CN101701025A - Method for extracting humus acid from concentrated waste percolate and treating waste water - Google Patents
Method for extracting humus acid from concentrated waste percolate and treating waste water Download PDFInfo
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- CN101701025A CN101701025A CN200910193512A CN200910193512A CN101701025A CN 101701025 A CN101701025 A CN 101701025A CN 200910193512 A CN200910193512 A CN 200910193512A CN 200910193512 A CN200910193512 A CN 200910193512A CN 101701025 A CN101701025 A CN 101701025A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract
The invention discloses a method for extracting humus acid from concentrated waste percolate and treating waste water, comprising the steps of adding coagulant into the concentrated waste percolate, stirring uniformly, adding coagulating agent, settling for 40 to 6 min, subsiding, separating to obtain supernatant, adjusting the PH value of supernatant to be 1.0 to 3;.0, settling for 4.0 to 8.0 h, subsiding, separating, concentrating the sediment to acquire high-concentrated liquid humus acid, and discharging after treating with advanced oxidization technique, wherein the coagulant is polymeric aluminum sulfate, polymeric ferric sulfate or polymeric ferric chloride and the coagulating agent is polyacrylamide. Treating the waste water with the method, the overall removing rates of COD and TOC are respectively above 96% and 97%, and the separated humus acid is semi-solid content which can be used as organic fertilizer to realize the comprehensive use of concentrated waste percolate and the treating target of treating pollution and changing waste into valuable.
Description
Technical field
The present invention relates to the comprehensive processing method that humic acid is recycled a kind of concentrated waste percolate after reverse osmosis membrane processing of environmental protection.
Background technology
China's municipal wastes adopts the method for landfill to handle mostly at present, adopts landfill method to handle municipal wastes and can produce a large amount of percolates.Percolate is a kind of liquid that contains high quality concentration suspended substance and high quality concentration organic or inorganic composition, wherein contain considerable toxic substance, and mass concentration is very high, enter rivers and lakes fully without handling, organic pollutant wherein, inorganic pollutant can make hydrobiont and farm crop be polluted, and by food chain and ecotope HUMAN HEALTH are produced harm.
Percolate water quality composition and concentration thereof change with the prolongation of the landfill time limit, and the percolate pH value of general later stage landfill yard is near neutrality, basicity height; Five-day BOD (BOD
5), chemical oxygen demand (COD) (COD
Cr), voltaile fatty acid (VFA) concentration and BOD
5/ COD
CrLower, biodegradability is poor; Concentration of metal ions descends, but content of humic acid and ammonia nitrogen concentration are higher.Though various countries carry out this respect research existing considerable time, still do not have effective treatment process so far,, be a global difficult problem particularly to the processing of the percolate (landfill yard uses more than 10 years) of later stage landfill yard always.
Because the NH of high density
3-N is inhibited to microorganism, and contain multiple poisonous and hazardous hard-degraded substance (as polycyclic aromatic hydrocarbons, polychlorobiphenyl etc.) and biorefractory material (as humic acid, tensio-active agent etc.) in the percolate, make the application of biological process be subjected to restriction significantly and can't make the percolate qualified discharge.Therefore adopt physical chemistry method, particularly reverse osmosis technology treating refuse percolate becomes a kind of trend just gradually.With respect to other treatment process, the reverse osmosis membrane separation process can be carried out at normal temperatures, and there is not phase transformation, less energy-consumption, can remove inorganic salt and organic molecule impurity effectively, have higher water reclamation rate, can guarantee good treatment effect, at present domestic existing bulky refuse landfill yard adopts reverse osmosis process to handle percolate.But reverse osmosis only is a sepn process, and reverse osmosis membrane technology treating refuse percolate certainly leads to concentrated solution, when reverse osmosis is isolated clear water from ooze drop liquid, also has one concentrated solution that accounts for feed liquor amount 30% to need further to handle.The reverse osmosis concentrated liquid of percolate is a kind of organic liquid waste of high density, and its COD and conductivity value be 3～4 times of primary percolate often, even 5 times, therefore the properly disposal of concentrated solution needs that contains the high density humic acid is in a large number arranged.The processing of concentrated solution mainly contains methods such as burning, curing, distillation is dry and recharge, but this type of processing exists serious problems such as power consumption is big, energy wastage.
Summary of the invention
The purpose of this invention is to provide a kind of concentrated waste percolate that after reverse-osmosis treated, produces and extract humic acid (humicsubstances, HS) and to it carry out the method for comprehensive utilization of advanced treatment, realize Pollution abatement and the target that turns waste into wealth, make the total clearance of COD and TOC reach 96.4% and 97.8% respectively.
Purpose of the present invention can realize by following measure:
A kind ofly extract humic acid and administer method for waste water, comprise the steps: from concentrated waste percolate
(1) adds coagulating agent at concentrated waste percolate, stir, add the coagulation auxiliary agent, slowly stir 1min, sedimentation 40～60min; The add-on of coagulating agent and coagulation auxiliary agent be respectively percolate quality 0.15%～0.35% and 0.005%～0.01%; Described coagulating agent is polyaluminium sulfate, bodied ferric sulfate or poly-ferric chloride; Described coagulation auxiliary agent is a polyacrylamide;
(2) precipitation, separation get supernatant liquor;
(3) supernatant liquor is regulated pH value to 1.0～3.0;
(4) sedimentation 4.0～8.0h, precipitation, separation; The concentrating and precipitating thing promptly gets the liquid humic acid of high density;
(5) precipitating, separate the supernatant liquor that obtains uses high-level oxidation technology to handle the back qualified discharge; Described high-level oxidation technology is to be in the catalyticreactor of light source with daylight, adds oxygenant and catalyzer, and the supernatant liquor oxidative degradation time is 20-30h; Described oxygenant is a hydrogen peroxide, and described catalyzer is a ferrous sulfate.
For further realizing the object of the invention, the separate mode of step (2) and step (4) is centrifugation.
The adjusting of step (3) pH is to regulate with sulfuric acid or hydrochloric acid.
The present invention has if any advantage and beneficial effect:
1, because percolate has been realized the comprehensive regulation, the total clearance of its COD and TOC reaches respectively more than 96.4% and 97.8%, has reached the purpose of administering waste water, does not produce secondary pollution simultaneously.
2, technology of the present invention is simple, equipment is few, investment is little, is fit to handle in the rubbish concentrated solution field.
3, extract the method for humic acid the concentrated waste percolate that after reverse-osmosis treated, produces, have certain economic benefits, social benefit and environmental benefit.Humic acid can be applicable to liquid state organic fertilizer to realize resource utilization.
This method is handled waste water, the total clearance of COD and TOC reaches respectively more than 96% and 97%, and isolated humic acid half solid substance can be made organic fertilizer, thereby realized comprehensive utilization, reached and administered the management goal of polluting and changing harmful to treasure concentrated waste percolate.And technology is easy, and equipment is few, invest little, when administering the three wastes, utilize resources synthetically, no secondary three waste discharge.The inventive method has overcome percolation liquid membrane process concentrated liquid and has extracted the big problem of energy consumption that the humic acid technology exists, and has good society and economic benefit.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but the scope of protection of present invention scope of representing in embodiment of limitation not.
Embodiment 1:
(1) detect concentrated waste percolate after certain reverse osmosis membrane processing, its TOC and COD are respectively 2584mg/L and 4285mg/L; This concentrated waste percolate of 1L is put into the 2.5L beaker, stir under the room temperature, add the bodied ferric sulfate coagulating agent of 0.15g, 200-300r/min stirs 2min fast, add 1ml 0.05% (weight concentration) coagulation auxiliary agent polyacrylamide, 200-300r/min stirs 2min fast, slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min.Measure supernatant liquor TOC and COD and be respectively 2196mg/L and 3513mg/L, clearance reaches 15% and 18% respectively.
(2) in the supernatant liquor of step (1), add hydrochloric acid, regulate pH to 1.5, sedimentation 4.0h, 4000r/min centrifugation 15min, 50 ℃ of vacuum drying ovens are concentrated into semi-solid state, can obtain the liquid humic acid 6.5g of high density.Measure through potassium dichromate oxidation, its content is higher than 90%.After testing, supernatant liquor TOC and COD are respectively 1493mg/L and 2213mg/L, and clearance reaches 33% and 37% respectively.
(3) with the supernatant liquor pH to 4.0 of hydrochloric acid regulating step (2), stir adding ferrous sulfate 2.5g under the room temperature, divide 3 times, add hydrogen peroxide (30wt%H every 10min
2O
2) 6mL, continue to stir 30min, leave standstill 24h.After testing, TOC and COD are respectively 92mg/L and 96mg/L, and clearance reaches 93.8% and 95.7% respectively.Reach " integrated wastewater discharge standard " primary standard (GB8978-1996).The portion-wise addition of oxygenant and the interval mode that adds the time have determined the height of clearance, also are advantages of the present invention.Can reach removal effect preferably with lower oxygenant dosage.
Embodiment 2:
(1) detect concentrated waste percolate after certain reverse osmosis membrane processing, its TOC and COD are respectively 2584mg/L and 4285mg/L; This rubbish concentrated solution of 1L is put into the 2.5L beaker, stir under the room temperature, add the polyaluminium sulfate coagulating agent (by weight percentage) of 0.25g, 200-300r/min stirs 2min fast, add 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min stirs 2min fast, slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min.Measure supernatant liquor TOC and COD and be respectively 2158mg/L and 3492mg/L, clearance reaches 16.5% and 18.5% respectively.
(2) in the supernatant liquor of step (1), add hydrochloric acid, regulate pH to 3.0, sedimentation 6.0h, 4000r/min centrifugation 15min, 50 ℃ of vacuum drying ovens are concentrated into semi-solid state, can obtain the liquid humic acid 6.2g of high density.Measure through potassium dichromate oxidation, its content is higher than 90%.After testing, supernatant liquor TOC and COD are respectively 1403mg/L and 2158mg/L, and clearance reaches 35% and 38.2% respectively.
(3) with the supernatant liquor pH to 4.0 of hydrochloric acid regulating step (2), stir adding ferrous sulfate 2.5g under the room temperature, divide 3 times every 10min adding hydrogen peroxide (30%H
2O
2) 6mL, continue to stir 30min, leave standstill 20h.After testing, TOC and COD are respectively 96.8mg/L and 84mg/L, and clearance reaches 93.1% and 96.1% respectively.Reach " integrated wastewater discharge standard " primary standard (GB8978-1996).The portion-wise addition of oxygenant and the interval mode that adds the time have determined the height of clearance, also are advantages of the present invention.Can reach removal effect preferably with lower oxygenant dosage.
Embodiment 3:
(1) detects concentrated waste percolate after certain reverse osmosis membrane processing, its TOC and COD are respectively 2584mg/L and 4285mg/L, this rubbish concentrated solution of 1L is put into the 2.5L beaker, stir under the room temperature, add the bodied ferric sulfate coagulating agent (by weight percentage) of 0.35g, 200-300r/min stirs 2min fast, add 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min stirs 2min fast, slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min.Measure supernatant liquor TOC and COD and be respectively 2106mg/L and 3424mg/L, clearance reaches 18.5% and 20.1% respectively.
(2) in the supernatant liquor of step (1), add sulfuric acid, regulate PH to 1.0, sedimentation 8.0h, 4000r/min centrifugation 15min, 50 ℃ of vacuum drying ovens are concentrated into semi-solid state, can obtain the liquid humic acid 10.3g of high density.Measure through potassium dichromate oxidation, its content is higher than 90%.After testing, supernatant liquor TOC and COD are respectively 1305mg/L and 2048mg/L, and clearance reaches 38% and 40.2% respectively.
(3) with the supernatant liquor pH to 4.0 of sulfuric acid regulating step (2), stir adding ferrous sulfate 2.5g under the room temperature, divide 3 times every 10min adding hydrogen peroxide (30%H
2O
2) 6mL, continue to stir 30min, leave standstill 24h.After testing, TOC and COD are respectively 83.5mg/L and 71mg/L, and clearance reaches 93.6% and 96.5% respectively.Reach " integrated wastewater discharge standard " primary standard (GB8978-1996).The portion-wise addition of oxygenant and the interval mode that adds the time have determined the height of clearance, also are advantages of the present invention.Can reach removal effect preferably with lower oxygenant dosage.
Embodiment 4
(1) detects concentrated waste percolate after certain reverse osmosis membrane processing, its TOC and COD are respectively 2584mg/L and 4285mg/L, this rubbish concentrated solution of 1L is put into the 2.5L beaker, stir under the room temperature, add the polyaluminium sulfate coagulating agent (by weight percentage) of 0.35g, 200-300r/min stirs 2min fast, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min stirs 2min fast, slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min.Measure supernatant liquor TOC and COD and be respectively 2126mg/L and 3509mg/L, clearance reaches 17.7% and 18.1% respectively.
(2) in the supernatant liquor of step (1), add sulfuric acid, regulate pH to 1.5, sedimentation 8.0h, 4000r/min centrifugation 15min, 50 ℃ of vacuum drying ovens are concentrated into semi-solid state, can obtain the liquid humic acid 10.5g of high density.Measure through potassium dichromate oxidation, its content is higher than 90%.After testing, supernatant liquor TOC and COD are respectively 1275mg/L and 2028mg/L, and clearance reaches 40% and 42.2% respectively.
(3) with the supernatant liquor pH to 4.0 of sulfuric acid regulating step (2), stir adding ferrous sulfate 2.5g under the room temperature, divide 3 times every 10min adding hydrogen peroxide (30%H
2O
2) 6mL, continue to stir 30min, leave standstill 24h.After testing, TOC and COD are respectively 84mg/L and 69mg/L, and clearance reaches 93.4% and 96.6% respectively.Reach " integrated wastewater discharge standard " primary standard (GB8978-1996).The portion-wise addition of oxygenant and the interval mode that adds the time have determined the height of clearance, also are advantages of the present invention.Can reach removal effect preferably with lower oxygenant dosage.
Embodiment 5
(1) detects concentrated waste percolate after certain reverse osmosis membrane processing, its TOC and COD are respectively 2584mg/L and 4285mg/L, this rubbish concentrated solution of 1L is put into the 2.5L beaker, stir under the room temperature, add the poly-ferric chloride coagulant (by weight percentage) of 0.25g, 200-300r/min stirs 2min fast, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min stirs 2min fast, slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min.Measure supernatant liquor TOC and COD and be respectively 2139mg/L and 3514mg/L, clearance reaches 17.2% and 18.0% respectively.
(2) in the supernatant liquor of step (1), add nitric acid, regulate pH to 2.0, sedimentation 4.0h, 4000r/min centrifugation 15min, 50 ℃ of vacuum drying ovens are concentrated into semi-solid state, can obtain the liquid humic acid 5.5g of high density.Measure through potassium dichromate oxidation, its content is higher than 90%.After testing, supernatant liquor TOC and COD are respectively 1347mg/L and 2136mg/L, and clearance reaches 37% and 39.2% respectively.
(3) with the supernatant liquor pH to 4.0 of nitric acid regulating step (2), stir adding ferrous sulfate 2.5g under the room temperature, divide 3 times every 10min adding hydrogen peroxide (30%H
2O
2) 6mL, continue to stir 30min, leave standstill 30h.After testing, TOC and COD are respectively 66mg/L and 51mg/L, and clearance reaches 95.1% and 97.6% respectively.Reach " integrated wastewater discharge standard " primary standard (GB8978-1996).The portion-wise addition of oxygenant and the interval mode that adds the time have determined the height of clearance, also are advantages of the present invention.Can reach removal effect preferably with lower oxygenant dosage.
Claims (3)
1. one kind is extracted humic acid and administers method for waste water from concentrated waste percolate, it is characterized in that comprising the steps:
(1) add coagulating agent at concentrated waste percolate, stir, add the coagulation auxiliary agent, after the stirring, sedimentation 40～60min; The add-on of coagulating agent and coagulation auxiliary agent be respectively percolate quality 0.15%～0.35% and 0.005%～0.01%; Described coagulating agent is polyaluminium sulfate, bodied ferric sulfate or poly-ferric chloride; Described coagulation auxiliary agent is a polyacrylamide;
(2) precipitation, separation get supernatant liquor;
(3) supernatant liquor is regulated pH value to 1.0～3.0;
(4) sedimentation 4.0～8.0h, precipitation, separation; The concentrating and precipitating thing promptly gets the liquid humic acid of high density;
(5) precipitating, separate the supernatant liquor that obtains uses high-level oxidation technology to handle the back qualified discharge; Described high-level oxidation technology is to be in the catalyticreactor of light source with daylight, adds oxygenant and catalyzer, and the supernatant liquor oxidative degradation time is 20-30h; Described oxygenant is a hydrogen peroxide, and described catalyzer is a ferrous sulfate.
2. according to claim 1ly extract humic acid and administer method for waste water from concentrated waste percolate, it is characterized in that: the separate mode of step (2) and step (4) is centrifugation.
3. according to claim 1ly extract humic acid and administer method for waste water from concentrated waste percolate, it is characterized in that: the adjusting of step (3) pH is to regulate with sulfuric acid or hydrochloric acid.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987766A (en) * | 2010-11-08 | 2011-03-23 | 华南理工大学 | Standard treatment method for concentrated leachate |
| CN104245164A (en) * | 2012-04-10 | 2014-12-24 | 迪普拉克奎有限责任公司 | Process for recovering humic substances from percolate originating from urban solid refuse dumps or the like, and humic substance obtained by the process |
| CN104310659A (en) * | 2014-11-12 | 2015-01-28 | 福州大学 | Separating reclaiming technology for humic acid in garbage leachate MBR+NF concentrated liquid containing high concentration of SO42 |
| CN105084592A (en) * | 2015-08-13 | 2015-11-25 | 广西大学 | Method for treating firecracker paper waste water |
| CN105731692A (en) * | 2016-04-13 | 2016-07-06 | 湖北合加环境设备有限公司 | Pretreatment method suitable for evaporative crystallization of landfill leachate stock solution |
| RU2595173C2 (en) * | 2011-12-22 | 2016-08-20 | Влодимир ЧЕРВОНЫЙ | Microbial organic fertiliser and production methods thereof |
| CN105923911A (en) * | 2016-06-16 | 2016-09-07 | 北京博力扬环保科技有限公司 | Refuse leachate pretreatment method |
| CN110386733A (en) * | 2019-08-05 | 2019-10-29 | 四川锐源能环科技有限公司 | The reclaimer and method of humic acid in a kind of garbage incinerating power plant percolate |
| CN110627255A (en) * | 2019-10-11 | 2019-12-31 | 上海康恒环境股份有限公司 | Method for nanofiltration water inlet pretreatment of percolate of waste incineration plant |
| CN114105360A (en) * | 2021-11-25 | 2022-03-01 | 河南力诚环保科技有限公司 | Advanced oxidation reaction-based high-concentration landfill leachate concentrated solution treatment method |
| CN115093054A (en) * | 2022-07-06 | 2022-09-23 | 山东理工大学 | Harmless treatment method for landfill leachate |
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| CN101987766A (en) * | 2010-11-08 | 2011-03-23 | 华南理工大学 | Standard treatment method for concentrated leachate |
| RU2595173C2 (en) * | 2011-12-22 | 2016-08-20 | Влодимир ЧЕРВОНЫЙ | Microbial organic fertiliser and production methods thereof |
| CN104245164A (en) * | 2012-04-10 | 2014-12-24 | 迪普拉克奎有限责任公司 | Process for recovering humic substances from percolate originating from urban solid refuse dumps or the like, and humic substance obtained by the process |
| CN104245164B (en) * | 2012-04-10 | 2016-11-16 | 迪普拉克奎有限责任公司 | The method reclaiming humus from the transudate deriving from urban solid garbage field etc. |
| CN104310659A (en) * | 2014-11-12 | 2015-01-28 | 福州大学 | Separating reclaiming technology for humic acid in garbage leachate MBR+NF concentrated liquid containing high concentration of SO42 |
| CN104310659B (en) * | 2014-11-12 | 2016-06-01 | 福州大学 | Containing high density SO42-Percolate MBR+NF concentrated solution in humic acids process for separating and recovering |
| CN105084592A (en) * | 2015-08-13 | 2015-11-25 | 广西大学 | Method for treating firecracker paper waste water |
| CN105731692A (en) * | 2016-04-13 | 2016-07-06 | 湖北合加环境设备有限公司 | Pretreatment method suitable for evaporative crystallization of landfill leachate stock solution |
| CN105923911A (en) * | 2016-06-16 | 2016-09-07 | 北京博力扬环保科技有限公司 | Refuse leachate pretreatment method |
| CN110386733A (en) * | 2019-08-05 | 2019-10-29 | 四川锐源能环科技有限公司 | The reclaimer and method of humic acid in a kind of garbage incinerating power plant percolate |
| CN110627255A (en) * | 2019-10-11 | 2019-12-31 | 上海康恒环境股份有限公司 | Method for nanofiltration water inlet pretreatment of percolate of waste incineration plant |
| CN114105360A (en) * | 2021-11-25 | 2022-03-01 | 河南力诚环保科技有限公司 | Advanced oxidation reaction-based high-concentration landfill leachate concentrated solution treatment method |
| CN115093054A (en) * | 2022-07-06 | 2022-09-23 | 山东理工大学 | Harmless treatment method for landfill leachate |
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