CN109626484B - A kind of percolate inorganic agent and leachate processing method - Google Patents
A kind of percolate inorganic agent and leachate processing method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Environmental & Geological Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides a kind of percolate inorganic agent and leachate processing methods, landfill leachate is pre-processed using Fenton method, then it is carrier loaded magnesia and iron compound as inorganic agent using active carbon and advanced treating is carried out to percolate, the removal rate of the substances such as COD in percolate, ammonia nitrogen, total phosphorus, solid suspension and heavy metal can be improved, quickly, economical and efficient, it not will cause secondary pollution problems, while inorganic agent of the invention has magnetism, facilitates recycling.
Description
Technical field
The present invention relates to environment protection fields, and in particular to a kind of percolate inorganic agent and leachate processing method.
Background technique
Landfill leachate is during dumping, landfill, due to fermentation, rain drop erosion and surface water, underground water logging
The sewage for steeping and then being percolated out, generally includes a variety of poisonous and hazardous inorganic matters and organic matter.Water quality is complicated, variation is big, COD and
BOD5 concentration, content of beary metal and ammonia-nitrogen content are high, and the imbalance of microbial nutrition element ratio is the main feature of landfill leachate,
Its pH usually between 4-9, COD content within the scope of 2000-62000mg/L, BOD5 content within the scope of 60-45000mg/L,
The concentration of heavy metal is almost the same in heavy metal concentration and municipal wastewater.
The processing method of landfill leachate generally includes following a few classes: (1) with municipal sewage merging treatment.This method is not required to
In addition percolate treatment plant is built, but landfill yard is typically remote from city, pipe network investment is larger, in addition, landfill leachate ingredient
It is complicated and unstable, it will increase the security risk of sewage treatment plant.(2) biological treatment.This method includes Aerobic biological process
The processing mode combined with anaerobic bio-treated and the two, treatment effect is preferable, but it is at high cost, operating condition is harsh, into
And it is difficult to promote.(3) physical-chemical process.The method mainly include ion exchange, activated carbon adsorption, chemical oxidation, electronation and
The methods of film dialysis, usual method are simple and efficient, but have processing cost high, are not suitable for processing large scale rubbish percolate
Disadvantage.(4) land treatment systems method.This method utilizes soil self-cleaning, and poisonous and harmful substance in plantation vegetation processing percolate is at low cost
It is honest and clean, have preferable loading but effective very long, and can threaten to soil safety, in the case where land resource scarcity not
It is worthy of popularization.(5) evaporation process.This method includes evaporator evaporation and natural evaporation, using heating and provides negative pressure,
The moisture of percolate is evaporated and collected, while dope being concentrated and is dehydrated into dry Slag treatment.Evaporation operation is simple and effect is managed
Think, but natural evaporation needs to occupy a large amount of soil, produces bigger effect to environment, and there will be big energies for evaporator evaporation
Consumption, while evaporator is easy fouling, and cleaning is more difficult.
In numerous processing methods, Fenton reagent is due to excellent oxidability, when handling organic wastewater with difficult degradation thereby
There is extremely strong advantage.Application No. is 201110104632.9 patents to disclose a kind of Fenton reagent processing landfill leachate
Method, the invention put into ferrous sulfate and hydrogen peroxide into landfill leachate, and Fenton oxygen is carried out after being thoroughly mixed
Change, this method is efficiently significant, simple and easy, and the removal rate of COD reaches as high as 99% or more, but simultaneously, peroxidating in the invention
Hydrogen is expensive, and then limits it and be used alone on a large scale in landfill leachate treatment.
Application No. is 201410179876.7 patents to disclose a kind of Fenton method joint supercritical water oxidation method processing
Landfill leachate, the invention are pre-processed using Fenton method, then carry out advanced treating using supercritical water oxidation method, should
Method can efficiently remove the pollutants such as ammonia nitrogen, coloration and the COD in water removal, while can save the cost of 15-25%.But the hair
The removal rate of bright middle ammonia nitrogen is 69-71%, though it is higher than the treatment effect of single Fenton method and single water oxidation, it is whole
For it is still relatively low.Meanwhile supercritical water oxidation method needs react under high temperature, condition of high voltage, reaction condition is more harsh,
Requirement to equipment is high and power consumption is big.
Application No. is 201510387734.4 patents to disclose a kind of percolate inorganic agent and leachate processing method, with
Mulberries leaf, chrysanthemum cauline leaf, honeysuckle-leaf, ginkgo leaf are raw material, by marinated, obtained pickling liquid, then secondary fermentation is undergone, it prepares
Inorganic agent out.The inorganic agent uses natural material for raw material, has that raw material sources are extensive, at low cost, easy to operate and effect is good
The advantages that, in addition, the invention using Fenton oxidation method and MAP combined pretreatment, recycle above-mentioned inorganic agent to percolate into
Row processing, reduces NH therein3N content, and then a large amount of ammonia nitrogen, microcosmic salt, microorganism and pathogen etc. in percolate are removed,
Final each pollutant such as COD, NH3- N, TP and SS suspended matter removal rate all reached 90% or more.But in this method
Fenton takes off NH3- N effect is poor, and NH3- N can inhibit the growth and breeding of microorganism in inorganic agent, need additionally to be added MAP method into
On the one hand row Combined Treatment increases the complexity of percolate treating process, on the other hand, if ammonium magnesium phosphate is costly and returns
It is improper it will cause secondary pollution to receive, and bears which in turns increases the cost of percolate processing and caused by environment.
Therefore, in view of the above-mentioned problems, need it is a kind of quickly, economic and efficient processing mode and one kind be by water quality impact
Lesser percolate inorganic agent, the removal rates such as COD, ammonia nitrogen, total phosphorus, solid suspension and heavy metal in improving landfill leachate
While, it can reduce landfill leachate treatment cost, while facilitating recycling, do not easily cause the environmental problems such as secondary pollution.
Summary of the invention
In view of the problems of the existing technology, the present invention pre-processes landfill leachate using Fenton method, then
Carry out advanced treating by percolate inorganic agent, quickly, economical and efficiently, wherein with active carbon be carrier loaded magnesia and
Going for the substances such as COD in percolate, ammonia nitrogen, total phosphorus, solid suspension and heavy metal can be improved as inorganic agent in iron compound
Except rate, it not will cause secondary pollution problems, while inorganic agent of the invention has magnetism, facilitates recycling.
To achieve the above object, The technical solution adopted by the invention is as follows:
Leachate processing method of the invention, comprising the following steps:
(1) Fenton method pre-processes: the pH of landfill leachate is adjusted, ferrous sulfate and hydrogen peroxide is added, it is quiet after stirring
It sets, obtains pretreated landfill leachate；
(2) advanced treating: adjusting the pH through step (1) pretreated landfill leachate, is stirred after inorganic agent is added
It mixes, completion processing.
In some specific embodiments, the pH that landfill leachate is adjusted described in step (1) and step (2) is used
Solution be sulfuric acid；
Further, pH described in step (1) is 3-5, and time of the stirring is 0.5h, the standing when
Between be 1-3h；PH described in step (2) is 2-3, and the time of the stirring is 0.5h；
Further, the molar ratio of hydrogen peroxide described in step (1) and ferrous sulfate is 4-6:1；
Further, inorganic agent described in step (2), preparation step include:
S1: magnesium salts is dissolved in water, and is stirred evenly, and magnesium salt solution is obtained；
S2: iron chloride is dissolved in water, and is stirred evenly, and ferric chloride solution is obtained；
S3: it carries out the magnesium salt solution that step S1 is obtained and the ferric chloride solution that step S2 is obtained to be mixed to get mixed liquor
A；
S4: active carbon being added and is impregnated into mixed liquor A, and drying is placed on tube furnace and lives under conditions of protecting gas
Change pyrolysis to get inorganic agent.
Further, magnesium salts described in step S1 be one of magnesium nitrate, magnesium sulfate, magnesium chloride and Magnesium Acrylate Prepared or
It is a variety of；
Further, stirring described in step S1 and step S2, stirring rate 400r/min；Described in step S4
Dipping, dip time 12h；
Further, the mass fraction of the magnesium salt solution in step S1 is 20%-35%；
Preferably, the mass fraction of magnesium salt solution described in step S1 is 30%；
In certain embodiments, the mass fraction of ferric chloride solution described in step S2 is 20%；
Further, the volume ratio of magnesium salt solution described in step S3 and the ferric chloride solution is 2-5:1；
Preferably, the volume ratio of magnesium salt solution described in step S3 and the ferric chloride solution is 3:1；
Further, dipping described in step S4, dip time 12h, the drying, drying time 12h；
Further, protection gas described in step S4 is nitrogen, helium, argon gas or neon, gas flow rate 100mL/
min；
Further, activation described in step S4 is pyrolyzed, and pyrolysis temperature is 600-900 DEG C, pyrolysis time 0.5-3h；
Preferably, activation described in step S4 is pyrolyzed, and pyrolysis temperature is 700 DEG C, pyrolysis time 1h；
Beneficial effect acquired by the present invention is:
(1) effect of inorganic agent removal ammonia nitrogen is preferable, can make up for it deficiency of the Fenton method in terms of removing ammonia nitrogen, and by
Environment influences smaller, will not influence its treatment effect because of the problems such as ammonia nitrogen in water.
(2) MgO-Supported is in activated carbon surface, and when handling landfill leachate, existing magnesia is for ammonia nitrogen and total phosphorus
The removal effect of equal substances, can substitute MPA method, not will cause secondary pollution problem；Activated carbon surface load has iron compound,
Have magnetism, facilitate recycling, and the loaded favourable of iron compound is in the absorption of water part heavy metal, meanwhile, active carbon has
Biggish specific surface area equally improves the removal rate of each substance.
(3) Fenton method is combined with inorganic agent, is not only reduced cost when Fenton processing percolate, is increased simultaneously
The removal rate of the substances such as COD, ammonia nitrogen, total phosphorus, solid suspension and heavy metal in percolate.
Specific embodiment
Embodiment 1
Leachate processing method, comprising the following steps:
(1) Fenton method pre-processes: adjusting the pH to 3 of landfill leachate using sulfuric acid solution, ferrous sulfate and mistake is added
Hydrogen oxide after stirring 0.5h, stands 1h, obtains pretreated landfill leachate；
(2) advanced treating: the pH to 2 through step (1) pretreated landfill leachate is adjusted using sulfuric acid solution, is added
0.5h, completion processing are stirred after inorganic agent.
Wherein, the molar ratio of hydrogen peroxide described in step (1) and ferrous sulfate is 5:1.
Further, inorganic agent described in step (2), preparation step include:
S1: magnesium nitrate is dissolved in water, and is stirred evenly, stirring rate 400r/min, and obtaining mass fraction is 30%
Magnesium nitrate solution；
S2: iron chloride is dissolved in water, and is stirred evenly, stirring rate 400r/min, and obtaining mass fraction is 20%
Ferric chloride solution；
S3: it carries out the magnesium nitrate solution that step S1 is obtained and the ferric chloride solution that step S2 is obtained to be mixed to get mixed liquor
The volume ratio of A, magnesium nitrate solution and ferric chloride solution is 3:1；
S4: active carbon being added into mixed liquor A and impregnates 12h, and it is 100mL/ that drying, which is placed on tube furnace in gas flow rate,
Activation pyrolysis is carried out under conditions of min nitrogen protection, pyrolysis temperature is 700 DEG C, and pyrolysis time is 1h to get inorganic agent.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that, in inorganic agent preparation step, the mass fraction of magnesium nitrate solution is
20%.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that, in inorganic agent preparation step, the mass fraction of magnesium nitrate solution is
35%.
Embodiment 4
Embodiment 4 the difference from embodiment 1 is that, in inorganic agent preparation step, magnesium nitrate solution and ferric chloride solution
Volume ratio is 2:1.
Embodiment 5
Embodiment 5 the difference from embodiment 1 is that, in inorganic agent preparation step, magnesium nitrate solution and ferric chloride solution
Volume ratio is 5:1.
Embodiment 6
Embodiment 6 the difference from embodiment 1 is that, in inorganic agent preparation step, pyrolysis temperature in step (4) is 600
℃。
Embodiment 7
Embodiment 6 the difference from embodiment 1 is that, in inorganic agent preparation step, pyrolysis temperature in step (4) is 900
℃。
Comparative example 1
Comparative example 1 the difference from embodiment 1 is that, in inorganic agent preparation step, the mass fraction of magnesium nitrate solution is
10%.
Comparative example 2
Comparative example 2 the difference from embodiment 1 is that, in inorganic agent preparation step, the mass fraction of magnesium nitrate solution is
40%.
Comparative example 3
Comparative example 3 the difference from embodiment 1 is that, in inorganic agent preparation step, magnesium nitrate solution and ferric chloride solution
Volume ratio is 1:1.
Comparative example 4
Comparative example 4 the difference from embodiment 1 is that, in inorganic agent preparation step, magnesium nitrate solution and ferric chloride solution
Volume ratio is 6:1.
Comparative example 5
Embodiment 6 the difference from embodiment 1 is that, in inorganic agent preparation step, pyrolysis temperature in step (4) is 500
℃。
Comparative example 6
Embodiment 6 the difference from embodiment 1 is that, in inorganic agent preparation step, pyrolysis temperature in step (4) is 950
℃。
Determination method
The measurement potassium dichromate method of COD:CJ/T 3018.12-1993 consumer waste leachate water chemistry oxygen demand (COD)；
Ammonia nitrogen: the measurement of ammonia nitrogen in HJ 535-2009 water quality；
Total phosphorus: the total phosphorus yield vanadium molybdophosphate spectrophotometry of CJ/T 3018.9-1993 consumer waste leachate water；
Solid suspension: the measurement gravimetric method of GB/T 11901-1989 water quality suspended matter；
Heavy metal (by taking Cr VI as an example): the measurement diphenylcarbazide spectrophotometric of GB 7467-87 water quality Cr VI
Method.
By the above detection method, finally obtain the pretreatment of Fenton method and advanced treating to COD, ammonia nitrogen, total phosphorus, solid
The removal rate of suspended matter and Cr (VI) are as shown in table 1 and table 2.
1 Fenton method of table pre-processes percolate result
2 advanced treating percolate result of table
By table 1 and table 2 it is found that in the pretreatment of Fenton method, embodiment 1-7 and comparative example 1-6 are for COD, ammonia nitrogen, total
The removal rate of phosphorus, solid suspension and Cr (VI) is more close；It is pre-processed compared to Fenton method, advanced treating improves diafiltration
The removal rate of each substance in liquid；Embodiment 1-7 has COD, ammonia nitrogen, total phosphorus, solid suspension and the Cr (VI) in percolate
Preferable removal effect, wherein the treatment effect of embodiment 1 is optimal；Comparative example 1-6 also there is certain processing to imitate each substance
Fruit, but it is weaker than embodiment 1-7, wherein comparative example 1-2 is for the removal effect of COD and ammonia nitrogen, and comparative example 3-4 is for total phosphorus
It is poor for the removal effect of heavy metal with the removal effect and comparative example 5-6 of solid suspension.
Using comprehensive physical property measuring system (PPMS-9T (EC-II), quantum sciences Instrument Ltd., the U.S.) to embodiment
The magnetic property of 1-7 and the inorganic agent in comparative example 1-6 is analyzed, and table 3 is obtained.
3 magnetometric analysis result of table
As shown in Table 3, the saturation magnetization of embodiment 1-7, comparative example 1-3 and comparative example 6 are higher, wherein implement
The saturation magnetization of example 4 and embodiment 7 is relatively large, and the saturation magnetization of comparative example 4 and comparative example 5 is relatively small, right
Although the saturation magnetization of ratio 3 is higher, it is weaker for the adsorption effect of substance each in percolate.
Absorption experiment is carried out using inorganic agent of the magnetite to embodiment 1-7 and comparative example 1-6, it is finally, embodiment 1-7, right
Inorganic agent in ratio 1-3 and comparative example 6 can be drawn by magnetite, and the inorganic agent in comparative example 4 and comparative example 5 cannot be by magnetite
It draws.
In summary, leachate processing method of the invention is to COD in percolate, ammonia nitrogen, total phosphorus, solid suspension and again
The substances such as metal removal rate with higher, and not will cause secondary pollution problems, meanwhile, inorganic agent of the invention has magnetic
Property, facilitate recycling.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than limiting the scope of the invention, ability
The simple modification or equivalent replacement that the those of ordinary skill in domain carries out technical solution of the present invention, all without departing from skill of the present invention
The spirit and scope of art scheme.
Claims (4)
1. a kind of leachate processing method, it is characterised in that: the processing method the following steps are included:
(1) Fenton method pre-processes: adjusting the pH of landfill leachate, ferrous sulfate and hydrogen peroxide is added, stands, obtains after stirring
To pretreated landfill leachate；
(2) advanced treating: adjusting the pH through step (1) pretreated landfill leachate, is stirred after inorganic agent is added, complete
At processing；
PH described in step (1) is 3-5, and the time of the stirring is 0.5h, and the time of the standing is 1-3h；Step
(2) pH described in is 2-3, and the time of the stirring is 0.5h；
Inorganic agent described in step (2), preparation step include:
S1: magnesium salts is dissolved in water, and is stirred evenly, and magnesium salt solution is obtained；
S2: iron chloride is dissolved in water, and is stirred evenly, and ferric chloride solution is obtained；
S3: it carries out the magnesium salt solution that step S1 is obtained and the ferric chloride solution that step S2 is obtained to be mixed to get mixed liquor A；
S4: active carbon being added and is impregnated into mixed liquor A, and the dry tube furnace that is placed on carries out activation heat under conditions of protecting gas
Solution is to get inorganic agent；
The mass fraction of magnesium salt solution described in step S1 is 20%-35%；
The mass fraction of ferric chloride solution described in step S2 is 20%；
The volume ratio of magnesium salt solution described in step S3 and the ferric chloride solution is 2-5:1；
Activation described in step S4 is antipyretic, and pyrolysis temperature is 600-900 DEG C, pyrolysis time 0.5-3h.
2. according to the method described in claim 1, it is characterized by: hydrogen peroxide described in step (1) and ferrous sulfate
Molar ratio is 4-6:1.
3. according to the method described in claim 1, it is characterized by: magnesium salts described in step S1 is magnesium nitrate, magnesium sulfate, chlorine
Change one of magnesium and Magnesium Acrylate Prepared or a variety of.
4. according to the method described in claim 1, it is characterized by: protection gas described in step S4 is nitrogen, helium, argon gas
Or neon, gas flow rate 100mL/min.
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| Fenton氧化-MAP法预处理垃圾渗滤液研究;张星;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑（月刊）》;20140515;摘要，第16页图2.1，第21页第3.2节，第29页第4.2节 * |
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Effective date of registration: 20210918 Address after: 411100 No. 32, Ji'an Road, Wulidui street, Yuetang District, Xiangtan City, Hunan Province Patentee after: Xiangtan Urban and rural innovative garden Engineering Co.,Ltd. Address before: 411100 No. 48, tanxia Road, Yuetang District, Xiangtan City, Hunan Province Patentee before: XIANGTAN LIANGXING MUNICIPAL TECHNOLOGY Co.,Ltd. |