CN102826724B - Acidic coal mine wastewater treatment device and method - Google Patents
Acidic coal mine wastewater treatment device and method Download PDFInfo
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- CN102826724B CN102826724B CN201210349386.8A CN201210349386A CN102826724B CN 102826724 B CN102826724 B CN 102826724B CN 201210349386 A CN201210349386 A CN 201210349386A CN 102826724 B CN102826724 B CN 102826724B
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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 processed, relate to especially the apparatus and method that a kind of acid mine drainage is processed.
Background technology
At present in the industry the processing of mining area acid waste water is mainly adopted to following three kinds of methods:
(1) take the chemical precipitation method that neutralization precipitation and sulfide precipitation be representative.It is mainly by adding neutralizing agent or vulcanizing agent that chemical precipitation method is processed high density acid wastewater in mine, increase waste water ph and generate oxyhydroxide or sulfide precipitation with the metal ion in waste water, finally by solid-liquid separation, throw out is removed to discharged wastewater met the national standard.Although chemical precipitation method is through development and improve maturation day by day, because its treating processes exists precipitation additive amount of medicament large, processing cost is high, process not thorough, produce secondary pollution, valuable constituent such as cannot reclaim at the deficiency, further the applying of restriction the method.Chinese patent CN1418831 disclosed " a kind of method of processing acidic waste-water contg. nonferrous metals " for example, the method is to adopt one section of lime neutralization to add two steps of two sections of bodied ferric sulfate precipitation process to process acidic waste-water contg. nonferrous metals.For another example Chinese patent CN1613796 disclosed " a kind for the treatment of process of acid waste water ", the method is directly added in barium slag in the waste water that contains a large amount of sulfate ions, barium ion in barium slag reacts generation barium sulfate precipitate with the sulfate ion in waste water, has purified acid waste water.In addition, Chinese patent CN1931729 discloses " a kind of method that acid waste water containing heavy metal is processed and utilized ", and the method comprises the following steps: that 1. acid waste waters containing heavy metal are respectively through two kinds of exotic materials filtration facility filtration, purifications; 2. the relieving haperacidity of purifying waste water; 3. the lower cycling utilization of wastewater containing acid concentration of facility exit after filtration.Also there is the deficiencies such as processing costs is high, the easy dirt of filter plant is stifled, working pressure is large, be unsuitable for high content acid wastewater and process.
(2) membrane separation process.Membrane separation process is to take selectivity to see through film be separating medium, while there is the impellents such as pressure difference, concentration difference, potential difference, temperature head when film both sides, thereby feed side compositional selecting ground see through film separated, purify.When Mo partition method is used for acid waste water technique, must adopt additive method to reclaim valuable metal, by neutralisation, guarantee the acid waste water pH qualified discharge of having purified simultaneously, or recycle the acid waste water of having purified.In addition,, because membrane separation process exists the deficiencies such as high, the easy dirt of processing costs is stifled, working pressure is large, be unsuitable for high content acid wastewater and process.Chinese patent CN1872742 disclosed " processing method of methd for treating mine wastewater by using membrane technology " for example, the technical process of the 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.For another example Chinese patent CN1872742 disclosed " processing method of methd for treating mine wastewater by using membrane technology ", the technical process of the 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 processed.Microbial method is the fresh approach of at present domestic and international same for treating acidic mine wastewater, and the method is to utilize sulphate reducing bacteria by the bioreduction of alienation vitriol, by sulfate reduction, is H
2s or S
2-, and then with waste water in metal ion generate sulfide precipitation, reclaim metallic sulfide; Bioreduction will discharge basicity simultaneously, improve wastewater pH.Utilize the microbial method same for treating acidic mine wastewater of sulphate reducing bacteria to there is the advantages such as expense is low, suitability strong, non-secondary pollution, recyclable valuable constituent, but due to pure microbial method exist be subject 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 process, therefore fail to apply.Chinese patent CN101219844 disclosed " a kind of technique of biological treatment of mine acidic wastewater " for example, this technique is to utilize the carbon source that sewage plant sludge acid fermentation product is sulphate reducing bacteria process hydrosulphate waste water and reclaim elemental sulfur: in anaerobic biological reactor, sulphate reducing bacteria SRB is H by biological sulphate reduction
2s or S
2-, in easy-to-keep biological membrane reactor, colorless sulfur bacteria is by H
2s or S
2-bio-oxidation is elemental sulfur.
These methods have its inherent defect, and the most important thing is, acid coal mine waste water, because it also has the SS value of superelevation, also has higher heavy metal content, thereby have increased the intractability of this waste water.
Summary of the invention
The invention provides a kind for the treatment of unit for acid mine drainage and method.
The described treatment unit for acid mine drainage, comprises coagulation basin, settling tank, filtration unit and bio-reactor.
Wherein, in coagulation basin, be provided with agitator, and the rotating speed of this agitator can regulate.
Wherein, filtration unit is Filter column, filters 1.5～1.8 meters of column lengths, 30 millimeters of pillar internal diameters, and the filtrate using in Filter column is the manganese sand soaking through potassium permanganate solution.
Wherein, bio-reactor arranges two, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactors all adopt biomembrance process, between described two reactors, connect.In reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material.
The described treatment process for acid mine drainage is as follows:
(1) pending waste water is introduced to 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, first use the rotating speed rapid stirring 1 minute of 200 revs/min, then change 40 revs/min into and stir 15 minutes.
(2) pit water that coagulation is good precipitates 40～50 minutes in settling tank.During precipitation, in pond, add milk of lime, the pH value of settling tank supernatant liquor is adjusted between 7.0～7.5.
(3) supernatant liquor of settling tank enters filtration unit, and by long 1.5～1.8 meters, the Filter column that pillar internal diameter is 30 millimeters filters, and the filtrate in Filter column is treated manganese sand, and filtering velocity is 10～11m/ hour, and the filter height of filtrate is 1 meter.
(4) filtrate flows in bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactors all adopt biomembrance process, between described two reactors, connect.In reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material, in anaerobic biofilter, to add volume be 50%～55% of reactor volume to carrier, and it is 20%～30% of reactor volume that aerobic biological fluid-bed middle carrier adds volume.Inoculation of activated-sludge in reactor, through domestication and the biofilm of about 15 days, reactor can enter the commencement of commercial operation stage.
The coagulating agent diesel alkaline residue wherein using in step (1) refers to the residue producing in diesel oil cleaning process, and its oleaginousness, lower than 5%, is configured to diesel alkaline residue water 20～40% alkaline residue slip, PAM is configured to 0.6～1 ‰ the aqueous solution.Described PAM solution mixes with the ratio that alkaline residue slip is 1: 2～1: 5 according to volume ratio, obtains the coagulating agent that step (1) is used.
The filtrate wherein using in step (2) is processed natural manganese sand and obtain.Specifically, exactly the common natural manganese sand that can buy on market is positioned over to concentration and is in 1%～1.5% potassium permanganate solution and soak 4～6 hours, the particle diameter of the natural manganese sand using is 0.3～0.4 millimeter.
Wherein the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material of take described in step (3) is prepared from by the following method, by 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 to alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed in to massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after alkalinisation treatment is carried out carrying out crosslinking reaction with excessive Ethylene glycol dimethacrylate after 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 to the dry suspended biological carrier that gets final product to obtain.
This cover of the present invention has the following advantages for treatment unit and the method for acid mine drainage.
1, cost is low, coagulating agent is used diesel alkaline residue to coordinate 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 conditioning agent, further reduces costs; The suspended biological carrier that uses in addition Exocarpium cocois (Cocos nucifera L) to make for raw material also has good performance, but cost is also very low.
2, filtration efficiency is high, the natural manganese sand of crossing through potassium permanganate solution immersion treatment than undressed natural manganese sand when filtering except elimination suspended solid more effectively, and can effectively remove the cupric ion containing in waste water, the heavy metal ion such as iron ion, this makes the microorganism in follow-up bio-reactor can not be subject to the threat of heavy metal.
Embodiment
The analytical procedure of using in the present invention: adopt potassium dichromate process to measure COD; Adopt potassium persulfate oxidation---determined by ultraviolet spectrophotometry total nitrogen (TN); Adopt filter paper filtering weighting method to measure suspended substance (SS); Adopt PHS-3C type Accurate pH instrumentation to determine 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.
First, pending waste water is introduced to 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, first uses the rotating speed rapid stirring 1 minute of 200 revs/min, then changes 40 revs/min into and stirs 15 minutes.Coagulating agent makes like this, and oleaginousness is configured to 25% alkaline residue slip lower than 5% diesel alkaline residue water, PAM is configured to 0.6 ‰ the aqueous solution, and the ratio that described PAM solution and alkaline residue slip are 1: 4 according to volume ratio is mixed to get coagulating agent.
Afterwards the good pit water of coagulation is precipitated to 45 minutes in settling tank.During precipitation, in pond, add milk of lime, the pH value of settling tank supernatant liquor is adjusted into 7.0.
The supernatant liquor of settling tank enters filtration unit, and by long 1.5 meters, the Filter column that pillar internal diameter is 30 millimeters filters, and the filtrate in Filter column is treated manganese sand, and filtering velocity is 10m/ hour, and the filter height of filtrate is 1 meter.It is to soak 6 hours in 1% potassium permanganate solution that the natural manganese sand that the preparation method of the filtrate that wherein used is is 0.3～0.4 millimeter by particle diameter is positioned over concentration.
Filtrate flows in bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactors all adopt biomembrance process, between described two reactors, connect.In reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material, in anaerobic biofilter, to add volume be 50% of reactor volume to carrier, and it is 20% of reactor volume that aerobic biological fluid-bed middle carrier adds volume.Inoculation of activated-sludge in reactor, through domestication and the biofilm of about 15 days, reactor can enter the commencement of commercial operation stage.The suspended biological carrier that the Exocarpium cocois (Cocos nucifera L) of wherein take is made as raw material is prepared from by the following method, by 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 to alkalinisation treatment: it is 15% sodium hydroxide solution that this particle is placed in to massfraction, soaks 5h; Exocarpium cocois (Cocos nucifera L) after alkalinisation treatment is carried out carrying out crosslinking reaction with excessive Ethylene glycol dimethacrylate after 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 to the dry suspended biological carrier that gets final product to obtain.
Effluent liquid during final detection is aerobic biological fluid-bed, its indices 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.
First, pending waste water is introduced to 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, first uses the rotating speed rapid stirring 1 minute of 200 revs/min, then changes 40 revs/min into and stirs 15 minutes.Coagulating agent makes like this, and oleaginousness is configured to 35% alkaline residue slip lower than 5% diesel alkaline residue water, PAM is configured to 0.8 ‰ the aqueous solution, and the ratio that described PAM solution and alkaline residue slip are 1: 5 according to volume ratio is mixed to get coagulating agent.
Afterwards the good pit water of coagulation is precipitated to 45 minutes in settling tank.During precipitation, in pond, add milk of lime, the pH value of settling tank supernatant liquor is adjusted into 7.0.
The supernatant liquor of settling tank enters filtration unit, and by long 1.8 meters, the Filter column that pillar internal diameter is 30 millimeters filters, and the filtrate in Filter column is treated manganese sand, and filtering velocity is 11m/ hour, and the filter height of filtrate is 1 meter.It is to soak 4 hours in 1.5% potassium permanganate solution that the natural manganese sand that the preparation method of the filtrate that wherein used is is 0.3～0.4 millimeter by particle diameter is positioned over concentration.
Filtrate flows in bio-reactor, and 2 bio-reactors are set altogether, is respectively anaerobic biofilter, aerobic biological fluid-bed.These two reactors all adopt biomembrance process, between described two reactors, connect.In reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material, in anaerobic biofilter, to add volume be 55% of reactor volume to carrier, and it is 30% of reactor volume that aerobic biological fluid-bed middle carrier adds volume.Inoculation of activated-sludge in reactor, through domestication and the biofilm of about 15 days, reactor can enter the commencement of commercial operation stage.The suspended biological carrier that the Exocarpium cocois (Cocos nucifera L) of wherein take is made as raw material is prepared from by the following method, by 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 to alkalinisation treatment: it is 17% sodium hydroxide solution that this particle is placed in to massfraction, soaks 5h; Exocarpium cocois (Cocos nucifera L) after alkalinisation treatment is carried out carrying out crosslinking reaction with excessive Ethylene glycol dimethacrylate after 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 to the dry suspended biological carrier that gets final product to obtain.
Effluent liquid during final detection is aerobic biological fluid-bed, its indices 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 and replacing or modification content of the present invention according to content disclosed by the invention and the art technology of grasping; but these replacements or modification should not be considered as departing from the present invention's design, and these replacements or modification are all in the claimed interest field of the present invention.
Claims (7)
1. the treatment unit for acid mine drainage, it is characterized in that it comprises coagulation basin, settling tank, filtration unit and bio-reactor, wherein in coagulation basin, throw in coagulating agent and be provided with agitator, and the rotating speed of this agitator can regulate, described filtration unit is Filter column, filter 1.5～1.8 meters of column lengths, 30 millimeters of pillar internal diameters, the filtrate using in Filter column is the manganese sand soaking through potassium permanganate solution, described bio-reactor arranges two, it is respectively anaerobic biofilter, aerobic biological fluid-bed, these two reactors all adopt biomembrance process, between described two reactors, connect, in reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material, wherein said coagulating agent makes by the following method, oleaginousness is less than to 5% diesel alkaline residue water and is configured to 20～40% alkaline residue slip, PAM is configured to 0.6～1 ‰ the aqueous solution, the ratio that described PAM solution is 1:2～1:5 with alkaline residue slip according to volume ratio is mixed, obtain the coagulating agent that step (1) is used.
2. the treatment unit for acid mine drainage described in claim 1, it is characterized in that described filtrate makes by the following method, it is to soak 4～6 hours in 1%～1.5% potassium permanganate solution that the common natural manganese sand that can buy on market is positioned over to concentration, and the particle diameter of the natural manganese sand using is 0.3～0.4 millimeter.
3. the treatment unit for acid mine drainage described in claim 1, it is characterized in that described take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material and making by the following method, by 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 to alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed in to massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after alkalinisation treatment is carried out carrying out crosslinking reaction with excessive Ethylene glycol dimethacrylate after 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 to the dry suspended biological carrier that gets final product to obtain.
4. for a treatment process for acid mine drainage, it is characterized in that the method is comprised of following steps:
(1) pending waste water is introduced to 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, first use the rotating speed rapid stirring 1 minute of 200 revs/min, then change 40 revs/min into and stir 15 minutes;
(2) pit water that coagulation is good precipitates 40～50 minutes in settling tank, adds milk of lime during precipitation in pond, and the pH value of settling tank supernatant liquor is adjusted between 7.0～7.5;
(3) supernatant liquor of settling tank enters filtration unit, and by long 1.5～1.8 meters, the Filter column that pillar internal diameter is 30 millimeters filters, and the filtrate in Filter column is treated manganese sand, and filtering velocity is 10～11m/ hour, and the filter height of filtrate is 1 meter;
(4) filtrate flows in bio-reactor, 2 bio-reactors are set altogether, it is respectively anaerobic biofilter, aerobic biological fluid-bed, these two reactors all adopt biomembrance process, between described two reactors, connect, in reactor, add biofilm carrier, the carrier using is for take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material, in anaerobic biofilter, to add volume be 50%～55% of reactor volume to carrier, it is 20%～30% of reactor volume that aerobic biological fluid-bed middle carrier adds volume, inoculation of activated-sludge in reactor, domestication and biofilm through about 15 days, reactor can enter the commencement of commercial operation stage.
5. the treatment process for acid mine drainage described in claim 4, it is characterized in that described coagulating agent makes by the following method, oleaginousness is less than to 5% diesel alkaline residue water and is configured to 20～40% alkaline residue slip, PAM is configured to 0.6～1 ‰ the aqueous solution, the ratio that described PAM solution is 1:2～1:5 with alkaline residue slip according to volume ratio is mixed, and obtains the coagulating agent that step (1) is used.
6. the treatment process for acid mine drainage described in claim 4, it is characterized in that described filtrate makes by the following method, it is to soak 4～6 hours in 1%～1.5% potassium permanganate solution that the common natural manganese sand that can buy on market is positioned over to concentration, and the particle diameter of the natural manganese sand using is 0.3～0.4 millimeter.
7. the treatment process for acid mine drainage described in claim 4, it is characterized in that described take the suspended biological carrier that Exocarpium cocois (Cocos nucifera L) makes as raw material and making by the following method, by 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 to alkalinisation treatment: it is 15%～17% sodium hydroxide solution that this particle is placed in to massfraction, soaks 4～6h; Exocarpium cocois (Cocos nucifera L) after alkalinisation treatment is carried out carrying out crosslinking reaction with excessive Ethylene glycol dimethacrylate after 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 to the dry suspended biological carrier that gets final product to obtain.
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| CN101503267B (en) * | 2009-03-13 | 2010-12-01 | 哈尔滨工业大学 | Coal chemical industry wastewater treating method |
| CN101830585A (en) * | 2010-05-21 | 2010-09-15 | 中国矿业大学(北京) | Acid mine water treatment system |
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