CN107265777B - Method for treating membrane filtration concentrated solution of landfill leachate - Google Patents
Method for treating membrane filtration concentrated solution of landfill leachate Download PDFInfo
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- CN107265777B CN107265777B CN201710652539.9A CN201710652539A CN107265777B CN 107265777 B CN107265777 B CN 107265777B CN 201710652539 A CN201710652539 A CN 201710652539A CN 107265777 B CN107265777 B CN 107265777B
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005374 membrane filtration Methods 0.000 title claims abstract description 25
- 239000000149 chemical water pollutant Substances 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000010865 sewage Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000011001 backwashing Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000004148 unit process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000010797 grey water Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 meanwhile Chemical compound 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- 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
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating landfill leachate membrane filtration concentrated solution, which comprises the following steps: performing primary Fenton reaction; precipitating with lime water and sodium hydroxide solution; the BAF processing unit processes; secondary fenton reaction and PAM precipitation. The treatment method for the membrane filtration concentrated solution of the landfill leachate provided by the invention has the following advantages: the membrane filtration concentrated solution of the landfill leachate can be efficiently treated with low cost, and various indexes of effluent are ensured to meet the discharge standard.
Description
Technical Field
The invention belongs to the technical field of garbage treatment, and particularly relates to a method for treating garbage leachate membrane filtration concentrated solution.
Background
Because the biodegradability of the leachate membrane filtration concentrate of the landfill site is poor, the salinity is high, the heavy metal content is high, the treatment difficulty is very high, the existing landfill site is generally not treated, a recharging mode is directly adopted, and long-term recharging can cause the accumulation of salinity and refractory organics, the biodegradability of the leachate is reduced, the treatment difficulty is increased, and the water flux of the membrane is reduced, so that how to effectively treat the leachate membrane filtration concentrate of the landfill site is a matter which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for treating the membrane filtration concentrated solution of the landfill leachate, which can effectively solve the problems.
The technical scheme adopted by the invention is as follows:
the invention provides a method for treating landfill leachate membrane filtration concentrated solution, which comprises the following steps:
step 1, adjusting the pH of a landfill leachate membrane filtration concentrated solution to be treated to 4-5.5 by using a dilute sulfuric acid solution with the mass fraction of 10% under stirring;
and 2, performing primary Fenton reaction, namely flowing the concentrated solution after the pH is adjusted to a Fenton oxidation tank, and adding ferrous sulfate heptahydrate into the Fenton oxidation tank under stirring, wherein the dosage of the ferrous sulfate heptahydrate is that 1g of concentrated solution COD is added with 0.005-0.02 mol/L Fe2+(ii) a After the ferrous sulfate heptahydrate is added, H is added2O2The dosage is as follows: adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Then, stirring and reacting for 2-4 h;
step 4, regulating the pH of the supernatant to 7-8.5 by using a dilute sulfuric acid solution with the mass fraction of 10%, and then, passing the supernatant through an anoxic BAF treatment unit from bottom to top at the filtering speed of 1-3m/h by adopting an up-flow mode; the filter material used by the anoxic BAF treatment unit is ceramsite with the particle size of 3-5 mm; the sewage treated by the anoxic BAF treatment unit passes through the aerobic BAF treatment unit at a filtering speed of 1-3m/h by adopting an up-flow mode through an intermediate water tank; wherein, the filter material used by the aerobic BAF treatment unit is ceramsite with the grain diameter of 3-5mm, the aeration pipe of the aerobic tank and the air backwashing pipe are independently arranged, and the aeration adopts a single-hole membrane air diffuser which is arranged above the pebble bearing layer and below the ceramsite filter material; part of the effluent of the aerobic BAF treatment unit flows back to the water inlet end of the anoxic BAF treatment unit, and the reflux ratio is 150-700%; the aerobic BAF treatment unit is provided with a water inlet pump independently; a delivery pump capable of adding a carbon source is arranged at the water inlet end of the anoxic BAF treatment unit, and when the carbon source is insufficient, an additional carbon source is added;
step 5, removing COD, ammonia nitrogen and total nitrogen in the sewage through BAF treatment in the step 4, and then flowing into a Fenton oxidation tank to perform a secondary Fenton reaction; wherein, the process of the secondary Fenton reaction is as follows: under the stirring, ferrous sulfate heptahydrate and H are simultaneously added into a Fenton oxidation tank2O2Wherein, 0.005-0.02 mol/L mol of Fe is added into 1g of concentrated solution COD2+(ii) a Adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Stirring and reacting for 2-4 h;
and 6, adjusting the pH of the concentrated solution after the secondary Fenton reaction to 7-8 by adopting a 100 g/L sodium hydroxide solution, then adding PAM, precipitating and separating, and discharging the supernatant when each index meets the discharge standard.
Preferably, in the step 2, the adding speed of the ferrous sulfate heptahydrate is as follows: 0.2-0.5 ml/min; h2O2The adding speed is as follows: 3-4 ml/min.
Preferably, in step 3, the lime water adding speed is as follows: 1.0-2.0 ml/min; the adding speed of the sodium hydroxide solution is as follows: 0.2-0.5 ml/min.
Preferably, in step 5, ferrous sulfate heptahydrate and H2O2The adding speed is as follows: 2-3 ml/min.
The treatment method for the membrane filtration concentrated solution of the landfill leachate provided by the invention has the following advantages:
the membrane filtration concentrated solution of the landfill leachate can be efficiently treated with low cost, and various indexes of effluent are ensured to meet the discharge standard.
Drawings
Fig. 1 is a schematic flow chart of a method for treating membrane filtration concentrated solution of landfill leachate provided by the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for treating landfill leachate membrane filtration concentrated solution, which comprises the following steps with reference to figure 1:
step 1, adjusting the pH of a landfill leachate membrane filtration concentrated solution to be treated to 4-5.5 by using a dilute sulfuric acid solution with the mass fraction of 10% under stirring;
and 2, performing primary Fenton reaction, namely flowing the concentrated solution after the pH is adjusted to a Fenton oxidation tank, and adding ferrous sulfate heptahydrate into the Fenton oxidation tank under stirring, wherein the dosage of the ferrous sulfate heptahydrate is that 1g of concentrated solution COD is added with 0.005-0.02 mol/L Fe2+(ii) a After the ferrous sulfate heptahydrate is added, H is added2O2The dosage is as follows: adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Then, stirring and reacting for 2-4 h;
the Fenton reaction is one of advanced oxidation methods, the strong oxidizing property of free hydroxyl generated by catalyzing hydrogen peroxide by ferrous ions is utilized to convert non-degradable macromolecular organic matters into easily degradable micromolecular organic matters or completely mineralize the micromolecular organic matters into carbon dioxide and water, meanwhile, ferric ions generated by the reaction are good flocculating agents, and part of pollutants can be removed by flocculation adsorption, so that Fenton has good removal rate on COD and chroma.
In the step, a great number of experiments of the inventor show that when the primary Fenton reaction is carried out, ferrous sulfate heptahydrate and H are added into the membrane filtration concentrated solution of the landfill leachate during the primary Fenton reaction2O2The rate, the dosage and the adding sequence of the components all affect various indexes of the finally treated discharge liquid. The process described in this step can significantly improve the properties of the final treated effluent. See the experimental examples below for specific experimental data.
In addition, because the dosage of the first-level Fenton reaction is large, the utilization efficiency of the medicament can be ensured by firstly adding ferrous sulfate and then adding hydrogen peroxide.
the concentrated solution of the refuse landfill contains various heavy metal ions, and lime water is added in the step to roughly adjust the pH value of the concentrated solution, so that the heavy metal ions are precipitated under the alkaline condition and removed from the water. The removal rate of heavy metal ion precipitation can be improved by adding lime water. Then, the PH is adjusted by using a sodium hydroxide solution, and the complete precipitation of the heavy metal ions is further realized.
Step 4, regulating the pH of the supernatant to 7-8.5 by using a dilute sulfuric acid solution with the mass fraction of 10%, and then, passing the supernatant through an anoxic BAF treatment unit from bottom to top at the filtering speed of 1-3m/h by adopting an up-flow mode; the filter material used by the anoxic BAF treatment unit is ceramsite with the particle size of 3-5 mm; the sewage treated by the anoxic BAF treatment unit passes through the aerobic BAF treatment unit at a filtering speed of 1-3m/h by adopting an up-flow mode through an intermediate water tank; wherein, the filter material used by the aerobic BAF treatment unit is ceramsite with the grain diameter of 3-5mm, the aeration pipe of the aerobic tank and the air backwashing pipe are independently arranged, and the aeration adopts a single-hole membrane air diffuser which is arranged above the pebble bearing layer and below the ceramsite filter material; part of the effluent of the aerobic BAF treatment unit flows back to the water inlet end of the anoxic BAF treatment unit, and the reflux ratio is 150-700%; the aerobic BAF treatment unit is provided with a water inlet pump independently; a delivery pump capable of adding a carbon source is arranged at the water inlet end of the anoxic BAF treatment unit, and when the carbon source is insufficient, an additional carbon source is added;
BAF is one of biomembrane methods, because of adopting the spherical filler of uniform size, not only provide the huge growth surface for the growth of microorganism, have filtering effects at the same time, have the splendid removal effect to COD, ammonia nitrogen, SS, the removal rate to ammonia nitrogen is above 90%, cooperate with adding the carbon source, the removal rate to total nitrogen can also reach above 70%. An anoxic BAF treatment unit and an aerobic BAF treatment unit which are connected in series are adopted, and in front of the anoxic BAF treatment unit, denitrification can be performed by utilizing a carbon source in inlet water, so that an external carbon source is reduced, and the treatment cost is reduced.
Step 5, removing COD, ammonia nitrogen and total nitrogen in the sewage through BAF treatment in the step 4, and then flowing into a Fenton oxidation tank to perform a secondary Fenton reaction; wherein, the process of the secondary Fenton reaction is as follows: under the stirring, ferrous sulfate heptahydrate and H are simultaneously added into a Fenton oxidation tank2O2Wherein, 0.005-0.02 mol/L mol of Fe is added into 1g of concentrated solution COD2+(ii) a Adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Stirring and reacting for 2-4 h;
and 6, adjusting the pH of the concentrated solution after the secondary Fenton reaction to 7-8 by adopting a 100 g/L sodium hydroxide solution, then adding PAM, precipitating and separating, and discharging the supernatant when each index meets the discharge standard.
Most of chroma and COD (chemical oxygen demand) of about 70 percent can be removed through a primary Fenton reaction, the biodegradability of the primary Fenton reaction is improved, after the primary Fenton reaction, the PH value is adjusted to 11-12 by adding lime water and a sodium hydroxide solution, heavy metal ions are precipitated and removed from water, the PH value of outlet water is adjusted to 7-9, the outlet water enters BAF, the BAF adopts preposed anoxia, ammonia nitrogen and total nitrogen are removed by refluxing nitrification liquid of an aerobic tank, the removal rate of the COD in the step is about 80 percent, the ammonia nitrogen and the total nitrogen are reduced to be below a discharge standard, but the COD of the outlet water still cannot reach the standard, the effluent water is subjected to a Fenton reaction again to remove the residual COD, and concentrated solution treated in the steps is mixed with 3 times of membrane production water, so that the COD concentration can be lower than 100 mg/L5Less than 30 mg/L, ammonia nitrogen concentration less than 25 mg/L, and total nitrogen concentration less than 40 mg/L.
The first embodiment is as follows:
step 1, adjusting the pH of a landfill leachate membrane filtration concentrated solution to be treated to 4 by adopting a dilute sulfuric acid solution with the mass fraction of 10% under stirring;
and 2, performing primary Fenton reaction, namely flowing the concentrated solution after the pH is adjusted to a Fenton oxidation tank, and adding ferrous sulfate heptahydrate into the Fenton oxidation tank under stirring, wherein the dosage of the ferrous sulfate heptahydrate is that 1g of concentrated solution COD is added with 0.005-0.02 mol/L Fe2+(ii) a After the ferrous sulfate heptahydrate is added, H is added2O2The dosage is as follows: adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Then, stirring and reacting for 2-4 h; wherein, the adding speed of the ferrous sulfate heptahydrate is as follows: 0.2 ml/min; h2O2The adding speed is as follows: 4 ml/min.
And 3, adding 100 g/L lime water into the concentrated solution after the primary Fenton reaction to adjust the pH of the concentrated solution to 10.5 roughly, then adding 100 g/L sodium hydroxide solution to adjust the pH of the concentrated solution to 12 finely, precipitating heavy metal ions under an alkaline condition, separating the precipitate, and taking a supernatant, wherein the adding speed of the grey water is 1.0ml/min, and the adding speed of the sodium hydroxide solution is 0.2 ml/min.
Step 4, regulating the pH of the supernatant to 7 by using a dilute sulfuric acid solution with the mass fraction of 10%, and then, passing the supernatant through an anoxic BAF treatment unit at the filtering speed of 3m/h by adopting an up-flow manner from bottom to top; the filter material used by the anoxic BAF treatment unit is ceramsite with the particle size of 3 mm; the sewage treated by the anoxic BAF treatment unit passes through the aerobic BAF treatment unit at a filtering speed of 3m/h by adopting an up-flow mode through an intermediate water tank; wherein, the filter material used by the aerobic BAF treatment unit is ceramsite with the grain diameter of 3mm, the aeration pipe of the aerobic tank and the air backwashing pipe are independently arranged, and the aeration adopts a single-hole membrane air diffuser which is arranged above the pebble supporting layer and below the ceramsite filter material; part of the effluent of the aerobic BAF treatment unit reflows to the water inlet end of the anoxic BAF treatment unit, and the reflow ratio is 150%; the aerobic BAF treatment unit is provided with a water inlet pump independently; a delivery pump capable of adding a carbon source is arranged at the water inlet end of the anoxic BAF treatment unit, and when the carbon source is insufficient, an additional carbon source is added;
step 5, removing COD, ammonia nitrogen and total nitrogen in the sewage through BAF treatment in the step 4, and then flowing into a Fenton oxidation tank to perform a secondary Fenton reaction; wherein, the process of the secondary Fenton reaction is as follows: under the stirring, ferrous sulfate heptahydrate and H are simultaneously added into a Fenton oxidation tank2O2Wherein, 0.005-0.02 mol/L mol of Fe is added into 1g of concentrated solution COD2+(ii) a Adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Stirring and reacting for 2 h; wherein, ferrous sulfate heptahydrate and H2O2The adding speed is as follows: 3 ml/min.
And 6, adjusting the pH of the concentrated solution after the secondary Fenton reaction to be acid by adopting a 100 g/L sodium hydroxide solution, then adding PAM, precipitating and separating, and discharging the supernatant liquid when all indexes meet the discharge standard.
Example two:
step 1, adjusting the pH of a landfill leachate membrane filtration concentrated solution to be treated to 5.5 by adopting a dilute sulfuric acid solution with the mass fraction of 10% under stirring;
and 2, performing primary Fenton reaction, namely flowing the concentrated solution after the pH is adjusted to a Fenton oxidation tank, and adding ferrous sulfate heptahydrate into the Fenton oxidation tank under stirring, wherein the dosage of the ferrous sulfate heptahydrate is that 1g of concentrated solution COD is added with 0.005-0.02 mol/L Fe2+(ii) a After the ferrous sulfate heptahydrate is added, H is added2O2The dosage is as follows: adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Then, stirring and reacting for 2-4 h; wherein, the adding speed of the ferrous sulfate heptahydrate is as follows: 0.5 ml/min; h2O2The adding speed is as follows: 3 ml/min.
And 3, adding 100 g/L lime water into the concentrated solution after the primary Fenton reaction to adjust the pH of the concentrated solution to 11 roughly, then adding 100 g/L sodium hydroxide solution to adjust the pH of the concentrated solution to 12 finely, precipitating heavy metal ions under an alkaline condition, and taking a supernatant after precipitation separation, wherein the adding speed of the grey water is 2.0ml/min, and the adding speed of the sodium hydroxide solution is 0.5 ml/min.
Step 4, regulating the pH of the supernatant to 8.5 by using a dilute sulfuric acid solution with the mass fraction of 10%, and then, passing the supernatant through an anoxic BAF treatment unit at the filtering speed of 1m/h by adopting an up-flow manner from bottom to top; the filter material used by the anoxic BAF treatment unit is ceramsite with the particle size of 5 mm; the sewage treated by the anoxic BAF treatment unit passes through the aerobic BAF treatment unit at a filtering speed of 1m/h by adopting an up-flow mode through an intermediate water tank; wherein, the filter material used by the aerobic BAF treatment unit is ceramsite with the particle size of 5mm, the aeration pipe of the aerobic tank and the air backwashing pipe are independently arranged, and the aeration adopts a single-hole membrane air diffuser which is arranged above the pebble supporting layer and below the ceramsite filter material; part of the effluent of the aerobic BAF treatment unit flows back to the water inlet end of the anoxic BAF treatment unit, and the reflux ratio is 700%; the aerobic BAF treatment unit is provided with a water inlet pump independently; a delivery pump capable of adding a carbon source is arranged at the water inlet end of the anoxic BAF treatment unit, and when the carbon source is insufficient, an additional carbon source is added;
step 5, removing COD, ammonia nitrogen and total nitrogen in the sewage through BAF treatment in the step 4, and then flowing into a Fenton oxidation tank for carrying outPerforming secondary Fenton reaction; wherein, the process of the secondary Fenton reaction is as follows: under the stirring, ferrous sulfate heptahydrate and H are simultaneously added into a Fenton oxidation tank2O2Wherein, 0.005-0.02 mol/L mol of Fe is added into 1g of concentrated solution COD2+(ii) a Adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Stirring and reacting for 4 hours; wherein, ferrous sulfate heptahydrate and H2O2The adding speed is as follows: 2 ml/min.
And 6, adjusting the pH of the concentrated solution after the secondary Fenton reaction to be acidic by adopting a 100 g/L sodium hydroxide solution, adding PAM, precipitating and separating, and discharging the supernatant liquid when all indexes meet the discharge standard.
Test example 1
Performing pilot test of treating the landfill leachate membrane filtration concentrated solution in the second landfill site of Dongyang city of Zhejiang, with treatment scale of 0.3m3The COD concentration of the concentrated solution in the field is 4200 mg/L5The concentration is 380 mg/L, the ammonia nitrogen concentration is 230 mg/L, and the total nitrogen concentration is 410 mg/L.
By adopting the treatment process of the first embodiment, after the primary Fenton reaction, the COD concentration is reduced to 1596 mg/L, the removal rate is 62 percent, and the BOD5The removal rate is increased to 430 mg/L and is-13.1 percent, the ammonia nitrogen concentration is reduced to 215 mg/L, the removal rate is 6.52 percent, the total nitrogen concentration is reduced to 370 mg/L, the removal rate is 9.75 percent, after anoxic BAF and aerobic BAF, the COD concentration can be continuously reduced to 483 mg/L, the removal rate is 69.7 percent, BOD is reduced5The concentration is reduced to 84 mg/L, the removal rate is 80.4 percent, the ammonia nitrogen is reduced to 14 mg/L, the removal rate is 93.4 percent, the total nitrogen concentration is reduced to 130 mg/L and 64.8 percent after the reaction by adding a carbon source, the COD concentration can be reduced to 290 mg/L after the secondary Fenton reaction is carried out on the BAF effluent, the removal rate is 55.1 percent, and the BOD5The concentration is reduced to 76 mg/L, the removal rate is 9.52 percent, the ammonia nitrogen concentration is 13 mg/L, the removal rate is 7.14 percent, the total nitrogen concentration is 121 mg/L, the removal rate is 6.92 percent, the water content of the concentrated solution accounts for 25 percent of the total amount of the percolate, the COD concentration of the outlet water of the nanofiltration membrane is lower than 50 mg/L, the treated concentrated solution is mixed with the outlet water of the nanofiltration membrane, and the COD of the mixed outlet water is 78 mg/L5The concentration is 21 mg/L, the ammonia nitrogen concentration is 3.3 mg/L, the total nitrogen concentration is 30.5 mg/L, and the requirement of the emission standard is met.
The concentrated solution is treated by the treatment process of the second embodiment, the test result is similar to the effect of the treatment process of the first embodiment, the treated concentrated solution is mixed with the outlet water of the nanofiltration membrane, and the COD of the mixed outlet water is 65 mg/L5The concentration is 18 mg/L, the ammonia nitrogen concentration is 2.3 mg/L, the total nitrogen concentration is 28.5 mg/L, and the requirement of the emission standard is met.
Test example two
And (3) adopting the treatment process of the first embodiment, only changing the adding sequence and the adding rate of the step (2), and carrying out treatment on the landfill leachate membrane filtration concentrated solution on the second landfill of east-yang city of Zhejiang province without changing other treatment steps. A total of four trials were performed:
test 1: in the step 2, ferrous sulfate heptahydrate is added into the Fenton oxidation tank at the speed of 0.2 ml/min; then, H is added into the Fenton oxidation tank at the speed of 4ml/min2O2. Namely: the process is exactly the same as the process of the first embodiment.
Test 2: in step 2, H is firstly added into the Fenton oxidation tank at the speed of 4ml/min2O2(ii) a Then, ferrous sulfate heptahydrate is added into the Fenton oxidation tank at the speed of 0.2 ml/min.
Test 3: in the step 2, ferrous sulfate heptahydrate is added into the Fenton oxidation tank at the speed of 4 ml/min; then, H is added into the Fenton oxidation tank at the speed of 0.2ml/min2O2. Namely: the process is exactly the same as the process of the first embodiment.
Test 4: in step 2, H is firstly added into the Fenton oxidation tank at the speed of 0.2ml/min2O2(ii) a Then, ferrous sulfate heptahydrate is added into the Fenton oxidation tank at the speed of 4 ml/min.
After 4 trials, the water output index is shown in the following table:
as can be seen from the above table, the water outlet index is optimal by adopting the process of the invention. Thus, it was confirmed that in the first-order Fenton reaction in step 2, ferrous sulfate heptahydrate and H were present2O2The adding speed and the adding sequence of the water treatment agent have obvious influence on the finally obtained effluent indexes.
Test example three
By adopting the treatment process of the first embodiment, only the step 3 is changed, and other treatment steps are not changed, so that the membrane filtration concentrated solution of the landfill leachate is treated in the second landfill site of east yang city of Zhejiang province. Two tests were performed in total:
experiment 1, the pH of the concentrated solution is adjusted to 11 by adding 100 g/L of lime water, and then the pH of the concentrated solution is adjusted to 12 by adding 100 g/L of sodium hydroxide solution, wherein the adding speed of the lime water is 2.0ml/min, and the adding speed of the sodium hydroxide solution is 0.5 ml/min.
Experiment 2, adding 100 g/L of sodium hydroxide solution, and adjusting the pH of the concentrated solution to 12, wherein the adding speed of the sodium hydroxide solution is 0.5 ml/min.
After 2 trials, the water output index is shown in the following table:
as can be seen from the above table, the water outlet index is optimal by adopting the process of the invention. Therefore, the effect of adding the lime water is better than that of only adding the sodium hydroxide solution when the PH is adjusted and precipitated in the step 3.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements should also be considered within the scope of the present invention.
Claims (3)
1. A method for processing membrane filtration concentrated solution of landfill leachate is characterized by comprising the following steps:
step 1, adjusting the pH of a landfill leachate membrane filtration concentrated solution to be treated to 4-5.5 by using a dilute sulfuric acid solution with the mass fraction of 10% under stirring;
step 2, primary Fenton reaction, comprising: the concentrated solution after pH adjustment flows into a Fenton oxidation tank and is stirredFirstly, ferrous sulfate heptahydrate is added into a Fenton oxidation tank, and the dosage of the ferrous sulfate heptahydrate is that 1g of concentrated solution COD is added with 0.005-0.02 mol/L of Fe2+(ii) a After the ferrous sulfate heptahydrate is added, H is added2O2The dosage is as follows: adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Then, stirring and reacting for 2-4 h;
step 3, adding 100 g/L of lime water into the concentrated solution after the first-stage Fenton reaction to roughly adjust the pH of the concentrated solution to 10.5-11, then adding 100 g/L of sodium hydroxide solution to finely adjust the pH of the concentrated solution to 12, precipitating heavy metal ions under an alkaline condition, and taking supernatant after precipitation separation;
step 4, regulating the pH of the supernatant to 7-8.5 by using a dilute sulfuric acid solution with the mass fraction of 10%, and then, passing the supernatant through an anoxic BAF treatment unit from bottom to top at the filtering speed of 1-3m/h by adopting an up-flow mode; the filter material used by the anoxic BAF treatment unit is ceramsite with the particle size of 3-5 mm; the sewage treated by the anoxic BAF treatment unit passes through the aerobic BAF treatment unit at a filtering speed of 1-3m/h by adopting an up-flow mode through an intermediate water tank; wherein, the filter material used by the aerobic BAF treatment unit is ceramsite with the grain diameter of 3-5mm, the aeration pipe of the aerobic tank and the air backwashing pipe are independently arranged, and the aeration adopts a single-hole membrane air diffuser which is arranged above the pebble bearing layer and below the ceramsite filter material; part of the effluent of the aerobic BAF treatment unit flows back to the water inlet end of the anoxic BAF treatment unit, and the reflux ratio is 150-700%; the aerobic BAF treatment unit is provided with a water inlet pump independently; a delivery pump capable of adding a carbon source is arranged at the water inlet end of the anoxic BAF treatment unit, and when the carbon source is insufficient, an additional carbon source is added;
step 5, removing COD, ammonia nitrogen and total nitrogen in the sewage through BAF treatment in the step 4, and then flowing into a Fenton oxidation tank to perform a secondary Fenton reaction; wherein, the process of the secondary Fenton reaction is as follows: under the stirring, ferrous sulfate heptahydrate and H are simultaneously added into a Fenton oxidation tank2O2Wherein, 0.005-0.02 mol/L mol of Fe is added into 1g of concentrated solution COD2+(ii) a Adding 0.02-0.04mol of H into 1g of concentrated solution COD2O2(ii) a Stirring and reacting for 2-4 h;
step 6, adjusting the pH of the concentrated solution after the secondary Fenton reaction to 7-8 by adopting a 100 g/L sodium hydroxide solution, then adding PAM, precipitating and separating, and discharging the supernatant when each index meets the discharge standard;
in the step 2, the adding speed of the ferrous sulfate heptahydrate is as follows: 0.2-0.5 ml/min; h2O2The adding speed is as follows: 3-4 ml/min.
2. The method for treating landfill leachate membrane filtration concentrate of claim 1, wherein in step 3, the lime water is added at a rate of: 1.0-2.0 ml/min; the adding speed of the sodium hydroxide solution is as follows: 0.2-0.5 ml/min.
3. The process according to claim 1, characterized in that in step 5, ferrous sulfate heptahydrate and H are added2O2The adding speed is as follows: 2-3 ml/min.
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| CN109809638A (en) * | 2019-02-28 | 2019-05-28 | 武汉天源环保股份有限公司 | Landfill leachate is without membrane treating method and system |
| TWI692449B (en) * | 2019-07-03 | 2020-05-01 | 國立高雄科技大學 | Method for treating organic wastewater |
| CN110950456B (en) * | 2019-11-29 | 2023-07-14 | 广东石油化工学院 | A harmless recovery process and device for waste biogas slurry and residue resources |
| CN116789305A (en) * | 2023-05-18 | 2023-09-22 | 南京万德斯环保科技股份有限公司 | Advanced treatment method of DT concentrated solution after MBR treatment of landfill leachate |
| CN117466477A (en) * | 2023-11-21 | 2024-01-30 | 广东锦帆环保科技有限公司 | High-salt membrane concentrate purification method and purification system |
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