CN101580294A - Method for processing landfill leachate through heterogeneous catalytic ozonation - Google Patents
Method for processing landfill leachate through heterogeneous catalytic ozonation Download PDFInfo
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- CN101580294A CN101580294A CNA2009100322108A CN200910032210A CN101580294A CN 101580294 A CN101580294 A CN 101580294A CN A2009100322108 A CNA2009100322108 A CN A2009100322108A CN 200910032210 A CN200910032210 A CN 200910032210A CN 101580294 A CN101580294 A CN 101580294A
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Abstract
The invention discloses a method for processing landfill leachate through heterogeneous catalytic ozonation in the field of wastewater treatment. Copper is used as an active component; kalium is used as a cocatalyst and loaded on an active carbon carrier to prepare an ozone catalysis catalyst; the weight percentage content of the copper as the active component is 0.5 to 3 percent of the ozone catalysis catalyst; the prepared ozone catalysis catalyst is thrown into an ozone catalysis oxidation reaction tower; simultaneously, the ozone and the landfill leachate with pH value of between 8 and 10 are input into the ozone catalysis oxidation reaction tower; and after the reaction continues for 60 and 120 minutes, wastewater is neutralized and discharged. The method completes the reaction of the solid catalyst, the landfill leachate and the ozone in a device; the degradation rate of COD reaches over 80 percent; and the removing rate of the ammonia-nitrogen number reaches over 97.5 percent. A processing unit is small and compact, has small occupied area, little power equipment and low power consumption, does not need the addition of water for thinning, has low operating expense and convenient operation and can be automatically controlled.
Description
Technical field
The present invention relates to field of waste water treatment, particularly a kind of employing heterogeneous catalyst ozone oxidation method treating refuse percolate.
Background technology
Percolate is a kind of big waste water of high-concentration hardly-degradable organism, complicated component and change of water quality that contains, and along with the prolongation of landfill time, its biochemical degradability progressively descends, and has been put into China's environment priority pollutants.Contain multiple toxicant and carcinogenic substance in the percolate, if degraded under field conditions (factors), needing its chemical oxygen demand (COD) of time in 15 years (is COD, down together), biochemical oxygen demand (BOD) (is BOD, down together) value just can reach discharging standards, and ammonia nitrogen needs the time in 24～26 years just can reach discharging standards.The characteristics of percolate are: 1) water quality complexity, not only contain miscellaneous organic pollutant, and also contain ammonia nitrogen and contents of many kinds of heavy metal ion; 2) COD, BOD concentration height, intractability is big; 3) change of water quality is big, the water quality instability.Percolate all can cause great pollution to surrounding enviroment, landfill yard soil layer and underground water, so it is very necessary that it is carried out appropriate processing.
The leachate treatment technology that refuse landfill is both at home and abroad at present used mainly contains: the combination of biologic treating technique, materialization treatment technology, incineration technology, membrane technology, soil treatment technology and above-mentioned treatment technology etc.Biologic treating technique mainly comprises technology such as activated sludge process, oxidation ditch, anaerobic biofilter, upflow anaerobic sludge blanket reactor, batch activated sludge method and aeration oxidation pond.Usually biological treatment and soil processing cost are lower, but too high salinity can suppress microbial growth usually in the percolate, and floor space is big, and initial investment is higher.Membrane technology and burning method treatment technology cost height are applied difficult.
Chemical oxidization method can decompose the organism of bio-refractory in the percolate, thereby improves the biodegradability of waste water.Usually the oxygenant of usefulness mainly contains hydrogen peroxide, ozone, chlorine and muriate etc.Because chemical oxidization method has advantage such as easy and simple to handle, that floor space is little thereby is subject to people's attention.
Ozone oxidation is a kind of traditional water technology, and water treatment field at home and abroad has a wide range of applications at present.Ozonation technology is to utilize partial organic substances matter in the oxidation susceptibility oxidative degradation water of ozone and some inorganic toxic substances to reach scrubbing and disinfectant purpose.But also exist some shortcomings when independent ozone oxidation, the utilising efficiency that exists stronger selectivity and ozone as the reaction between ozone and the organism is not high, causes processing cost to rise.When independent ozone Oxidation Treatment percolate, oxidizing reaction 120 minutes can only reach 25.3% to the COD clearance in the percolate.
Summary of the invention
The objective of the invention is for overcoming the deficiencies in the prior art, a kind of method of processing landfill leachate through heterogeneous catalytic ozonation is provided, in ozone oxidation percolate reactor, add catalyzer and improve the oxidation capacity of ozone and the utilising efficiency of ozone, improve the usefulness of hardly degraded organic substance in the ozone oxidation percolate.
The technical solution used in the present invention is: be that active ingredient, potassium are that promotor loads on preparation catalysis ozone catalyzer on the absorbent charcoal carrier with copper, wherein the weight percentage of copper activity component accounts for 0.5～3% of catalysis ozone catalyzer; The catalysis ozone catalyzer for preparing is dropped in the O3 catalytic oxidation reaction tower; Simultaneously, input ozone and input pH value are 8～10 percolate in the O3 catalytic oxidation reaction tower, react 60～120 minutes; Waste water after the processing is discharged after neutralizing.
Described catalysis ozone Preparation of catalysts method is: with contain the copper activity component, concentration is 0.1～0.6mol/L solubility nitrate aqueous solution and saltpetre aqueous solution Immesion active carbon carrier, the volume ratio of the aqueous solution and absorbent charcoal carrier is 1.0: 1～1.5: 1; Room temperature condition ventilate down place 10～15 hours, at 110～120 ℃ of temperature range inner dryings, solidified 15～20 hours at 220～260 ℃ of roasting temperatures, get final product after the cooling.
The invention has the beneficial effects as follows:
1, solid catalyst, percolate and the ozone of preparation are finished reaction in a device, constitute the gas, liquid, solid three-phase system of forming by ozone, percolate and solid catalyst.Under the effect of catalyzer, excite ozone in solution, to decompose the higher active oxidation species of formation reaction activity, as hydroxyl radical free radical and ultra-oxygen anion free radical etc., attack the macromolecular substance in the waste water, and then make organic composition in the waste water be converted into to be easy to remove, the micromolecular compound of nontoxic or low toxicity, make the organism in the waste water obtain all or part of mineralising, gac through the modified load metal ion can effectively be removed percolate COD and ammonia nitrogen number, it is integrated to realize that percolate COD and ammonia nitrogen are counted oxidation removal, further improves the biodegradability of subsequent disposal.
2, with copper be the catalyzer that active ingredient makes, in the reaction times identical with independent ozone oxidation, can be so that the COD degradation rate in the percolate reach more than 80%, ammonia nitrogen is counted clearance and is reached more than 97.5%, and processing efficiency has improved 3.2 times.Need not required complicated technology and the equipment of biochemical treatment in the treating processes, processing unit is little and compact, floor space is little, consumer is few, current consumption is low, need not to add diluting water, working cost is low, easy to operate and can control automatically, simplified requirement, for practical engineering application provides better operability to execute-in-place.
3, the gac source is abundant, cheap; Used metallic copper catalyzer is a non-precious metal, moderate cost, and the source is abundant; Catalyzer can use for a long time, when processing efficiency descends, can carry out regeneration, thereby further reduce processing cost.
4, when water quantity and quality changes, can carry out the adjusting of the water yield and water quality, it is strong to have stronger anti impulsion load ability and adaptive faculty.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Fig. 1 is multinomial O3 catalytic oxidation percolate system process synoptic diagram.
Among the figure: 1. mixing screw; 2. waste water basin; 3. lift pump; 4. liquid meter; 5. strainer; 6. O3 catalytic oxidation reaction tower; 7. catalyst layer; 8. overflow weir; 9. neutralization tank; 10. gas meter; 11. ozone generation system; 12. gas distribution system; 13. water distribution system; 14. blower fan; 15. odor removal.
Embodiment
Catalyzer is made up of active ingredient, promotor and carrier.Specifically be active ingredient with copper, potassium is that promotor loads on and makes catalyzer on the absorbent charcoal carrier, and the specific surface area of absorbent charcoal carrier is 620～860m
2/ g, tap density is 450～600g/L.Wherein the weight percentage of active metal component copper is 0.5～3%, and all the other are absorbent charcoal carrier and promotor.This catalyzer adopts immersion process for preparing, with containing solubility nitrate aqueous solution and the saltpetre aqueous solution Immesion active carbon carrier that metal copper ion is an active ingredient, contain the solubility nitrate aqueous solution of activity component metal cupric ion and the concentration of the saltpetre aqueous solution and be 0.1～0.6mol/L, the volume ratio of the aqueous solution and absorbent charcoal carrier is 1.0: 1～1.5: 1, under room temperature condition, ventilate behind the Immesion active carbon carrier and placed 10～15 hours, in 110～120 ℃ of scopes, carry out drying again, carrying out roasting again in 220～260 ℃ of temperature ranges solidified 15～20 hours, need starvation during roasting, can obtain finished product after the cooling.
As accompanying drawing, adopt percolate and salkali waste (acid) in mixing screw 1, to mix earlier, pH value to percolate is regulated, making the pH value is 8～10, in the percolate input that the pH value is regulated and the waste water basin 2 that mixing screw 1 communicates, this waste water basin 2 is communicated with lift pump 3, liquid meter 4, strainer 5 and water distribution system 13 successively, and water distribution system 13 is located at O3 catalytic oxidation reaction tower 6 bottoms., enter then in the O3 catalytic oxidation reaction tower 6 successively by the conveying and the filtration of lift pump 3, liquid meter 4, strainer 5 and water distribution system 13 from the percolate of waste water basin 2 output.
After 6 pairs of wastewater treatments of O3 catalytic oxidation reaction tower, contain certain density ozone in the tail gas that O3 catalytic oxidation reaction tower 6 produces, this tail gas is entered the gas distribution system 12 of waste water basin 2 bottoms by blower fan 14 pressurizations from the top, can carry out the pre-oxidation treatment of percolate, the tail gas that produces in the waste water basin 2 carries out the deodorization processing from its top input odor removal 15 and enters atmosphere again.
Embodiment 1
With copper is active ingredient, and potassium is that promotor loads on the absorbent charcoal carrier, and the specific surface area of absorbent charcoal carrier is 620m
2/ g, tap density is 450g/L, and the weight percentage of copper is 0.5%, and the weight percentage of potassium is 0.2%, and all the other are carrier.With the concentration that contains cupric ion is solubility nitrate aqueous solution and the saltpetre aqueous solution Immesion active carbon carrier of 0.1mol/L, the volume ratio of the aqueous solution and active carrier is 1.0: 1, the dipping back ventilates down in room temperature condition and placed 10 hours, under 110 ℃ of conditions, carry out drying again, carrying out roasting under 220 ℃ solidified 15 hours, need starvation during roasting, can obtain finished product after the cooling.
Adopting as shown in drawings, system carries out the heterogeneous catalyst ozone Oxidation Treatment to percolate, pH value with percolate before the input waste water basin 2 is adjusted to 8, the influx of percolate is 5ml/min, the influx of ozone is 5mg/min, in O3 catalytic oxidation reaction tower 6, add the solid catalyst for preparing as stated above simultaneously, percolate is carried out O3 catalytic oxidation reaction 60 minutes continuously under the effect of catalyzer, water outlet records the COD value and is 930mg/L, with the COD value 5230mg/L contrast of being surveyed before the water inlet, its clearance is 82.2%.It is 25mg/L that water outlet records the ammonia nitrogen number, counts the 2130mg/L contrast with the ammonia nitrogen of being surveyed before the water inlet, and its clearance is 98.8%.
Embodiment 2
With copper is activeconstituents, and potassium is that promotor loads on the absorbent charcoal carrier, and the specific surface area of absorbent charcoal carrier is 730m
2/ g, tap density is 520g/L, and the weight percentage of copper is 2%, and the weight percentage of potassium is 1%, and all the other are carrier.With the concentration that contains cupric ion is solubility nitrate aqueous solution and the saltpetre aqueous solution Immesion active carbon carrier of 0.3mol/L, the volume ratio of the aqueous solution and active carrier is 1.3: 1, the dipping back ventilates down in room temperature condition and placed 13 hours, under 115 ℃ of conditions, carry out drying again, carrying out roasting under 240 ℃ solidified 17 hours, need starvation during roasting, can obtain finished product after the cooling.
Adopting as shown in drawings, system carries out the heterogeneous catalyst ozone Oxidation Treatment to percolate, pH value with percolate before the input waste water basin 2 is adjusted to 9, the influx of percolate is 5ml/min, the influx of ozone is 4mg/min, in O3 catalytic oxidation reaction tower 6, add the solid catalyst for preparing as stated above simultaneously, percolate is carried out O3 catalytic oxidation reaction 100 minutes continuously under the effect of catalyzer, water outlet records the COD value and is 945mg/L, with the COD value 5114mg/L contrast of being surveyed before the water inlet, its clearance is 81.5%.It is 45mg/L that water outlet records the ammonia nitrogen number, counts the 2100mg/L contrast with the ammonia nitrogen of being surveyed before the water inlet, and its clearance is 97.8%.
Embodiment 3
With copper is activeconstituents, and potassium is that promotor loads on the absorbent charcoal carrier, and the specific surface area of absorbent charcoal carrier is 860m
2/ g, tap density is 600g/L, and the weight percentage of copper is 3%, and the weight percentage of potassium is 3%, and all the other are carrier.With the concentration that contains cupric ion is solubility nitrate aqueous solution and the saltpetre aqueous solution Immesion active carbon carrier of 0.6mol/L, the volume ratio of the aqueous solution and active carrier is 1.5: 1, the dipping back ventilates down in room temperature condition and placed 15 hours, under 120 ℃ of conditions, carry out drying again, carrying out roasting under 260 ℃ solidified 20 hours, need starvation during roasting, can obtain finished product after the cooling.
System carries out the heterogeneous catalyst ozone Oxidation Treatment to percolate shown in the employing accompanying drawing, pH value with percolate before the input waste water basin 2 is adjusted to 10, the influx of percolate is 5ml/min, the influx of ozone is 6mg/min, in O3 catalytic oxidation reaction tower 6, add the solid catalyst for preparing as stated above, percolate is carried out O3 catalytic oxidation reaction 120 minutes continuously under the effect of catalyzer, water outlet records the COD value and is 1054mg/L, with the COD value 5320mg/L contrast of being surveyed before the water inlet, its clearance is 80.2%.It is 34mg/L that water outlet records the ammonia nitrogen number, counts the 2004mg/L contrast with the ammonia nitrogen of being surveyed before the water inlet, and its clearance is 98.3%.
Claims (4)
1, a kind of method of processing landfill leachate through heterogeneous catalytic ozonation is characterized in that adopting following steps:
1) be that active ingredient, potassium are that promotor loads on preparation catalysis ozone catalyzer on the absorbent charcoal carrier with copper, wherein the weight percentage of copper activity component accounts for 0.5～3% of catalysis ozone catalyzer;
2) the catalysis ozone catalyzer for preparing is dropped in the O3 catalytic oxidation reaction tower (6); Simultaneously, input ozone and input pH value are 8～10 percolate in O3 catalytic oxidation reaction tower (6), react 60～120 minutes;
3) waste water after the processing is discharged after neutralizing.
2, a kind of processing landfill leachate through heterogeneous catalytic ozonation method according to claim 1, it is characterized in that: catalysis ozone Preparation of catalysts method is in the step 1):
1) with contain the copper activity component, concentration is 0.1～0.6mol/L solubility nitrate aqueous solution and saltpetre aqueous solution Immesion active carbon carrier, the volume ratio of the aqueous solution and absorbent charcoal carrier is 1.0: 1～1.5: 1;
2) room temperature condition ventilate down place 10～15 hours, at 110～120 ℃ of temperature range inner dryings;
3) solidified 15～20 hours at 220～260 ℃ of roasting temperatures, get final product after the cooling.
3, a kind of processing landfill leachate through heterogeneous catalytic ozonation method according to claim 1 is characterized in that: step 2) O3 catalytic oxidation reaction tower (6) in the ozone amount of every liter of percolate input be 0.8～1.2g.
4, a kind of processing landfill leachate through heterogeneous catalytic ozonation method according to claim 1, it is characterized in that: the specific surface area of absorbent charcoal carrier is 620～860m
2/ g, tap density is 450～600g/L.
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| CN102363548A (en) * | 2011-06-20 | 2012-02-29 | 上海明诺环境科技有限公司 | Treatment system for non-membrane garbage leachate |
| CN102432125A (en) * | 2011-11-11 | 2012-05-02 | 华南理工大学 | Device and method for treating pulping wastewater by using catalytic ozone |
| CN102583894A (en) * | 2012-02-24 | 2012-07-18 | 浙江省农业科学院 | Method for treating landfill leachate tail water through magnetic carbon catalyzed ozonation |
| CN102784644A (en) * | 2012-08-29 | 2012-11-21 | 张振慧 | Heterogeneous catalysis ozonization load type catalyst and preparation method thereof |
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| CN103586026A (en) * | 2013-11-26 | 2014-02-19 | 北京碧水源科技股份有限公司 | Carbon supported catalyst for ozone oxidation, and preparation method and use thereof |
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| CN107032521A (en) * | 2017-04-25 | 2017-08-11 | 大连广泰源环保科技有限公司 | Advanced treatment system and method after a kind of percolate evaporation gas washing |
| CN108439572A (en) * | 2018-05-24 | 2018-08-24 | 嘉兴市六承环保科技有限公司 | For reducing the Heterodisperse type ozone oxidation catalyst and its application method of COD of waste leachate value |
| CN113149179A (en) * | 2021-03-12 | 2021-07-23 | 中南大学 | Method for improving ozone degradation of landfill leachate |
| CN113680349A (en) * | 2021-09-28 | 2021-11-23 | 中冶南方都市环保工程技术股份有限公司 | Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater |
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- 2009-06-05 CN CN2009100322108A patent/CN101580294B/en not_active Expired - Fee Related
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| CN102432125A (en) * | 2011-11-11 | 2012-05-02 | 华南理工大学 | Device and method for treating pulping wastewater by using catalytic ozone |
| CN103159340A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Inferior heavy oil sewage purification and biochemical degradation coupling device |
| CN102583894A (en) * | 2012-02-24 | 2012-07-18 | 浙江省农业科学院 | Method for treating landfill leachate tail water through magnetic carbon catalyzed ozonation |
| CN102784644A (en) * | 2012-08-29 | 2012-11-21 | 张振慧 | Heterogeneous catalysis ozonization load type catalyst and preparation method thereof |
| CN103586026A (en) * | 2013-11-26 | 2014-02-19 | 北京碧水源科技股份有限公司 | Carbon supported catalyst for ozone oxidation, and preparation method and use thereof |
| CN104150578A (en) * | 2014-07-10 | 2014-11-19 | 唐国民 | Catalytic ozonation water treatment device |
| CN104353418A (en) * | 2014-11-06 | 2015-02-18 | 山西新华化工有限责任公司 | Preparation method of deodorization adsorbing material |
| CN105000706A (en) * | 2015-06-25 | 2015-10-28 | 沈阳化工大学 | Treating method for plate-making waste water |
| CN106693974A (en) * | 2016-11-11 | 2017-05-24 | 大连理工大学 | Preparation method and application of supported metal oxide catalyst for removing ammonia nitrogen in water through catalytic ozonation |
| CN107032521A (en) * | 2017-04-25 | 2017-08-11 | 大连广泰源环保科技有限公司 | Advanced treatment system and method after a kind of percolate evaporation gas washing |
| CN108439572A (en) * | 2018-05-24 | 2018-08-24 | 嘉兴市六承环保科技有限公司 | For reducing the Heterodisperse type ozone oxidation catalyst and its application method of COD of waste leachate value |
| CN113149179A (en) * | 2021-03-12 | 2021-07-23 | 中南大学 | Method for improving ozone degradation of landfill leachate |
| CN113680349A (en) * | 2021-09-28 | 2021-11-23 | 中冶南方都市环保工程技术股份有限公司 | Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater |
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