CN101701025B - 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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- 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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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 60 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 process mostly at present, adopts landfill method to process municipal wastes and can produce a large amount of percolates.Percolate is a kind of liquid that contains high concentration suspended substance and high concentration organic or inorganic composition, wherein contain considerable toxic substance, and mass concentration is very high, enter rivers and lakes fully without processing, 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 approaches neutral, and basicity is high; 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.Although various countries carry out this respect research existing considerable time, there is no so far effective treatment process, to the processing of the percolate (landfill yard uses more than 10 years) of later stage landfill yard, be a global difficult problem particularly always.
Because the NH of high density
3-N is inhibited to microorganism, and the material (such as humic acid, tensio-active agent etc.) that contains the degraded of multiple poisonous and hazardous hard-degraded substance (such as polycyclic aromatic hydrocarbons, polychlorobiphenyl etc.) and antibiont in the percolate makes the application of biological process be subject to significantly restriction 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 without phase transformation, less energy-consumption, can effectively remove inorganic salt and organic molecule impurity, have higher reusing rate, can guarantee good treatment effect, at present domestic existing large-scale landfill adopts reverse osmosis process to process 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 process.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 in a large number the high density humic acid is arranged.The processing of concentrated solution mainly contains the methods such as burning, curing, distillation is dry and recharge, but this type of processing exists serious problems such as power consumption is large, energy wastage.
Summary of the invention
The purpose of this invention is to provide extracted humic acid (humic substances a kind of concentrated waste percolate that after reverse-osmosis treated, produces, 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 respectively 96.4% and 97.8%.
Purpose of the present invention can realize by following measures:
A kind of from the concentrated waste percolate extracted humic acid and administer method for waste water, comprise the steps:
(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 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 namely gets the liquid humic acid of high density;
(5) precipitating, separate the supernatant liquor that obtains uses high-level oxidation technology to process rear qualified discharge; Described high-level oxidation technology is in the catalyticreactor take daylight as light source, adds oxygenant and catalyzer, and the supernatant liquor oxidative degradation time is 20-30h; Described oxygenant is hydrogen peroxide, and described catalyzer is 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, technique of the present invention is simple, equipment is few, the investment is little, is fit to process in the rubbish concentrated solution field.
3, the method for extracted humic acid the concentrated waste percolate that produces after reverse-osmosis treated has certain economic benefit, social benefit and environmental benefit.Humic acid can be applicable to liquid state organic fertilizer to realize resource utilization.
The method is processed 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 the comprehensive utilization to concentrated waste percolate, reached and administered the management goal of polluting and changing harmful to treasure.And simple process, equipment is few, invests littlely, and when administering the three wastes, utilize resources synthetically is without the secondary three waste discharge.The inventive method has overcome the large problem of energy consumption that percolation liquid membrane process concentrated liquid extracted humic acid technology exists, and has good society and economic benefit.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, 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 rapid stirring 2min, add 1ml 0.05% (weight concentration) coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min 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 respectively 15% and 18%.
(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 respectively 33% and 37%.
(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 respectively 93.8% and 95.7%.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 preferably removal effect 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 rapid stirring 2min, add 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min 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 respectively 16.5% and 18.5%.
(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 respectively 35% and 38.2%.
(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 respectively 93.1% and 96.1%.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 preferably removal effect 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 rapid stirring 2min, add 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min 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 respectively 18.5% and 20.1%.
(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 respectively 38% and 40.2%.
(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 respectively 93.6% and 96.5%.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 preferably removal effect 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 rapid stirring 2min, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min 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 respectively 17.7% and 18.1%.
(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 respectively 40% and 42.2%.
(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 respectively 93.4% and 96.6%.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 preferably removal effect 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 rapid stirring 2min, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min 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 respectively 17.2% and 18.0%.
(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 respectively 37% and 39.2%.
(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 respectively 95.1% and 97.6%.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 preferably removal effect with lower oxygenant dosage.
Claims (5)
1. one kind from the concentrated waste percolate extracted humic acid and administer method for waste water, it is characterized in that comprising the steps:
(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 rapid stirring 2min, the coagulation auxiliary agent polyacrylamide that adds 1ml weight concentration 0.05%, 200-300r/min rapid stirring 2min slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min; Get supernatant liquor;
(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;
(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 30wt% hydrogen peroxide 6mL every 10min, continue to stir 30min, leave standstill 24h.
2. one kind from the concentrated waste percolate extracted humic acid and administer method for waste water, it is characterized in that comprising the steps:
(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 of 0.25g, 200-300r/min rapid stirring 2min adds 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min, slowly stir 1min, sedimentation 60min; 4000r/min centrifugation 15min; Get supernatant liquor;
(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;
(3) with the supernatant liquor pH to 4.0 of hydrochloric acid regulating step (2), stir to add ferrous sulfate 2.5g under the room temperature, add 30% hydrogen peroxide 6mL every 10min minutes for 3 times, continue to stir 30min, leave standstill 20h.
3. one kind from the concentrated waste percolate extracted humic acid and administer method for waste water, it is characterized in that comprising the steps:
(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 of 0.35g, 200-300r/min rapid stirring 2min, add 2ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min; Get supernatant liquor;
(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;
(3) with the supernatant liquor pH to 4.0 of sulfuric acid regulating step (2), stir to add ferrous sulfate 2.5g under the room temperature, add 30% hydrogen peroxide 6mL every 10min minutes for 3 times, continue to stir 30min, leave standstill 24h.
4. one kind from the concentrated waste percolate extracted humic acid and administer method for waste water, it is characterized in that comprising the steps:
(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 of 0.35g, 200-300r/min rapid stirring 2min, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min; Get supernatant liquor;
(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;
(3) with the supernatant liquor pH to 4.0 of sulfuric acid regulating step (2), stir to add ferrous sulfate 2.5g under the room temperature, add 30% hydrogen peroxide 6mL every 10min minutes for 3 times, continue to stir 30min, leave standstill 24h.
5. one kind from the concentrated waste percolate extracted humic acid and administer method for waste water, it is characterized in that comprising the steps:
(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 of 0.25g, 200-300r/min rapid stirring 2min, add 1ml 0.05% coagulation auxiliary agent polyacrylamide, 200-300r/min rapid stirring 2min slowly stirs 1min, sedimentation 60min; 4000r/min centrifugation 15min; Get supernatant liquor;
(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;
(3) with the supernatant liquor pH to 4.0 of nitric acid regulating step (2), stir to add ferrous sulfate 2.5g under the room temperature, add 30% hydrogen peroxide 6mL every 10min minutes for 3 times, continue to stir 30min, leave standstill 30h.
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