CN117923684A - MDEA-containing wastewater treatment method - Google Patents
MDEA-containing wastewater treatment method Download PDFInfo
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- CN117923684A CN117923684A CN202211263632.8A CN202211263632A CN117923684A CN 117923684 A CN117923684 A CN 117923684A CN 202211263632 A CN202211263632 A CN 202211263632A CN 117923684 A CN117923684 A CN 117923684A
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- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 title claims abstract 8
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 title claims abstract 8
- 238000004065 wastewater treatment Methods 0.000 title description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 31
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000005273 aeration Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 239000010802 sludge Substances 0.000 claims abstract description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 13
- 239000006228 supernatant Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract description 4
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 70
- -1 hydroxyl free radical Chemical class 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 10
- 239000002957 persistent organic pollutant Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010865 sewage Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Abstract
The invention provides a method for treating MDEA-containing wastewater, which comprises the following steps: (1) Regulating the pH value of the wastewater containing MDEA to 4-6, adding persulfate, and reacting; (2) Regulating the pH value of the wastewater to 9-11, hydrolyzing at 70-90 ℃, and cooling; (3) Adjusting pH to 7-8, introducing activated sludge, reacting under aeration condition, settling, collecting supernatant, and filtering to obtain effluent. The invention creatively adopts persulfate to oxidize MDEA wastewater, utilizes the oxidation selectivity of sulfate radical to successfully open C-N bond to generate amide or nitro compounds, then hydrolyzes the amide or nitro compounds into ammonium salt and small molecular acid under alkaline condition, and directly mineralizes organic matters in the wastewater by an activated sludge process, thereby greatly improving the biodegradability of MDEA wastewater and facilitating subsequent hydrolysis and biochemical treatment.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating MDEA-containing industrial wastewater.
Background
N-Methyl Diethanolamine (MDEA) is an alkanolamine alkaline solvent, and is often used as a desulfurization decarbonization agent by virtue of the advantages of good selectivity, small corrosiveness, low energy consumption and the like, and is widely applied to device maintenance, cleaning and passivation processes. However, in industrial application, N-methyldiethanolamine can enter a water body due to leakage, overhauling, cleaning and the like, and MDEA is an organic solvent with strong oxidation stability and biochemical resistance, and has the characteristics of high COD, easy dissolution in water, difficult adsorption, difficult degradation, certain toxicity to microorganisms and the like, so that certain difficulty is caused to a conventional wastewater treatment process, and pretreatment is needed. Therefore, efficient degradation of MDEA wastewater has become one of the major environmental problems that plague part of industry development.
At present, aiming at the degradation of N-methyldiethanolamine wastewater, technologies such as adsorption, micro-electrolysis, hydrolytic acidification, oxidant, advanced oxidation and the like are mainly adopted, but the problems of low treatment efficiency and incomplete degradation exist. Wang Bing and the like degrade MDEA wastewater by adopting a method of filling particles as a three-dimensional electrode, wherein the COD removal rate is only 60%; ni Zhongli adopts a high-temperature wet oxidation method to treat MDEA wastewater, and the COD removal rate reaches 66.6%; wang Bo and the like adopt acidification and aeration firstly, and then Fenton oxidation and ozone catalytic oxidation are combined to use, so that the removal rate of MDEA wastewater is up to 96%, a better removal effect is obtained, but the combined use of advanced oxidation technology also greatly improves the wastewater treatment cost. By combining the prior art, the MDEA wastewater is effectively pretreated, macromolecular organic matters are converted into micromolecular matters and then degraded, and convenience is provided for the whole mineralization process.
Patent CN103833168a discloses a microwave chemical treatment method of methyl diethanolamine industrial wastewater, which comprises adding oxidant into wastewater, aerating to mix uniformly, adding sensitizer and coagulant, absorbing and precipitating under the action of microwave, separating mud from water, collecting supernatant, irradiating with microwave electrodeless lamp, mineralizing methyl diethanolamine with generated ozone and hydroxyl free radical, and removing rate up to 90%. The invention effectively combines the methods of oxidation, coagulation, microwaves and the like, and the use of the sensitizer strengthens the degradation of the methyldiethanolamine and promotes the reaction process; however, with the sequential addition of the oxidizing agent, the sensitizer and the coagulant, the dosage of the medicament is increased, and meanwhile, the sensitizer generates solid waste, so that a certain secondary pollution exists, and the post-treatment increases the reaction cost.
Patent CN103833166a discloses a process method for treating MDEA wastewater by coupling various technologies, which gradually degrades MDEA and other pollutants in the wastewater by iron-carbon micro-electrolysis-Fenton oxidation-flocculation-oxidation, and achieves better treatment effect by multi-step oxidation of the wastewater in experiments, wherein the removal rate of COD can reach 98%. However, the whole process flow is complex to operate, the oxidation process of pollutants is not well controlled, unnecessary waste of the oxidant is easy to be caused, and in addition, secondary pollution is caused by adding iron, carbon and flocculating agent in wastewater treatment.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a treatment method of MDEA-containing wastewater, which uses persulfate as an oxidant to oxidize the MDEA wastewater, opens the C-N bond of the MDEA, and controls the reaction condition to lead the oxidation product to be mainly amide or nitro compounds; and then hydrolyzing the oxidation product into organic matters such as small molecular acid and the like under alkaline conditions, so that subsequent biodegradation is facilitated, and the purposes of reducing the consumption of an oxidant and effectively improving the MDEA wastewater removal rate are achieved, and the wastewater treatment cost is greatly reduced.
The technical purpose of the invention is realized by the following technical scheme:
a method for treating MDEA-containing wastewater comprises the following steps:
(1) Regulating the pH value of the wastewater containing MDEA to 4-6, adding persulfate, and reacting;
(2) Regulating the pH value of the wastewater to 9-11, hydrolyzing at 70-90 ℃, and cooling;
(3) Adjusting pH to 7-8, introducing activated sludge, reacting under aeration condition, settling, collecting supernatant, and filtering to obtain effluent.
Further, the reaction temperature after adding persulfate in the step (1) is 50 to 70 ℃, preferably 60 to 65 ℃. The reaction time is 1-2 hours. Preferably, the reaction temperature is adjusted first, and then persulfate is added to carry out the reaction. The persulfate is activated by heating, so that the speed of generating persulfate radicals is increased, the oxidative decomposition of N-methyldiethanolamine in water is enhanced, macromolecular organic matters are degraded into micromolecular matters, and subsequent degradation is facilitated.
Further, the persulfate is at least one selected from the group consisting of Peroxomonosulfate (PMS) and Peroxodisulfate (PDS), preferably sodium persulfate.
Furthermore, the adding amount of the persulfate is 1:3-1:1 in terms of persulfate radical and/or hydrogen persulfate radical, and the molar ratio of the persulfate to the COD corresponding to the MDEA in the wastewater is generally 180mg/L of the COD corresponding to 100mg/L of the MDEA.
Further, in the step (1), the pH of the wastewater is preferably adjusted to 5 to 5.5.
Further, in the step (2), the pH of the wastewater is preferably adjusted to 10 to 10.5.
Further, the hydrolysis reaction temperature in the step (2) is preferably 80-90 ℃, and the hydrolysis reaction time is 1-2 hours. The heating reaction can effectively accelerate the hydrolysis speed of the organic pollutants.
Further, the MLSS of the activated sludge in the step (3) is 1500-2000mg/L.
Further, in the step (3), aeration is carried out to ensure that the oxygen content in the water is more than 3 mg/L; the aeration reaction time is 4-7 hours, preferably 6-7 hours, so as to ensure complete degradation of organic pollutants such as small molecular acid in the wastewater.
The pH is adjusted by sulfuric acid or NaOH solution with a mass concentration of 2-10%, preferably 3-8%.
It will be appreciated by those skilled in the art that the MDEA (N-methyldiethanolamine) -containing wastewater of the present invention generally refers to wastewater containing a concentration of MDEA which may also inevitably contain other organic contaminants, which may occur during desulfurization and decarbonization or during equipment maintenance in the industry. The waste water treated by the invention mainly uses MDEA as main pollutant, and 100mg/L MDEA approximately generates 180mg/L COD, and the invention finally thoroughly mineralizes the MDEA, so that the degradation condition of organic pollutant in the waste water is indicated directly by COD value when the effluent is monitored.
Compared with the prior art, the invention has the following advantages:
(1) The MDEA is a tertiary amine with stable property, is not easy to generate hydrolysis reaction, and in addition, the existence of methyl on N increases the difficulty of biodegradation.
(2) The invention opens the C-N bond of MDEA by controlling the adding amount of persulfate oxidant and the pH value of reaction, controls the oxidation process of reaction, ensures that the oxidation products are mainly amides or nitro compounds, reduces the generation of side reaction, and then directly hydrolyzes the oxidation products to generate micromolecular organic matters, shortens the oxidation reaction time, reduces the consumption of oxidant and saves the cost of MDEA wastewater treatment. In the prior art, some advanced oxidation technologies, such as Fenton and ozone catalysis technologies, mainly oxidize MDEA in water by hydroxyl radicals, the survival time of the hydroxyl radicals is short and the hydroxyl radicals are not selective, and after one MDEA molecule is directly oxidized into small molecule acid, the next MDEA molecule is oxidized, so that excessive oxidant is needed to be added.
(3) The invention adopts the combination means of oxidation, hydrolysis and biochemistry to effectively improve the treatment effect of MDEA wastewater, so that the removal rate of the MDEA wastewater reaches more than 90 percent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The pH value in the invention is measured by a method of measuring the pH value of water by a glass electrode method (GB/T6920), and the COD is measured by a method of measuring the COD of water by a potassium dichromate method (GB/T11914).
Example 1
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.7, the MDEA content is 234mg/L, and a certain amount of other organic pollutants are also contained in the wastewater, wherein the MDEA shows about 421.2mg/L of COD and the total COD is 530mg/L.
Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 65 ℃, adding 1.9g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:2, reacting for 1 hour; adjusting the pH value to 10 by using 5% NaOH solution, raising the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 26mg/L, wherein the total COD removal rate is 95.09%.
Example 2
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.9, the MDEA content is 251mg/L, and the wastewater also contains a certain amount of other organic pollutants, wherein the MDEA shows COD of about 451.8mg/L and the total COD is 552mg/L.
Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 60 ℃, adding 1.32g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:1, reacting for 1 hour; adjusting the pH value to 10 by using 5% NaOH solution, raising the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 48mg/L, wherein the total COD removal rate is 91.30%.
Example 3
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.3, the MDEA content is 203mg/L, and a certain amount of other organic pollutants are also contained in the wastewater, wherein the MDEA shows COD of about 365.4mg/L and the total COD is 506mg/L.
Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 50 ℃, adding 1.82g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:2, reacting for 1 hour; adjusting the pH value to 10 by using 5% NaOH solution, raising the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 74mg/L and the total COD removal rate is 85.37%.
Example 4
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.5, the MDEA content is 250mg/L, and the wastewater also contains a certain amount of other organic pollutants, wherein the MDEA shows COD of about 450mg/L and the total COD is 541mg/L.
Taking 500mL of MDEA wastewater in a beaker, adjusting the pH of the wastewater to 5.5 by using 5% sulfuric acid, heating the wastewater to 65 ℃, adding 1.19g/L sodium persulfate (NaHSO 5), wherein the molar ratio of hydrogen persulfate to COD is 1:2, reacting for 2 hours; adjusting the pH value to 10 by using 5% NaOH solution, raising the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to adjust the pH of the wastewater to 8, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 95mg/L and the total COD removal rate reaches 82.44%.
Example 5
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.4, the MDEA content is 210mg/L, and a certain amount of other organic pollutants are also contained in the wastewater, wherein the MDEA shows COD of about 378mg/L and the total COD is 517mg/L.
Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 60 ℃, adding 1.86g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:2, reacting for 1 hour; adjusting the pH to 9 by using 5% NaOH solution, raising the temperature of the wastewater to 70 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 158mg/L, wherein the total COD removal rate reaches 69.44%.
Example 6
The wastewater containing MDEA is from a sewage treatment plant, the pH is 8.7, the MDEA content is 237mg/L, and a certain amount of other organic pollutants are also contained in the wastewater, wherein the MDEA shows COD of about 426.6mg/L and the total COD is 519mg/L.
Taking 500mL of raw wastewater in a beaker, regulating the pH of the wastewater to 6 by using 5% sulfuric acid, heating the wastewater to 60 ℃, adding 1.87mg/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:2, reacting for 1 hour; adjusting the pH value to 9 by using 5% NaOH solution, increasing the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 135mg/L, wherein the total COD removal rate is 73.99%.
Comparative example 1
The MDEA containing wastewater was the same as in example 1.
Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 65 ℃, adding 0.65g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:6, reacting for 1 hour; adjusting the pH value to 10 by using 5% NaOH solution, raising the temperature of the wastewater to 90 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 227mg/L and the total COD removal rate reaches 57.17%.
Comparative example 2
The MDEA containing wastewater was the same as in example 1. Taking 500mL of MDEA wastewater in a beaker, regulating the pH of the wastewater to 5 by using 5% sulfuric acid, heating the wastewater to 65 ℃, adding 1.9g/L sodium persulfate, wherein the molar ratio of persulfate radical to COD is 1:2, reacting for 1 hour; adjusting the pH to 7 by using 5% NaOH solution, raising the temperature of the wastewater to 50 ℃ and hydrolyzing for 2 hours; adding 5% sulfuric acid to regulate the pH of the wastewater to 7.5, adding 2000mg/L of activated sludge, reacting for 7 hours under aeration condition, settling, taking supernatant, filtering, and detecting that the COD of the effluent is 284mg/L, wherein the total COD removal rate reaches 46.42%.
Comparative example 3
The MDEA containing wastewater was the same as in example 1.
Taking 500mL of raw wastewater in a beaker, regulating the pH of the wastewater to 3 by using 5% sulfuric acid, heating the wastewater to 80 ℃, adding 4g/L of sodium persulfate, reacting for 2 hours, taking supernatant, filtering, and detecting that the COD of the effluent is 320.13mg/L and the COD removal rate is 39.6%. If the persulfate is directly used for oxidizing the MDEA wastewater, an excessive amount of oxidant is added, the removal rate of COD in the wastewater is limited, and the MDEA cannot be completely degraded.
Claims (10)
1. A method for treating MDEA-containing wastewater comprises the following steps:
(1) Regulating the pH value of the wastewater containing MDEA to 4-6, adding persulfate, and reacting;
(2) Regulating the pH value of the wastewater to 9-11, hydrolyzing at 70-90 ℃, and cooling;
(3) Adjusting pH to 7-8, introducing activated sludge, reacting under aeration condition, settling, collecting supernatant, and filtering to obtain effluent.
2. The process according to claim 1, wherein the reaction temperature after adding persulfate in step (1) is 50 to 70℃and the reaction time is 1 to 2 hours.
3. The method according to claim 1, wherein the persulfate is at least one selected from the group consisting of a peroxymonosulfate and a peroxydisulfate.
4. The method according to claim 1, wherein the amount of persulfate to be added is 1:3 to 1:1 in terms of persulfate and/or hydrogen persulfate, relative to the COD of MDEA in wastewater.
5. The process according to claim 1, wherein the pH of the wastewater is adjusted to 5-5.5 in step (1).
6. The process according to claim 1, wherein the pH of the wastewater is adjusted to 10 to 10.5 in step (2).
7. The process according to claim 1, wherein the hydrolysis reaction in step (2) is carried out at a temperature of 80 to 90℃for a period of 1 to 2 hours.
8. The process according to claim 1, wherein the activated sludge in step (3) has an MLSS of 1500-2000mg/L.
9. The process according to claim 1, wherein the aeration reaction in step (3) is carried out for a period of 4 to 7 hours.
10. The process of claim 1, wherein the pH is adjusted using sulfuric acid or NaOH solution.
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