CN101062799A - Method for adsorbing phosphor contaminant in waste water by refuse ore - Google Patents
Method for adsorbing phosphor contaminant in waste water by refuse ore Download PDFInfo
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- CN101062799A CN101062799A CN 200710021702 CN200710021702A CN101062799A CN 101062799 A CN101062799 A CN 101062799A CN 200710021702 CN200710021702 CN 200710021702 CN 200710021702 A CN200710021702 A CN 200710021702A CN 101062799 A CN101062799 A CN 101062799A
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Abstract
The invention discloses a method with tailings to absorb phosphoric contaminant in waste water, which comprises the following steps: (1) sorting ore with grain size not less than 1cm and doped root system of plant from the tailings; sharing out; natural airing; jevigating to 200 order; (2) putting the jevigating tailings into muffle furnace; baking with high temperature; controlling the baking temperature at 300-500 deg. c and time above 1. 5h; (3) adding the baking tailings with 1. 5g-2. 2g/100ml proportion into waste water with phosphorus content at 0. 5-50mg/L; adjusting the pH value of the waste water at 5-10; mixing completely; reacting with clearance of phosphor above 90%. This invention provides optimum condition for absorbing tailings, which realizes comprehensive utilization of the tailings.
Description
Technical field
The present invention relates to a kind of method, thereby say so more specifically with the phosphorus Removal of Phosphorus in Wastewater in the mine tailing absorption waste water with comprehensive utilization of tailing.
Background technology
Mine tailing is the chief component of China's industrial solid castoff.Storing up of mine tailing taken vast land area, caused environmental pollution and ecological hazard, and makes that the potential useful matter can not get rational application in the mine tailing.
The comprehensive utilization of existing mine tailing mainly comprises two aspects: the one, and mine tailing selects as secondary resource again, reclaims valuable mineral.The 2nd, the direct utilization of mine tailing (the whole utilization) is about to utilize as a certain class or a few class non-metallic minerals without the mine tailing of choosing again.As making silicate cement as batching with the mine tailing substitute for clay; Mine tailing is baked bricks; Use mine tailing as the casting resin worked-out section in filling mine on the spot; Mine tailing storehouse afforestation is reclaimed, and mine tailing is produced crystallized glass article or the like.
The domestic and international at present removal method for phosphorus mainly contains the precipitator method, Coagulation Method, biological process, absorption method or the like.Wherein absorption method is because technology is simple, easy to operate, economy, and the good and extremely researchist concern of treatment effect, and wherein the selection of sorbent material is the key of absorption method.Seek a kind of efficient, convenient, cheap and good-quality sorbent material and become the focus that people pay close attention to.
Summary of the invention
1. invent the technical problem that will solve
Serious existence at phosphorus pollutes in order to utilize mine tailing better, realizes the treatment of wastes with processes of wastes against one another, the invention provides the method for phosphor contaminant in a kind of mine tailing absorption waste water, utilizes mine tailing is carried out processing treatment to adsorb phosphor contaminant in the waste water afterwards.
2. technical scheme of the present invention is as follows
The method of phosphor contaminant in a kind of mine tailing absorption waste water, its key step comprises:
(1) particle diameter in the mine tailing is sorted out greater than ore and some adulterated root systems of plant of 1cm, spread out nature and dry back levigate to 200 orders;
(2) the levigated mine tailing is placed on high-temperature roasting in the retort furnace, maturing temperature is controlled at 300 ℃～500 ℃, and the time is controlled at more than the 1.5h;
(3) mine tailing after the roasting is joined in the waste water that phosphorus content is 0.5～50mg/L in 1.5g～2.2g/100ml ratio, the pH value of regulating waste water is 5～10, and tp removal rate reaches more than 90% in the waste water of thorough mixing reaction back.
Step (1) is the pre-treatment of mine tailing, because existing technique of preparing can not all be selected all metallic ores, so from the mine tailing storehouse, adopt the non-ferrous metal impurity that the mine tailing that comes contains a little bulk hard, at first these particle diameters are sorted out greater than the ore of 1cm and some adulterated root systems of plant, spread out nature and dry that the back is levigate to get final product to 200 orders.Mine tailing is levigate, can effectively increase its specific surface area and dispersing property, help absorption.
Step (2) is the mine tailing thermal activation stage, and mine tailing is placed on high-temperature roasting in the retort furnace.The purpose of high-temperature roasting mainly is to make mine tailing along with temperature raises, and successively loses surface water, the combination water in middle water and the structural framework, and some impurity in the space, reduce the absorption resistance of moisture film, improve the voidage and the specific surface area of mine tailing, improve adsorptive power pollution substance.Maturing temperature will be controlled at 300 ℃～500 ℃, though along with the increase of temperature, the mine tailing rate of weight loss presents the trend of rising, when temperature surpasses 600 ℃, may destroy the structure that helps adsorbing, and causes the structure sintering, piles up, and has reduced adsorption effect on the contrary.
In the step (3) mine tailing after the roasting is joined in the waste water that phosphorus content is 0.5～50mg/L in 1.5g～2.2g/100ml ratio, the pH value of regulating waste water is 5～10, and temperature is controlled to be 20～40 ℃.Effect was better when wherein add-on was 1.8～2.2g/100ml, and is when add-on surpasses this scope, little for the treatment effect influence.Mine tailing and well-mixed time of waste water in the step (3) after the roasting are that 1～3h is good, like this can be so that sufficient reacting.The pH value of waste water is high more, and the effect of processing is good more, but considers the cost of processing, and suggestion is controlled at 5～10 and is advisable.
Principle of the present invention is: mine tailing belongs to complicated silicate minerals mixture, comprising with the more symbiotic gangue minerals of ore mineral and reaching a small amount of clean ore mineral that do not select, certain electric charge is with on the surface, has bigger specific surface area, and contain aluminium, iron, calcium, magnesium oxide isoreactivity material, can combine with the ion in the water, thereby reach the effect that absorption is removed.
3. beneficial effect
The invention discloses the method for phosphor contaminant in a kind of mine tailing absorption waste water, do not need through traditional technological transformation or processing according to mine tailing of the present invention, simple levigate back promptly promptly has good adsorption effect for the phosphor contaminant in the waste water by high-temperature activation, and clearance reaches more than 90%.By research mine tailing dosage, oscillation rate, temperature of reaction, duration of contact, pH value, be the research of factor such as waste water starting point concentration, the invention provides the top condition that mine tailing adsorbs.The present invention has really realized the comprehensive utilization of mine tailing, turns waste into wealth, and has made full use of the potential value of mine tailing, can alleviate the useless admittedly accumulation of mine tailing simultaneously to a certain extent, has purified environment, is to achieve many things at one stroke.
Description of drawings
Fig. 1 is the graph of a relation of the clearance of phosphorus in original debris dosage and the waste water;
Fig. 2 is original debris and the thermal activation mine tailing absorption comparison diagram to phosphorus-containing wastewater;
Fig. 3 is thermal activation mine tailing and the waste water duration of contact figure that influences to tp removal rate;
Fig. 4 be in the waste water temperature to the figure that influences of tp removal rate;
Fig. 5 is the influence figure of the pH value of waste water solution to tp removal rate;
Fig. 6 is the influence figure of the concentration of waste water solution to tp removal rate;
Fig. 7 is the adsorption isothermal line of thermal activation mine tailing;
Fig. 8 is the fitted figure of testing data and the linear adsorption isotherm equation of Langmuir;
Fig. 9 is the fitted figure of testing data and the linear adsorption isotherm equation of Freundlich.
Embodiment
In order to determine the top condition of phosphorus in the mine tailing absorption tail water, carry out the adsorption test of series of influence factors with simulated wastewater earlier.Use KH
2PO
4With the phosphorous simulated wastewater of configuration, mine tailing is mixed with simulated wastewater, in the Erlenmeyer flask of packing into, in constant temperature oscillator, vibrate, fully supernatant liquid filtering is got in absorption after the standing over night, measures residual concentration.Contrast starting point concentration and residual concentration can learn that mine tailing is to absorption properties such as the clearance of phosphorus in the waste water, adsorptive capacitys.
The test method of each influence factor is as follows:
(1) mine tailing dosage: fixing preliminary examination waste strength, temperature of reaction, oscillation rate, the pH value changes the dosage of mine tailing duration of contact, measures its influence to absorption.
(2) temperature of reaction: fixing preliminary examination waste strength, the mine tailing dosage, the pH value changes temperature of reaction duration of contact, measures its influence to absorption.
(3) duration of contact: fixing preliminary examination waste strength, the mine tailing dosage, temperature of reaction, the pH value is measured the absorption situation of differential responses time mine tailing to pollution substance in the waste water, determines saturated adsorption time.
(4) pH value: fixing preliminary examination waste strength, the mine tailing dosage, temperature of reaction changes preliminary examination pH duration of contact, measures its influence to absorption.
(5) waste water preliminary examination concentration: fixing mine tailing dosage, temperature of reaction, oscillation rate, the pH value, is done the adsorption test of mine tailing to different preliminary examination concentration waste water at duration of contact, and, make adsorption isothermal line according to residual concentration and adsorptive capacity separately, draw some absorption properties of mine tailing.
1. mine tailing pre-treatment and solution allocation
Adopt the copper mine tailing from Tongling, Anhui, the wherein iron ore of bulk (particle diameter is greater than 1cm), root system of plant sorted out, spread out dry after, be milled to 200 orders.Use KH
2PO
4Dispose phosphorous (with PO
4 3+Meter) standardized solution of 1g/L is stand-by.
2. original debris is to the absorption of phosphorus-containing wastewater
Dispose the simulated wastewater of phosphorous 50mg/L with standardized solution, get the 200 order original debris of 0.2g, 0.4g, 0.6g, 0.8g, 1.0g, 1.2g, 1.4g, 1.6g, 1.8g, 2.0g, 2.2g respectively, add in the 100ml waste water, under constant 25 ℃, with 200r/min vibration 2h, after the standing over night, get supernatant liquor determination and analysis adsorption effect.Find the increase facing to the mine tailing dosage, in rising trend to the clearance of phosphorus, when dosage was between 1.6g/100ml～2.0g/100ml, clearance tended towards stability, and about 83%, went out water concentration about 8.2mg/L.(as Fig. 1)
3. the thermal activation mine tailing is to the absorption of phosphorus-containing wastewater
(1) mine tailing optimal heat activation temperature determines
Get a certain amount of original debris respectively at 300 degree, 400 degree, 500 degree, heat under the 600 degree conditions, discovery is along with the rising of temperature, the percentage of water loss of mine tailing rises gradually, get each 2.0g of mine tailing of each temperature heating, do adsorption test, discovery is from 300 heat-activated mine tailings to 500 degree heat-activated mine tailing, clearance increases gradually, 600 degree roasting mine tailings descend on the contrary to some extent to the clearance of phosphorus, this is because temperature is too high, destroyed the crystalline structure that mine tailing helps adsorbing on the contrary,, found that simultaneously roasting time is to almost not influence of absorption property so determine that the maturing temperature about 500 degree is the optimum temps that improves the mine tailing absorption property.
(2) the different dosages of thermal activation mine tailing are to the influence of clearance
Get the 500 degree thermal activation mine tailings of 1.0g, 1.2g, 1.4g, 1.6g, 1.8g, 2.0g, 2.2g, 2.4g respectively, to the 100ml50mg/L simulated wastewater at 25 ℃, the 200r/min 2h that vibrate, the concentration of residual phosphorus in the survey solution after the standing over night.Discovery is along with the increase of dosage, and clearance increases, and when dosage during at 2.0g/100ml～2.4g/100ml, it is stable that clearance reaches, and about 96.5%, goes out water concentration and be reduced to about 1.7mg/L from 50mg/L.Clearance is not enhanced with respect to heating mine tailing, and the highest clearance has been brought up to about 96.5% from about 83%.(see figure 2)
(3) duration of contact is to the influence of clearance
Get 2g thermal activation mine tailing, to the 100ml50mg/L simulated wastewater at 25 ℃, do adsorption test under the 200r/min oscillation rate, when 5min, 15min, 30min, 45min, 60min, 75min, 90min, 105min, 120min, measure the residual phosphorus concentration of absorption back solution respectively.Discovery is along with the increase of duration of contact, and clearance increases gradually, and when reached 60min duration of contact, absorption reached capacity, and it is stable that clearance reaches.(as Fig. 3)
(4) temperature of reaction is gone the influence of clearance
Get 2g thermal activation mine tailing, respectively under 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ constant temperature to the 100ml50mg/L simulated wastewater, behind the 200r/min vibration 1h, standing over night is measured residual phosphorus concentration in the solution, discovery is along with the rising of temperature, clearance increases gradually, and when temperature reached 35 ℃, clearance reached extreme value 98.4%, when temperature was elevated to 40 ℃ again, clearance descended on the contrary to some extent.(as Fig. 4)
(5) the pH value is to the influence of clearance
Get 2g thermal activation mine tailing, the starting point concentration of regulating simulated wastewater respectively be 2.56,3.33,4.53,7.14,9.29,10.90,11.71 under 25 ℃ of constant temperature to the 100ml50mg/L simulated wastewater, behind the 200r/min vibration 1h, standing over night is measured residual phosphorus concentration in the solution.The result shows that clearance is in rising trend along with the increase of pH value, and the pH value is 4.53 when above, and clearance reaches more than 96.5%, when the pH value reaches 11.71, almost measures in the solution less than residual phosphorus, and clearance almost reaches 100%.(as Fig. 5)
(6) the primary simulation waste strength is to the influence and the adsorption isothermal line of absorption
The configuration starting point concentration is each 100ml of simulated wastewater of 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 80mg/L, 100mg/L, mix with 2g thermal activation mine tailing, at 25 ℃ of constant temperature, the 1h that vibrates under the 200r/min oscillation rate surveys residual phosphorus concentration after the standing over night.Along with the increase of starting point concentration, clearance constantly descends, and (see figure 6) is also made the adsorption isothermal line of thermal activation mine tailing thus, and along with the increase of starting point concentration, adsorptive capacity is in rising trend.(see figure 7)
This group testing data is carried out match (as Fig. 8, Fig. 9) with linear adsorption isotherm equation of Langmuir and the linear adsorption isotherm equation of Freundlich respectively, and fitting degree is better, and standard deviation is respectively 0.987 and 0.9814.Further analyze Langmuir constant and Freundlic constant (as table 1), can draw some absorption properties of thermal activation mine tailing, by the Langmuir constant as can be seen, the thermal activation mine tailing is to the maximal absorptive capacity q of phosphorus
MaxBe 4.56mg/L, in the Freundlic constant, 1/n can characterize the absorption property of sorbent material, when 1/n is between 0～0.5, illustrates that sorbent material is suitable for adsorbing this adsorbate, when 1/n＞0.5, illustrate that this sorbent material is bad for the absorption property of adsorbate, after the absorption and Freundlic equation model of thermal activation mine tailing to phosphorus, 1/n is 0.4388, illustrate that absorption property is better, the thermal activation mine tailing is a kind of effective phosphorus adsorbent.
Table 1 Langmuir constant and Freundlic constant
| The Langmulr constant | The Freundlic constant | |||||
| R 2 | q max(mg/L) | b(L/mg) | R 2 | k | 1/n | |
| Phosphorus (PO 4 3-) | 0.987 | 4.56 | 0.93 | 0.9814 | 1.72 | 0.4388 |
Take from the iron tailings of Tangshan Area, carry out pre-treatment according to embodiment 1 same method, thermal activation, under the equivalent responses condition, mine tailing after the roasting is joined in the waste water that phosphorus content is 0.5～50mg/L in 1.5g～2.2g/100ml ratio, the pH value of regulating waste water is 5～10, and thorough mixing reaction back mine tailing is more or less the same to the clearance of phosphorus-containing wastewater and the adsorption effect of Tongling copper mine tailing.
Take from the water sample in Nanjing Forestry University side bilge downstream in the school, total phosphorus concentration is about 1.3mg/L, pH is about 7.5, get the 2g mine tailing according to embodiment 1 described step this water sample of 100ml is adsorbed sample with thermal activation copper mine tailing and thermal activation iron tailings respectively, (not regulating pH), clearance is respectively about 95% and 94%, and tangible adsorption effect is arranged, and absorption back strength of solution has dropped to below the 0.06mg/L.
Take from the water sample in community wastewater ditch downstream, Nanjing, total phosphorus concentration is about 1.6mg/L, pH is about 7.2, get the 2g mine tailing according to embodiment 1 described step this water sample of 100ml is adsorbed sample with thermal activation copper mine tailing and thermal activation iron tailings respectively, (not regulating pH), clearance is respectively about 95% and 93%, and tangible adsorption effect is also arranged, and absorption back strength of solution has dropped to below the 0.06mg/L.
Claims (5)
1. the method for phosphor contaminant in the mine tailing absorption waste water, its step comprises:
(1) particle diameter in the mine tailing is sorted out greater than ore and some adulterated root systems of plant of 1cm, spread out nature and dry back levigate to 200 orders;
(2) the levigated mine tailing is placed on high-temperature roasting in the retort furnace, maturing temperature is controlled at 300 ℃～500 ℃, and the time is controlled at more than the 1h;
(3) mine tailing after the roasting is joined in the waste water that phosphorus content is 0.5～50mg/L in 1.5g～2.2g/100ml ratio, the pH value of regulating waste water is 5～10, and temperature is controlled to be 20～40 ℃, and tp removal rate reaches more than 90% in the waste water of thorough mixing reaction back.
2. the method for phosphor contaminant is characterized in that described mine tailing is a non-ferro metals debris in a kind of mine tailing absorption waste water according to claim 1.
3. the method for phosphor contaminant is characterized in that described non-ferro metals debris is copper mine tailing or iron tailings in a kind of mine tailing absorption waste water according to claim 2.
4. the method for phosphor contaminant is characterized in that in the step (3) mine tailing after the roasting being joined in the phosphorus-containing wastewater in 1.8g～2.2g/100ml ratio in a kind of mine tailing absorption waste water according to claim 2.
5. according to the method for phosphor contaminant in each described a kind of mine tailing absorption waste water in the claim 1～4, it is characterized in that mine tailing and the well-mixed time of waste water after the roasting is 1～3h in the step (3).
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| CN101966444A (en) * | 2010-11-15 | 2011-02-09 | 西北农林科技大学 | Preparation method of dephosphorisation absorptive material and application thereof |
| CN102531143A (en) * | 2011-12-31 | 2012-07-04 | 浙江大学 | Method for preparing wastewater treatment agent from slag of gold mine tailings, wastewater treatment agent prepared by the method and application |
| CN103253727A (en) * | 2013-04-28 | 2013-08-21 | 重庆科技学院 | Method for deeply purifying phosphorus wastewater through utilizing high-phosphorus iron ores |
| CN103395907A (en) * | 2013-08-20 | 2013-11-20 | 陈双喜 | Method of filtering oil stains by adopting waterproof and ventilating sands |
| CN107032439A (en) * | 2017-06-20 | 2017-08-11 | 安徽师范大学 | A kind of method that modified copper tailing adsorbs phosphate in waste water pollutant |
| CN108499547A (en) * | 2018-05-23 | 2018-09-07 | 常州清流环保科技有限公司 | A kind of adsorbent and its methods and applications prepared using polyaluminium chloride lime scum |
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| CN1332896C (en) * | 2004-07-02 | 2007-08-22 | 桂林工学院 | Process for removing nitrogen and phosphor from sewage capable of being built by separate periods |
| CN1238275C (en) * | 2004-09-02 | 2006-01-25 | 上海交通大学 | Filter material having phosphor adsorbing and biological membrane function and its preparing method |
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| JP4536493B2 (en) * | 2004-11-25 | 2010-09-01 | Ｄｏｗａホールディングス株式会社 | Phosphorus removal method and regeneration method of phosphorus adsorbent |
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| CN101966444A (en) * | 2010-11-15 | 2011-02-09 | 西北农林科技大学 | Preparation method of dephosphorisation absorptive material and application thereof |
| CN101966444B (en) * | 2010-11-15 | 2012-11-14 | 西北农林科技大学 | Preparation method of dephosphorisation absorptive material and application thereof |
| CN102531143A (en) * | 2011-12-31 | 2012-07-04 | 浙江大学 | Method for preparing wastewater treatment agent from slag of gold mine tailings, wastewater treatment agent prepared by the method and application |
| CN102531143B (en) * | 2011-12-31 | 2013-07-24 | 浙江大学 | Method for preparing wastewater treatment agent from slag of gold mine tailings, wastewater treatment agent prepared by the method and application |
| CN103253727A (en) * | 2013-04-28 | 2013-08-21 | 重庆科技学院 | Method for deeply purifying phosphorus wastewater through utilizing high-phosphorus iron ores |
| CN103253727B (en) * | 2013-04-28 | 2015-09-16 | 重庆科技学院 | A kind of method of high-phosphorus iron ore mine tailing deep purifying Removal of Phosphorus in Wastewater |
| CN103395907A (en) * | 2013-08-20 | 2013-11-20 | 陈双喜 | Method of filtering oil stains by adopting waterproof and ventilating sands |
| CN103395907B (en) * | 2013-08-20 | 2016-01-20 | 陈双喜 | A kind of method adopting waterproof and breathable sand to filter greasy dirt |
| CN107032439A (en) * | 2017-06-20 | 2017-08-11 | 安徽师范大学 | A kind of method that modified copper tailing adsorbs phosphate in waste water pollutant |
| CN108499547A (en) * | 2018-05-23 | 2018-09-07 | 常州清流环保科技有限公司 | A kind of adsorbent and its methods and applications prepared using polyaluminium chloride lime scum |
| CN112979277A (en) * | 2021-03-03 | 2021-06-18 | 东北大学 | Preparation method of porous functional material for self-crystallization construction of adsorption sites |
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