that a kind of waste-water from coal mine is handled, relate to the apparatus and method that a kind of acid waste-water from coal mine is handled especially.
Background technology
At present in the industry following three kinds of methods are mainly adopted in the processing of mining area acid waste water:
(1) be the chemical precipitation method of representative with neutralization precipitation and sulfide precipitation.Chemical precipitation method treatment of high concentration acid wastewater in mine mainly is through adding neutralizing agent or vulcanizing agent; Increase waste water ph and generate oxyhydroxide or sulfide precipitation with metals ion in the waste water; Through 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 deposition 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 ", this method comprise the following steps: 1. contain heavy metal acid waste water respectively through two kinds of exotic materials filtration facility filtration, purifications; 2. the relieving haperacidity of purifying waste water; 3. through filtering the low cycling utilization of wastewater that contains acid concentration of facility exit.Also there are deficiencies such as processing costs is high, the easy dirt of straining installation is stifled, working pressure is big, are inappropriate 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.The Mo separation processes for acidic waste water must be used when other methods recovery of valuable metals, and in the same time with assurance of purified acidic pH of the wastewater discharge standards, use or recycling of acidic waste water has been purified.In addition, because there are deficiencies such as processing costs is high, dirt is stifled easily, working pressure is big in membrane separation process, are inappropriate for high content acid wastewater and handle.Chinese patent CN1872742 disclosed " process 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 " process 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 through alienation vitriol, is H with sulfate reduction
2S or S
2-, and then with waste water in metals 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 receive the restriction of organism self-ability, treatable pH scope little, to deficiencies such as metal ion tolerance ability, processing efficiency are low; Also be inappropriate 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.
These methods all have its vice proper, and the most important thing is, acid coal mine waste water also has higher heavy metal content, thereby increased the intractability of this waste water because it also has the SS value of superelevation.
Summary of the invention
The invention provides a kind of treatment unit and method that is used for acid waste-water from coal mine.
The described treatment unit that is used for acid waste-water from coal mine comprises coagulation basin, settling tank, filtration unit and bio-reactor.
Wherein, be provided with whisking appliance in the coagulation basin, and the rotating speed of this whisking appliance can be regulated.
Wherein, filtration unit is a Filter column, filters 1.5～1.8 meters of column lengths, and 30 millimeters of pillar internal diameters, the filtrate that uses in the Filter column are the manganese sand that soaked through potassium permanganate solution.
Wherein, bio-reactor is provided with two, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum, employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L).
The said treatment process that is used for acid waste-water from coal mine is following:
(1) pending waste water is introduced coagulation basin; In coagulation basin, add coagulating agent, coagulating agent is selected the mixture of the solution of diesel alkaline residue and PAM, and its consumption is 4.5～6ml/L; Use 200 rev/mins rotating speed to stir 1 minute fast earlier, change 40 rev/mins then into and stirred 15 minutes.
(2) pit water that coagulation is good precipitates 40～50 minutes in settling tank.In the pond, add milk of lime during deposition, the pH value of settling tank supernatant is adjusted between 7.0～7.5.
(3) supernatant of settling tank gets into filtration unit, and through long 1.5～1.8 meters, the Filter column that the pillar internal diameter is 30 millimeters filters, and the filtrate in the Filter column is treated manganese sand, and filtering velocity is 10～11m/ hour, and the filtering layer height of filtrate is 1 meter.
(4) filtrate flows in the bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum; Employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L); To add volume be 50%～55% of reactor volume to carrier in the anaerobic biofilter, aerobic biological fluid-bed in carrier to add volume be 20%～30% of reactor volume.Inoculation of activated-sludge in the reactor drum, through about 15 days domestications and extension film, reactor drum can get into the commencement of commercial operation stage.
Wherein employed coagulating agent diesel alkaline residue is meant the residue that in the diesel oil cleaning process, produces in the step (1), and its oleaginousness is lower than 5%, and the diesel alkaline residue water is configured to 20～40% alkaline residue slip, PAM is configured to 0.6～1 ‰ the aqueous solution.Described PAM solution and alkaline residue slip are that 1: 2～1: 5 ratio is mixed according to volume ratio, obtain the employed coagulating agent of step (1).
Wherein employed filtrate is handled natural manganese sand and get in the step (2).Specifically, exactly the common natural manganese sand that can buy on the market being positioned over concentration is to soak 4～6 hours in 1%～1.5% the potassium permanganate solution, and the particle diameter of employed natural manganese sand is 0.3～0.4 millimeter.
Be that the suspended biological carrier that raw material is processed is prepared from through following method with the Exocarpium cocois (Cocos nucifera L) described in the step (3) wherein, with Exocarpium cocois (Cocos nucifera L) clean, oven dry, pulverization process, pulverize and reach 30～40 orders; Exocarpium cocois (Cocos nucifera L) particle after pulverizing is carried out alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after the alkalinisation treatment is carried out carrying out crosslinking reaction with excessive TGM 1 after the processed; Solid product and Trimethylamine 99 alcoholic solution that crosslinking reaction is generated carry out quaternary ammonium reaction, obtain solid product; Solid product is cleaned, drying get final product suspended biological carrier.
Treatment unit and method that this cover of the present invention is used for acid waste-water from coal mine have the following advantages.
1, cost is low; Coagulating agent uses diesel alkaline residue to cooperate a small amount of PAM can obtain good coagulation effect, and cost is very low, and diesel alkaline residue is alkalescence; When playing coagulation effect; This coagulating agent can also improve the pH value of waste water, reduces the consumption of follow-up pH value regulator, further reduces cost; The suspended biological carrier that uses Exocarpium cocois (Cocos nucifera L) to process as raw material in addition also has good performance, but cost is also very low.
2, filtration efficiency is high; The natural manganese sand of crossing through the potassium permanganate solution immersion treatment than undressed natural manganese sand when filtering except elimination suspended solid more effectively; And can remove the cupric ion that contains in the waste water effectively; Heavy metal ion such as iron ion, this makes the mikrobe in the follow-up bio-reactor can not receive the threat of heavy metal.
Embodiment
The analytical procedure of using among the present invention: adopt potassium dichromate process to measure COD; Adopt Potassium Persulphate oxidation---determined by ultraviolet spectrophotometry total nitrogen (TN); Adopt the filter paper filtering weighting method to measure suspended substance (SS); Adopt PHS-3C type Accurate pH instrumentation to decide the pH value, adopt spectrophotometer method to measure the content of cupric ion, iron ion and mn ion.
Embodiment 1
Experimental water is taken from colliery, the Zhao Ge village, Tangshan City mine water.The pH value 3.3 of water inlet, the COD value 110mg/l of water inlet, the TN value 70mg/l of water inlet, the SS value 4300mg/l of water inlet, the content of cupric ion, iron ion and mn ion is respectively 30.5mg/L, 67mg/L and 54.4mg/L.
At first, pending waste water is introduced coagulation basin, in coagulation basin, add coagulating agent; Coagulating agent is selected the mixture of the solution of diesel alkaline residue and PAM; Its consumption is 5ml/L, uses 200 rev/mins rotating speed to stir 1 minute fast earlier, changes 40 rev/mins then into and stirs 15 minutes.Coagulating agent makes like this, oleaginousness is lower than 5% diesel alkaline residue water and is configured to 25% alkaline residue slip, and PAM is configured to 0.6 ‰ the aqueous solution, and described PAM solution and alkaline residue slip are that 1: 4 ratio is mixed and obtained coagulating agent according to volume ratio.
Afterwards that coagulation is good pit water precipitates 45 minutes in settling tank.In the pond, add milk of lime during deposition, the pH value of settling tank supernatant is adjusted into 7.0.
The supernatant of settling tank gets into filtration unit, and through long 1.5 meters, the Filter column that the pillar internal diameter is 30 millimeters filters, and the filtrate in the Filter column is treated manganese sand, and filtering velocity is 10m/ hour, and the filtering layer height of filtrate is 1 meter.Wherein the preparation method of employed filtrate is to be that to be positioned over concentration be to soak 6 hours in 1% the potassium permanganate solution for 0.3～0.4 millimeter natural manganese sand with particle diameter.
Filtrate flows in the bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum; Employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L); To add volume be 50% of reactor volume to carrier in the anaerobic biofilter, aerobic biological fluid-bed in carrier to add volume be 20% of reactor volume.Inoculation of activated-sludge in the reactor drum, through about 15 days domestications and extension film, reactor drum can get into the commencement of commercial operation stage.Wherein be that the suspended biological carrier that raw material is processed is prepared from through following method with the Exocarpium cocois (Cocos nucifera L), with Exocarpium cocois (Cocos nucifera L) clean, oven dry, pulverization process, pulverize and reach 30 orders; Exocarpium cocois (Cocos nucifera L) particle after pulverizing is carried out alkalinisation treatment: it is 15% sodium hydroxide solution that this particle is placed massfraction, soaks 5h; Exocarpium cocois (Cocos nucifera L) after the alkalinisation treatment is carried out carrying out crosslinking reaction with excessive TGM 1 after the processed; Solid product and Trimethylamine 99 alcoholic solution that crosslinking reaction is generated carry out quaternary ammonium reaction, obtain solid product; Solid product is cleaned, drying get final product suspended biological carrier.
Effluent during final detection is aerobic biological fluid-bed, its each item index is: pH value 7.2, COD value 23mg/l, TN value 34mg/l, SS value 60mg/l, the content of cupric ion, iron ion and mn ion is respectively 0.42mg/L, 0.64mg/L and 0.35mg/L.
Embodiment 2
Experimental water is taken from colliery, the Zhao Ge village, Tangshan City mine water.The pH value 3.1 of water inlet, the COD value 133mg/l of water inlet, the TN value 91mg/l of water inlet, the SS value 3400mg/l of water inlet, the content of cupric ion, iron ion and mn ion is respectively 22.5mg/L, 87.3mg/L and 65mg/L.
At first, pending waste water is introduced coagulation basin, in coagulation basin, add coagulating agent; Coagulating agent is selected the mixture of the solution of diesel alkaline residue and PAM; Its consumption is 6ml/L, uses 200 rev/mins rotating speed to stir 1 minute fast earlier, changes 40 rev/mins then into and stirs 15 minutes.Coagulating agent makes like this, oleaginousness is lower than 5% diesel alkaline residue water and is configured to 35% alkaline residue slip, and PAM is configured to 0.8 ‰ the aqueous solution, and described PAM solution and alkaline residue slip are that 1: 5 ratio is mixed and obtained coagulating agent according to volume ratio.
Afterwards that coagulation is good pit water precipitates 45 minutes in settling tank.In the pond, add milk of lime during deposition, the pH value of settling tank supernatant is adjusted into 7.0.
The supernatant of settling tank gets into filtration unit, and through long 1.8 meters, the Filter column that the pillar internal diameter is 30 millimeters filters, and the filtrate in the Filter column is treated manganese sand, and filtering velocity is 11m/ hour, and the filtering layer height of filtrate is 1 meter.Wherein the preparation method of employed filtrate is to be that to be positioned over concentration be to soak 4 hours in 1.5% the potassium permanganate solution for 0.3～0.4 millimeter natural manganese sand with particle diameter.
Filtrate flows in the bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum; Employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L); To add volume be 55% of reactor volume to carrier in the anaerobic biofilter, aerobic biological fluid-bed in carrier to add volume be 30% of reactor volume.Inoculation of activated-sludge in the reactor drum, through about 15 days domestications and extension film, reactor drum can get into the commencement of commercial operation stage.Wherein be that the suspended biological carrier that raw material is processed is prepared from through following method with the Exocarpium cocois (Cocos nucifera L), with Exocarpium cocois (Cocos nucifera L) clean, oven dry, pulverization process, pulverize and reach 40 orders; Exocarpium cocois (Cocos nucifera L) particle after pulverizing is carried out alkalinisation treatment: it is 17% sodium hydroxide solution that this particle is placed massfraction, soaks 5h; Exocarpium cocois (Cocos nucifera L) after the alkalinisation treatment is carried out carrying out crosslinking reaction with excessive TGM 1 after the processed; Solid product and Trimethylamine 99 alcoholic solution that crosslinking reaction is generated carry out quaternary ammonium reaction, obtain solid product; Solid product is cleaned, drying get final product suspended biological carrier.
Effluent during final detection is aerobic biological fluid-bed, its each item index is: pH value 7.1, COD value 17mg/l, TN value 38mg/l, SS value 55mg/l, the content of cupric ion, iron ion and mn ion is respectively 0.29mg/L, 0.45mg/L and 0.24mg/L.
Those skilled in the art can make replacement or modification to content of the present invention according to content disclosed by the invention and the art technology of being grasped; But these replacements or modification should not be regarded as breaking away from the present invention's design, and these replacements or modification are all in the interest field that the present invention requires to protect.
Claims (9)
1. a treatment unit that is used for acid waste-water from coal mine is characterized in that it comprises coagulation basin, settling tank, filtration unit and bio-reactor.
2. the treatment unit that is used for acid waste-water from coal mine described in the claim 1 it is characterized in that being provided with whisking appliance in the coagulation basin, and the rotating speed of this whisking appliance can be regulated; Said filtration unit is a Filter column; Filter 1.5～1.8 meters of column lengths, 30 millimeters of pillar internal diameters, the filtrate that uses in the Filter column are the manganese sand that soaked through potassium permanganate solution; Described bio-reactor is provided with two, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum, employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L).
3. the treatment unit that is used for acid waste-water from coal mine described in the claim 2; It is characterized in that described coagulating agent makes through following method; Oleaginousness is configured to 20～40% alkaline residue slip less than 5% diesel alkaline residue water, PAM is configured to 0.6～1 ‰ the aqueous solution.Described PAM solution and alkaline residue slip are that 1: 2～1: 5 ratio is mixed according to volume ratio, obtain the employed coagulating agent of step (1).
4. the treatment unit that is used for acid waste-water from coal mine described in the claim 2; It is characterized in that described filtrate makes through following method; It is to soak 4～6 hours in 1%～1.5% the potassium permanganate solution that the common natural manganese sand that can buy on the market is positioned over concentration, and the particle diameter of employed natural manganese sand is 0.3～0.4 millimeter.
5. the treatment unit that is used for acid waste-water from coal mine described in the claim 2; It is characterized in that the described suspended biological carrier that with the Exocarpium cocois (Cocos nucifera L) is raw material is processed makes through following method; With Exocarpium cocois (Cocos nucifera L) clean, oven dry, pulverization process, pulverize and reach 30～40 orders; Exocarpium cocois (Cocos nucifera L) particle after pulverizing is carried out alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after the alkalinisation treatment is carried out carrying out crosslinking reaction with excessive TGM 1 after the processed; Solid product and Trimethylamine 99 alcoholic solution that crosslinking reaction is generated carry out quaternary ammonium reaction, obtain solid product; Solid product is cleaned, drying get final product suspended biological carrier.
6. treatment process that is used for acid waste-water from coal mine is characterized in that this method is made up of following steps:
(1) pending waste water is introduced coagulation basin; In coagulation basin, add coagulating agent, coagulating agent is selected the mixture of the solution of diesel alkaline residue and PAM, and its consumption is 4.5～6ml/L; Use 200 rev/mins rotating speed to stir 1 minute fast earlier, change 40 rev/mins then into and stirred 15 minutes;
(2) pit water that coagulation is good precipitates 40～50 minutes in settling tank.In the pond, add milk of lime during deposition, the pH value of settling tank supernatant is adjusted between 7.0～7.5;
(3) supernatant of settling tank gets into filtration unit, and through long 1.5～1.8 meters, the Filter column that the pillar internal diameter is 30 millimeters filters, and the filtrate in the Filter column is treated manganese sand, and filtering velocity is 10～11m/ hour, and the filtering layer height of filtrate is 1 meter;
(4) filtrate flows in the bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactor drums all adopt biomembrance process, connect between said two reactor drums.Add biofilm carrier in the reactor drum; Employed carrier is for being the suspended biological carrier that raw material is processed with the Exocarpium cocois (Cocos nucifera L); To add volume be 50%～55% of reactor volume to carrier in the anaerobic biofilter, aerobic biological fluid-bed in carrier to add volume be 20%～30% of reactor volume.Inoculation of activated-sludge in the reactor drum, through about 15 days domestications and extension film, reactor drum can get into the commencement of commercial operation stage.
7. the treatment process that is used for acid waste-water from coal mine described in the claim 6; It is characterized in that described coagulating agent makes through following method; Oleaginousness is configured to 20～40% alkaline residue slip less than 5% diesel alkaline residue water, PAM is configured to 0.6～1 ‰ the aqueous solution.Described PAM solution and alkaline residue slip are that 1: 2～1: 5 ratio is mixed according to volume ratio, obtain the employed coagulating agent of step (1).
8. the treatment process that is used for acid waste-water from coal mine described in the claim 6; It is characterized in that described filtrate makes through following method; It is to soak 4～6 hours in 1%～1.5% the potassium permanganate solution that the common natural manganese sand that can buy on the market is positioned over concentration, and the particle diameter of employed natural manganese sand is 0.3～0.4 millimeter.
9. the treatment process that is used for acid waste-water from coal mine described in the claim 6; It is characterized in that the described suspended biological carrier that with the Exocarpium cocois (Cocos nucifera L) is raw material is processed makes through following method; With Exocarpium cocois (Cocos nucifera L) clean, oven dry, pulverization process, pulverize and reach 30～40 orders; Exocarpium cocois (Cocos nucifera L) particle after pulverizing is carried out alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after the alkalinisation treatment is carried out carrying out crosslinking reaction with excessive TGM 1 after the processed; Solid product and Trimethylamine 99 alcoholic solution that crosslinking reaction is generated carry out quaternary ammonium reaction, obtain solid product; Solid product is cleaned, drying get final product suspended biological carrier.
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| CN103449671A (en) * | 2013-09-05 | 2013-12-18 | 安徽工程大学 | Treatment system for acid coal mine drainage and treatment process thereof |
| CN111392922A (en) * | 2020-05-18 | 2020-07-10 | 范誉委 | Coal washing wastewater and mine wastewater comprehensive treatment system |
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| CN111392922A (en) * | 2020-05-18 | 2020-07-10 | 范誉委 | Coal washing wastewater and mine wastewater comprehensive treatment system |
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| CN102826724B (en) | 2014-01-22 |
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