CN112299547A - Method for degrading landfill leachate membrane concentrated solution by catalyzing hydrogen peroxide with single copper salt - Google Patents
Method for degrading landfill leachate membrane concentrated solution by catalyzing hydrogen peroxide with single copper salt Download PDFInfo
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- oxidation reaction
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000149 chemical water pollutant Substances 0.000 title claims abstract description 36
- 150000001879 copper Chemical class 0.000 title claims abstract description 19
- 230000000593 degrading effect Effects 0.000 title claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 66
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- -1 halogen ions Chemical class 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 25
- 239000010949 copper Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- 239000002351 wastewater Substances 0.000 description 13
- 238000003828 vacuum filtration Methods 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- XYNZKHQSHVOGHB-UHFFFAOYSA-N copper(3+) Chemical compound [Cu+3] XYNZKHQSHVOGHB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for degrading landfill leachate membrane concentrated solution by catalyzing hydrogen peroxide with single copper salt, which comprises the steps of adding a copper salt catalyst and hydrogen peroxide into the landfill leachate membrane concentrated solution, and carrying out oxidation reaction under the conditions that the pH of a system is controlled to be 4-8 and the temperature is controlled to be 40-60 ℃. The method fully utilizes the characteristic that Cu (II) can catalyze hydrogen peroxide in multiple stages to generate active oxidation substances to degrade organic matters in the membrane concentrated solution, can achieve better oxidative degradation effect even under the condition of near neutrality, simultaneously, the oxidation reaction is a homogeneous reaction process, no precipitated sludge is generated, the dosage of a copper salt catalyst is small, the cost of the catalyst is reduced, and the addition amount of Cu (II) is lower than the pollution control standard of a domestic garbage landfill by 40mg/L (GB 16889-2008).
Description
Technical Field
The invention relates to a method for treating landfill leachate membrane concentrated solution, in particular to a method for degrading landfill leachate membrane concentrated solution by using single copper salt to catalyze hydrogen peroxide through multi-stage oxidation, and belongs to the technical field of organic wastewater treatment.
Background
The landfill leachate is high-concentration toxic and harmful organic wastewater with complex components, and is mainly treated by adopting a biochemical treatment and membrane treatment technology combined process in the prior art. This process produces a large amount of membrane concentrate. The membrane concentrated solution contains a large amount of organic matters which are difficult to degrade, and has high salinity and poor biodegradability. Currently, the treatment and disposal of membrane concentrate mainly comprises three modes: first, transfer and export, such as recharge; second, reduction, such as evaporation and membrane distillation; and thirdly, innocent treatment, such as advanced oxidation. The difficult-to-degrade organic matters and salt in the membrane concentrated solution can be continuously enriched through recharging, the treatment burden of the leachate of the refuse landfill is increased, and the stability of the system is damaged. The evaporation method is operated under high temperature conditions, which causes equipment corrosion and high energy consumption. The membrane distillation method can not really degrade organic matters, produces concentrated solution with higher concentration and is more difficult to process. The advanced oxidation method can mineralize organic matters into CO2And H2O, is a hotspot in the field of organic wastewater treatment. Particularly, the Fenton treatment technique is simple to operate, generates highly oxidizing OH, and can efficiently and rapidly degrade organic substances, but the conventional Fenton treatment technique is a Fenton treatment techniqueThe technology has the defects of narrow pH range (2-3), iron sludge generation and incapability of regeneration.
Chinese patent (publication No. CN111453923A) discloses treatment equipment and a treatment process for a landfill leachate membrane concentrated solution, wherein the membrane concentrated solution after the combined processes of a pretreatment tank, a first pH adjusting tank, an ultraviolet catalytic oxidation device, a second pH adjusting tank, a sedimentation tank, a denitrification reaction tank, a nitrification reaction tank, an MBR reaction tank and the like can be discharged up to the standard, but the flow is long, and a large amount of chemical reagents are consumed; chinese patent (publication No. CN111253013A) discloses a physicochemical combined biochemical treatment process, which comprises the steps of removing a large amount of humic acid in a garbage leachate membrane concentrated solution by using acidification-precipitation treatment, removing and decomposing refractory organic matters by two-stage electro-Fenton oxidation treatment, and removing pollutants such as residual organic matters, ammonia nitrogen, heavy metals and the like by using electro-catalytic oxidation treatment. Although the effluent can be stably discharged after reaching the standard, a large amount of acid is needed for adjusting the pH value, secondary precipitation pollutants are generated, and subsequent treatment is needed. Chinese patent (publication No. CN111320316A) discloses a method for treating a landfill leachate membrane concentrated solution, which comprises the steps of sequentially carrying out electrocatalytic oxidation, coagulating sedimentation, ultrafiltration and evaporation treatment to realize the purification treatment of the landfill leachate membrane concentrated solution, wherein the electrocatalytic oxidation process needs to adjust the pH to 3-6, the coagulating sedimentation process needs to adjust the pH to 8-11, a large amount of acid-base reagents are consumed, precipitated sludge is generated, and the energy consumption of the electrocatalytic process and the evaporation process is high. Chinese patent (publication No. CN110818000A) discloses a garbage leachate membrane concentrated solution reduction and recycling treatment system and method, firstly, a saturated membrane concentrated solution is obtained by using an immersion combustion evaporation method, then the saturated membrane concentrated solution is sent to a forced circulation evaporation crystallizer, KCl is separated out by cooling in a cooling section, and NaCl is separated out in an evaporation section. Although the evaporation process realizes reduction and resource utilization in the industrial salt preparation stage, the equipment is seriously corroded under the high-temperature and high-pressure operation condition and the energy consumption is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for realizing the rapid and efficient oxidative degradation treatment of the landfill leachate membrane concentrated solution by adopting a 'Cu (II) -catalyzed hydrogen peroxide homogeneous Fenton-like' technology, the method fully utilizes Cu (II) to catalyze hydrogen peroxide in a multistage way to generate active oxidation substances to realize the high-efficiency oxidative degradation of organic matters in the degradation membrane concentrated solution, even under the condition of near neutrality, the method can achieve better oxidative degradation effect, overcomes the defect of lower effective pH (range of 2-4) of the traditional Fenton oxidation method, meanwhile, the reaction is a homogeneous reaction process, no precipitated sludge is generated, Cu (II) can be subjected to multi-stage catalysis, the dosage of the catalyst is reduced, the cost is saved, and the addition amount of Cu (II) is less than 40mg/L (GB16889-2008) of the pollution control standard of the household garbage landfill.
In order to achieve the technical purpose, the invention provides a method for degrading landfill leachate membrane concentrated solution by catalyzing hydrogen peroxide with single copper salt, which comprises the steps of adding divalent copper salt and hydrogen peroxide into the landfill leachate membrane concentrated solution, and carrying out oxidation reaction under the conditions that the pH of a system is controlled to be 4-8 and the temperature is controlled to be 40-60 ℃.
According to the technical scheme, in the process of promoting hydrogen peroxide to oxidize and degrade the landfill leachate membrane concentrated solution, the cupric salt is adopted, the high-efficiency and rapid oxidative degradation of the landfill leachate membrane concentrated solution can be realized by controlling the pH and temperature conditions, the pH range of the oxidative degradation reaction is wide, the oxidative degradation reaction can be carried out even in a weakly acidic or neutral environment, and the defect that the existing Fenton oxidation process needs to be carried out under the acidic condition with the pH of about 3 is overcome. The oxidative degradation reaction is carried out under a proper temperature condition, has the characteristics of high speed and high efficiency, and can achieve more than 80% of high-efficiency degradation within about 4 hours. In addition, the cupric salt has the function of multi-stage catalysis, can reduce the dosage of the catalyst, reduce the cost and reduce the residue of the cupric salt in the oxidation waste liquid.
As a preferred scheme, hydrogen peroxide is added into the landfill leachate membrane concentrated solution in three batches, and a primary oxidation reaction, a secondary oxidation reaction and a tertiary oxidation reaction are sequentially carried out; and when the first batch of hydrogen peroxide is added into the garbage leachate membrane concentrated solution to complete the primary oxidation reaction, if the primary oxidation reaction solution reaches the discharge standard, directly discharging, if the primary oxidation reaction solution does not reach the discharge standard, adding the second batch of hydrogen peroxide into the primary oxidation reaction solution to complete the secondary oxidation reaction, if the secondary oxidation reaction solution reaches the discharge standard, directly discharging, and if the secondary oxidation reaction solution does not reach the discharge standard, adding the third batch of hydrogen peroxide into the secondary oxidation reaction solution to complete the tertiary oxidation reaction.
The invention utilizes the main principle that the copper salt catalyzes the hydrogen peroxide to degrade the membrane concentrated solution to be as follows:
Cu(II)+H2O2→Cu(I)+O2·-+H+；
Cu(I)+H2O2→Cu(II)+·OH+OH-；
Cu(I)+H2O2→Cu(Ⅲ)+2OH-；
meanwhile, the membrane concentrated solution contains high-concentration Cl-The reaction can be accelerated, and the specific equation is as follows:
Cu(II)-Cln+H2O2→Cu(I)-Cln+O2·-+H+；
Cu(I)-Cln+H2O2→Cu(II)-Cln+·OH+OH-；
Cu(I)-Cln+H2O2→Cu(Ⅲ)-Cln+2OH-；
according to the reaction principle, the copper salt can catalyze the hydrogen peroxide to continuously carry out three-stage oxidation reaction.
The copper salt of the present invention is preferably CuSO4·5H2O。
As a preferred scheme, the addition amount of hydrogen peroxide in the three batches is 0.5 to 3 times of the theoretical amount demand, wherein the theoretical amount demand is the molar amount of hydrogen peroxide required for complete oxidation of 1 mole of COD to water and carbon dioxide. Preferably, the addition amount of the hydrogen peroxide in the three batches is 1-2 times of the theoretical amount demand.
As a preferable scheme, the mole ratio of the cupric salt to the hydrogen peroxide in the three batches is 1: 10-5000. More preferably, the molar ratio of the cupric salt to the hydrogen peroxide is 1:1000 to 2000.
As a preferable scheme, in the oxidation reaction process, the pH of the system is controlled to be 5-7, and the temperature is controlled to be 45-55 ℃.
As a preferable scheme, halogen ions are added in the oxidation reaction process to promote the oxidation reaction.
As a preferred scheme, the halogen ion is Cl-、Br-And I-At least one of (1); wherein, Cl-The addition amount of the garbage percolate membrane concentrated solution is less than 200g/L, and Br is-The addition amount of the landfill leachate membrane concentrated solution is less than 100mg/L, I-The addition amount of the landfill leachate membrane concentrated solution is less than 100 mg/L.
As a preferable scheme, the initial COD of the garbage leachate membrane concentrated solution is 1000-8000 mg/L, and the TOC is 800-2000 mg/L.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention utilizes Cu (II) to catalyze H2O2The generated high-activity Cu (III) and OH has strong oxidation activity and high oxidation efficiency, and Cu (II) in the liquid phase does not generate precipitate and can be repeatedly used for multi-stage oxidation.
2. The invention overcomes the defect that the traditional Fenton method has effect under the strong acid condition, and the removal rate of COD can reach more than 80 percent under the condition that the pH value is 5.
3. The Fenton-like process of the invention introduces less copper salt, has low cost, Cu (II) is less than 40mg/L (GB16889-2008) of pollution control standard of the domestic garbage landfill, and has no secondary pollution.
4. The technical scheme of the invention has the advantages of simple steps, mild reaction conditions, simple equipment operation and maintenance, high treatment efficiency and contribution to industrial application.
5. The invention can adopt single copper salt as the catalyst, and can continuously carry out multi-stage oxidation, thereby greatly reducing the using amount of the catalyst.
6. The invention can promote the oxidation reaction by temperature control and halogen ions, thereby greatly shortening the oxidation reaction time.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
Example 1
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0225g of CuSO is added at room temperature4·5H2Adjusting the pH value of the solution to 5.0 by using dilute sulfuric acid, adding 9.2mL of hydrogen peroxide with the concentration of 30%, reacting for 4 hours in a water bath at 50 ℃, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the COD (chemical oxygen demand) and the TOC (total organic carbon) concentrations are respectively 271mg/L and 140.05mg/L, and the removal rates are respectively 80.92% and 77.15%.
Comparative example 1
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, 0.02254g of CuSO is added at room temperature4·5H2Adjusting the pH value of the solution to 5.0 by using dilute sulfuric acid, adding 9.2mL of hydrogen peroxide with the concentration of 30%, reacting for 4 hours at room temperature, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the COD (chemical oxygen demand) and the TOC (total organic carbon) concentrations are 1395mg/L and 609.05mg/L respectively, and the removal rates are 1.81% and 0.66% respectively. The comparative example compares the single temperature factor with example 1, and illustrates that when a single copper salt is used as the catalyst for promoting decomposition of hydrogen peroxide to perform fenton-like oxidation of organic matters, the temperature has a large influence on the oxidation reaction process, and if the oxidation reaction process is almost difficult to perform at room temperature, the temperature is controlled to about 50 ℃, so that the oxidation reaction can be rapidly and efficiently performed.
Comparative example 2
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0225g of CuSO is added at room temperature4·5H2Adjusting the pH value of the solution to 3.0 by using dilute sulfuric acid, adding 9.2mL of 30% hydrogen peroxide, reacting for 4 hours in a water bath at 50 ℃, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the COD (chemical oxygen demand) and the TOC (total organic carbon) concentrations are 787.8mg/L and 448.8mg/L respectively, and the removal rates are 44.55 and 26.79 respectively. The comparative example compares the single pH factor with example 1, and illustrates that when a single copper salt is used as a catalyst for promoting decomposition of hydrogen peroxide to perform fenton-like oxidation of organic matters, pH is also an important condition influencing the oxidation reaction process, which is more biased to a neutral environment, and overcomes the limitation that the existing fenton oxidation process requires pH of about 3.
Example 2
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 3356mg/L, TOC concentration of 785mg/L and the pH value of 8.2 and is treated by NF + RO is taken in a 500mL beaker, 0.0281g of CuSO is added at room temperature4·5H2Adjusting the pH value of the solution to 5.0 by using dilute sulfuric acid, adding 11.5mL of hydrogen peroxide with the concentration of 30%, reacting for 4 hours at 50 ℃, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the COD (chemical oxygen demand) and the TOC (total organic carbon) concentrations are 652mg/L and 268mg/L respectively, and the removal rates are 77.66% and 60.73% respectively.
Example 3
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 3459.58mg/L, TOC concentration of 857mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0169g of CuSO is added in the beaker at room temperature4·5H2Adjusting the pH value of the solution to 4.0 by using dilute sulfuric acid, adding 6.9mL of 30% hydrogen peroxide, reacting at room temperature for 18h, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the TOC concentration is 685.25mg/L, and the removal rate is 13.7%.
Example 4
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 3459.58mg/L, TOC concentration of 857mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0169g of CuSO is added in the beaker at room temperature4·5H2O solids and 50.41g NaCl. Adjusting the pH value of the solution to 4.0 by using dilute sulfuric acid, adding 6.9mL of 30% hydrogen peroxide, reacting at room temperature for 18h, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the TOC concentration is 586.55mg/L, and the removal rate is 26.13%. Relative to example 3, it is shown that the introduction of a proper amount of chloride ions can accelerate the TOC degradation efficiency of the landfill leachate membrane concentrate.
Example 5
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 3459.58mg/L, TOC concentration of 857mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0169g of CuSO is added in the beaker at room temperature4·5H2Solid O and 2.57mg NaBr. Adjusting the pH value of the solution to 4.0 by using dilute sulfuric acid, adding 6.9mL of 30% hydrogen peroxide, reacting at room temperature for 18h, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the TOC concentration is 625.37mg/L, and the removal rate is 21.22% respectively. Compared with example 3, the introduction of a proper amount of bromide ions can accelerate the TOC degradation efficiency of the landfill leachate membrane concentrated solution, and compared with example 4, the bromide ions have better effects of promoting the copper salt to catalyze the oxidative decomposition of the landfill leachate membrane concentrated solution by hydrogen peroxide compared with chloride ions.
Comparative example 3
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 3459.58mg/L, TOC concentration of 857mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0169g of CuSO is added in the beaker at room temperature4·5H2O solid and 2.36mg NaI. Adjusting the pH value of the solution to 4.0 by using dilute sulfuric acid, adding 6.9mL of 30% hydrogen peroxide, reacting at room temperature for 18h, and performing vacuum filtration to obtain wastewater with organic matters removed, wherein the TOC concentration is 603.37mg/L, and the removal rate is 19.03%. Compared with example 3, the introduction of a proper amount of iodide ions can accelerate the TOC degradation efficiency of the landfill leachate membrane concentrated solution, and compared with example 4, the iodide ions have better effects of promoting the copper salt to catalyze the hydrogen peroxide to oxidize and decompose the landfill leachate membrane concentrated solution.
Example 6
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken in a 500mL beaker, and 0.0225g of CuSO is added in the beaker under the condition of room temperature4·5H2Adjusting the pH value of the solution to 5.0 by adopting dilute sulfuric acid, adding 9.2mL of 30% hydrogen peroxide, and reacting for 4 hours at 50 ℃, wherein the reaction is primary oxidation. After the reaction is finished, the pH value of the solution is continuously adjusted to 5.0 by using dilute sulfuric acid, 2mL of 30% hydrogen peroxide is added to react for 4 hours at 50 ℃, the secondary oxidation is carried out, after the reaction is finished, the wastewater with the organic matters removed is obtained by vacuum filtration, the COD concentration is 140.83mg/L, and the removal rate is 90.08%.
Example 7
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken to be arranged in a 500mL beaker, and 0.0225g of CuSO is added4·5H2Adjusting the pH value of the solution to 5.0 by adopting dilute sulfuric acid, adding 9.2mL of 30% hydrogen peroxide, and stirring at 50 ℃ for 4 hours, wherein the step is first-stage oxidation; after the reaction is finished, the pH value of the solution is adjusted to 5.0 by using dilute sulfuric acid, 2mL of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred for 4 hours at the temperature of 50 ℃, which is secondary oxidation; after the reaction is finished, the pH value of the solution is adjusted to 5.0 by using dilute sulfuric acid, 22mL of hydrogen peroxide with the concentration of 30% is added and stirred for 4 hours at the temperature of 50 ℃, the three-stage oxidation is carried out, the waste water with residual organic matters removed is obtained by vacuum filtration after the reaction is finished, the measured COD (chemical oxygen demand) is 78mg/L, and the three-stage discharge standard (COD) in the domestic garbage landfill pollution control standard (GB16889-2008) is metcr<100mg/L)。
Example 8
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken to be arranged in a 500mL beaker, and 0.0225g of CuSO is added into the beaker4·5H2Adjusting the pH value of the solution to 5.0 by adopting dilute sulfuric acid, adding 9.2mL of 30% hydrogen peroxide, stirring for 4 hours at 40 ℃, and carrying out vacuum filtration to obtain the wastewater with the organic matters removed, wherein the COD is 445.6mg/L, and the removal rate is 68.65%.
Example 9
200mL of refuse leachate membrane concentrated solution which is generated in certain refuse landfill and has the COD concentration of 1633mg/L, TOC concentration of 705mg/L and the pH value of 8.3 and is treated by NF + RO is taken to be arranged in a 500mL beaker, and 0.0225g of CuSO is added into the beaker4·5H2Adjusting the pH value of the solution to 5.0 by adopting dilute sulfuric acid, adding 9.2mL of 30% hydrogen peroxide, stirring for 4 hours at 60 ℃, and carrying out vacuum filtration to obtain waste water with organic matters removed, wherein the COD is 394mg/L, and the removal rate is 72.25%.
Claims (8)
1. A method for degrading landfill leachate membrane concentrated solution by catalyzing hydrogen peroxide with single copper salt is characterized by comprising the following steps: and (3) adding a cupric salt and hydrogen peroxide into the landfill leachate membrane concentrated solution, and carrying out oxidation reaction under the conditions that the pH of a system is controlled to be 4-8 and the temperature is controlled to be 40-60 ℃.
2. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 1, wherein the method comprises the following steps: adding hydrogen peroxide into the landfill leachate membrane concentrated solution in three batches, and sequentially carrying out primary oxidation reaction, secondary oxidation reaction and tertiary oxidation reaction; after the first batch of hydrogen peroxide is added into the garbage leachate membrane concentrated solution to complete the primary oxidation reaction, if the primary oxidation reaction solution reaches the discharge standard, directly discharging, if the primary oxidation reaction solution does not reach the discharge standard, adding the second batch of hydrogen peroxide into the primary oxidation reaction solution to complete the secondary oxidation reaction, if the secondary oxidation reaction solution reaches the discharge standard, directly discharging, and if the secondary oxidation reaction solution does not reach the discharge standard, adding the third batch of hydrogen peroxide into the secondary oxidation reaction solution to complete the tertiary oxidation reaction.
3. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 2, wherein the method comprises the following steps: the addition amount of the hydrogen peroxide in the three batches is 0.5-3 times of the theoretical amount demand, wherein the theoretical amount demand is the molar amount of the hydrogen peroxide needed for completely oxidizing 1 mole of COD into water and carbon dioxide.
4. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 2, wherein the method comprises the following steps: the molar ratio of the cupric salt to the hydrogen peroxide in each batch is 1: 10-5000.
5. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 1, wherein the method comprises the following steps: in the oxidation reaction process, the pH of the system is controlled to be 5-7, and the temperature is controlled to be 45-55 ℃.
6. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 1, wherein the method comprises the following steps: and adding halogen ions to promote the oxidation reaction in the oxidation reaction process.
7. The method for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 6, wherein the method comprises the following steps: the halide ion is Cl-、Br-And I-At least one of (1); wherein, Cl-The addition amount of the garbage percolate membrane concentrated solution is less than 200g/L, and Br is-The addition amount of the landfill leachate membrane concentrated solution is less than 100mg/L, I-The addition amount of the landfill leachate membrane concentrated solution is less than 100 mg/L.
8. The process for the catalytic hydrogen peroxide degradation of landfill leachate membrane concentrate of claim 1 or 2, wherein the hydrogen peroxide degradation is performed with a single copper salt: the initial COD of the landfill leachate membrane concentrated solution is 1000-8000 mg/L, and the TOC is 800-2000 mg/L.
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