CN115925084A - Method for treating salt-containing organic wastewater - Google Patents
Method for treating salt-containing organic wastewater Download PDFInfo
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- CN115925084A CN115925084A CN202211382637.2A CN202211382637A CN115925084A CN 115925084 A CN115925084 A CN 115925084A CN 202211382637 A CN202211382637 A CN 202211382637A CN 115925084 A CN115925084 A CN 115925084A
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- salt
- pms
- containing organic
- organic wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- 150000003839 salts Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 20
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 15
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 15
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 14
- 231100000719 pollutant Toxicity 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052976 metal sulfide Inorganic materials 0.000 claims 1
- 230000033558 biomineral tissue development Effects 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 33
- 239000000460 chlorine Substances 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 231100000086 high toxicity Toxicity 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- -1 and the like Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for treating salt-containing organic wastewater, which contains chloride ions, rhodamine B, benzoic acid and other pollutants, and comprises the following steps: adding a catalyst into the salt-containing organic wastewater, and adding PMS and H 2 O 2 Stirring for reaction, and performing solid-liquid separation after the reaction is finished, wherein the supernatant is the treated salt-containing organic wastewater. The invention adds H into the original PMS catalytic system 2 O 2 The efficient degradation of pollutants in the salt-containing organic wastewater is realized, and the generation of organic halides is inhibited; the point used in the inventionThe method effectively reduces the toxicity of the reaction system, greatly improves the mineralization degree of pollutants, obviously improves the water quality after the treatment of the salt-containing organic wastewater and ensures the water safety.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a method for treating salt-containing organic wastewater.
Background
The organic wastewater is common organic industrial wastewater and has the characteristics of high salt content, large chromaticity, large pH change amplitude, difficult degradation, strong biological toxicity and the like. Advanced oxidation technologies developed in recent years include ozone oxidation, electrochemical oxidation, fenton and Fenton-like systems, persulfate catalytic systems, and the like. Wherein, the persulfate catalytic system can generate SO with strong oxidizing ability 4 - Free radical, high selectivity to organic aromatic benzene ring, and the like, and can efficiently oxidize and degrade organic pollutants in wastewater.
However, most of the existing persulfate catalytic oxidation systems do not consider the real water quality condition of industrial dye wastewater. The actual dye wastewater usually contains a large amount of chloride ions (Cl) - ) They will scavenge HO and SO produced by PMS decomposition 4 ·- And reacts therewith to produce chlorine species (Cl/Cl) having a lower oxidizing power 2 ·- ) Or directly reacted with PMS to form Cl 2 /HClO。Cl·/Cl 2 · The existence of the chlorine free radicals and HClO can generate a large amount of adsorbable organic halide (AOX) in the system, and the AOX has high toxicity and is difficult to further degrade, so that the solution after reaction has high toxicity and low mineralization degree of organic matters. Therefore, the existing persulfate oxidation system for treating high-salt dye wastewater has the problems of high AOX content, low mineralization rate, high toxicity and the like, so that the application of the persulfate system in the actual wastewater treatment process is greatly limited.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems in the prior art, the invention aims to provide a method for treating salt-containing organic wastewater, which has high organic pollutant removal rate, low toxicity of a reaction system and high mineralization degree.
The technical scheme is as follows: book (I)The method for treating the salt-containing organic wastewater contains chloride ions, and comprises the following steps: adding a catalyst into the salt-containing organic wastewater, and adding PMS and H 2 O 2 Stirring for reaction, and performing solid-liquid separation after the reaction is finished, wherein the supernatant is the treated salt-containing organic wastewater.
Further, the PMS and the H 2 O 2 The molar ratio of (1-5) to (1), the concentration of PMS is 0.1-2mM, and the mass ratio of the catalyst to PMS is 0.1-0.5.
Further, the pollutants in the salt-containing organic wastewater comprise rhodamine B and benzoic acid.
The invention principle is as follows: the invention adds H 2 O 2 Reacting with HClO and Cl-in a salt-containing organic wastewater system to generate Cl-and 1 O 2 the contents of HClO and Cl-in the system are reduced, the generation amount of AOX is reduced, and the aims of improving the mineralization and reducing organic chlorine intermediate products and biological toxicity in reaction liquid are fulfilled.
Catalyst activation PMS to generate SO 4 · The procedure of (c) is as follows:
Co 2+ +HSO 5 - →Co 3+ +SO 4 ·- +OH -
the process of activating PMS by the catalyst to generate HO & comprises the following steps:
Co 2+ +HSO 5 - →Co 3+ +HO·+SO4 2-
SO 4 ·- with Cl - The reaction process of (A) is as follows:
Cl - +SO 4 ·- →SO 4 2- +Cl·
the reaction process of HO & Cl-is as follows:
Cl-+·OH→HClO - ·
HClO - ·+H + →Cl·+H 2 O
the reaction process of PMS and Cl-is as follows:
Cl - +HSO 5 - →HClO+SO 4 2-
H 2 O 2 the reaction with Cl · proceeded as follows:
H 2 O 2 +Cl·→Cl - +H + +HO 2 ·
H 2 O 2 the reaction with HClO proceeds as follows:
H 2 O 2 +HClO→H + +Cl - +H 2 O+ 1 O 2
in salt-containing organic wastewater, cl - HClO and Cl are generated by the reaction with PMS, and the HClO and Cl generate a large amount of chlorination byproducts in a system, so that the problems of high AOX content, high toxicity, low mineralization degree and the like of a solution after the reaction are caused. Therefore, the invention adds a proper amount of H into the original PMS system 2 O 2 By means of H 2 O 2 By reaction with HClO 1 O 2 The concentration of HClO in the system is reduced, and the amount of AOX generated is reduced.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the invention adds H into the original PMS catalytic system 2 O 2 The method has the advantages that the efficient degradation of pollutants in the salt-containing organic wastewater is realized, the toxicity of a reaction system is reduced, and the mineralization degree of the pollutants is greatly improved, and experimental results show that the removal rate of rhodamine B in the salt-containing organic wastewater is as high as 98.8%, the content of HClO is reduced from 24.24mg/L to 1.57mg/L and is reduced by 15.4 times, the content of AOX is obviously reduced from 0.457mg/L to 0.026mg/L, the removal rate of TOC can reach 85.6%, the AOX is a refractory organic matter, the generation amount of AOX is large, and the mineralization degree of the organic matter is low. The invention adopts PMS/H 2 O 2 The generation amount of AOX is synergistically reduced, so that the mineralization degree of the organic matter is also improved. In conclusion, the preparation method adopted by the invention obviously improves the quality of the treated salt-containing organic wastewater and ensures the water safety.
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1: the method for treating the salt-containing organic wastewater comprises the following specific steps: adding CoS @ FeS catalyst into the salt-containing organic wastewater according to the proportion of 20mg/L, wherein the salt-containing organic wastewater containsThe pollutant is rhodamine B, the concentration of the rhodamine B is 20mg/L, the concentration of chloride ions is 500mM, and PMS and H with the molar ratio of 1 2 O 2 The concentration of PMS was 1mM, and the reaction was stirred for 10min.
Example 2: the difference from example 1 is that PMS and H 2 O 2 2.
Example 3: the difference from example 1 is that PMS and H 2 O 2 Is 5.
Example 4: the method for treating the salt-containing organic wastewater comprises the following specific steps: adding a catalyst into the salt-containing organic wastewater according to the proportion of 20mg/L, adding PMS and H with the molar ratio of 1 2 O 2 The concentration of PMS was 2mM, and the reaction was stirred for 80min.
Comparative example 1: the difference from example 1 is that the catalyst and H are not included 2 O 2 The amount of PMS added was 1mM.
Comparative example 2: the difference from example 1 is that PMS, H were not included 2 O 2 The amount of (2) added was 1mM.
Comparative example 3: the difference from example 1 is that H is not included 2 O 2 The amount of PMS added was 1mM.
Comparative example 4: the difference from example 4 is that H is not included 2 O 2 The amount of PMS added was 2mM.
The wastewater treated in examples 1 to 4 and comparative examples 1 to 4 was subjected to the measurement of the content of each contaminant, and the results are summarized in tables 1 and 2.
Table 1 summary of the contents of each pollutant in the saline organic wastewater after the treatment of examples 1 to 3
Table 2 summary table of contents of each pollutant in salt-containing organic wastewater after treatment of example 4 and comparative example 4
As can be seen from Table 1, examples 1 to 3 follow H 2 O 2 The adding proportion is increased, the degradation rate and the mineralization degree of rhodamine B are gradually increased, and the contents of HClO and AOX in the system are reduced; through comparison of different oxidation treatment methods, the oxidation system in the comparative example 1 independently uses PMS, the HClO content in the system is high, the AOX generation amount is large, and the TOC removal rate is low; in the oxidation system in the comparative example 3, the PMS is activated by the catalyst to treat the organic wastewater, the HClO content in the added system of the catalyst is reduced by about 43.0 percent, the AOX generation amount is reduced by 14.9 percent, and the TOC removal rate is increased by 39.0 percent; example 1 catalysis of PMS + H with a catalyst 2 O 2 The double oxidants treat the salt-containing organic wastewater, the content of HClO is low, the generation amount of AOX is small, and the TOC removal rate is as high as 85.6%.
As can be seen from Table 2, unlike rhodamine B, chloride ions reacted with PMS to produce HClO, whereas benzoic acid was not oxidized by HClO in the system. The degradation rate of benzoic acid in PMS alone system under salt containing conditions is therefore very slow. Followed by the addition of H 2 O 2 Then, H 2 O 2 By reaction with HClO 1 O 2 。
In conclusion, the double oxidant H of the invention is adopted 2 O 2 The excellent pollutant degradation effect is obtained by processing the salt-containing organic wastewater by PMS, which shows that when double oxidants coexist, the synergistic oxidation promotion effect is exerted, so that the rhodamine B removal rate is up to 98.8 percent, the TOC removal rate is up to 85.6 percent, and the AOX generation amount is very little and is 0.026mg/L.
In addition, rhodamine B and benzoic acid are two representative contaminants in the present invention. In saline wastewater, chloride ions react with PMS to form hypochlorous acid, which is oxidizing and can oxidize some pollutants, such as rhodamine, and the like, and other pollutants cannot be oxidized by hypochlorous acid, such as benzoic acid and the like. This is related to the structure and functional groups of the contaminants themselves.
RhodamineRepresents a class of contaminants that can be oxidized by hypochlorous acid. (1) Even in the absence of catalyst and H 2 O 2 Under the condition of (1), hypochlorous acid generated by PMS and chloride ions has high degradation rate to the PMS and the chloride ions, and the pollutants have the problems of large generation amount of organic halides and high toxicity of the solution after reaction in the saline wastewater; (2) The addition of the catalyst can reduce the generation amount of AOX and reduce the toxicity; (3) Adding H based on PMS and catalyst 2 O 2 Converting hypochlorous acid and chlorine radicals into 1 O 2 The reaction of chlorine free radical and hypochlorous acid with organic matter is reduced, and the AOX is generated in small amount and has low toxicity.
Benzoic acid represents a class of contaminants that cannot be oxidized by hypochlorous acid, which in saline wastewater consumes large amounts of PMS to produce hypochlorous acid, which cannot oxidize them. (1) In a salt-containing system only with PMS, chloride ions react with PMS to generate hypochlorous acid which cannot degrade benzoic acid, and a small amount of PMS is left in the system and almost cannot degrade benzoic acid; (2) In the system of PMS and catalyst, part of PMS is consumed by chloride ions, and the rest small amount of PMS is activated by catalyst to generate sulfate radical, hydroxyl radical and catalyst 1 O 2 The benzoic acid is degraded by oxidation, but the oxidation capacity of the contaminants such as the benzoic acid is limited, so the degradation rate of the contaminants such as the benzoic acid is low; (3) When PMS, catalyst and H are added 2 O 2 In the case of (H) 2 O 2 Reacting with hypochlorous acid in the system to generate 1 O 2 Converting hypochlorous acid, which is not capable of degrading benzoic acid, to singlet oxygen, which is capable of degrading benzoic acid: ( 1 O 2 ) Thereby greatly improving the degradation rate of a salt-containing system, reducing the generation of AOX and reducing the reaction toxicity.
Claims (6)
1. A method for treating salt-containing organic wastewater, wherein the salt-containing organic wastewater contains chloride ions, is characterized by comprising the following steps: adding a catalyst into the salt-containing organic wastewater, and then adding PMS and H 2 O 2 Stirring for reaction, solid-liquid separation, and treating the supernatant to obtain salt-containing organic wasteAnd (3) water.
2. The method of claim 1, wherein said PMS and H are 2 O 2 In a molar ratio of 1 to 5.
3. The method according to claim 1, wherein the concentration of PMS is 0.1-2mM.
4. The method according to claim 1, wherein the mass ratio of the catalyst to the PMS is 0.1-0.5.
5. The method of claim 1, wherein the catalyst is a metal sulfide or metal oxide and a carbon-based material capable of activating PMS.
6. The method as claimed in claim 1, wherein the pollutants in the salt-containing organic wastewater comprise rhodamine B and benzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211382637.2A CN115925084A (en) | 2022-11-07 | 2022-11-07 | Method for treating salt-containing organic wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211382637.2A CN115925084A (en) | 2022-11-07 | 2022-11-07 | Method for treating salt-containing organic wastewater |
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| CN115925084A true CN115925084A (en) | 2023-04-07 |
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| CN202211382637.2A Pending CN115925084A (en) | 2022-11-07 | 2022-11-07 | Method for treating salt-containing organic wastewater |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570115A (en) * | 2013-10-31 | 2014-02-12 | 哈尔滨工业大学 | Method of treating reverse osmosis concentrate by using high-activity singlet oxygen |
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| CN107244728A (en) * | 2017-06-22 | 2017-10-13 | 哈尔滨理工大学 | A kind of method that permonosulphuric acid salt treatment high salt waste water from dyestuff is activated using secondary iron mineral |
| CN108187723A (en) * | 2017-12-27 | 2018-06-22 | 浙江大学 | A kind of Fe-Im- carried catalysts, preparation method and application |
| US20190241452A1 (en) * | 2018-02-06 | 2019-08-08 | Oxytec Llc | Soil and water remediation method and apparatus for treatment of recalcitrant halogenated substances |
-
2022
- 2022-11-07 CN CN202211382637.2A patent/CN115925084A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570115A (en) * | 2013-10-31 | 2014-02-12 | 哈尔滨工业大学 | Method of treating reverse osmosis concentrate by using high-activity singlet oxygen |
| CN105692858A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | A method of degrading organic pollutants in waste water through a Fenton-like process |
| CN107244728A (en) * | 2017-06-22 | 2017-10-13 | 哈尔滨理工大学 | A kind of method that permonosulphuric acid salt treatment high salt waste water from dyestuff is activated using secondary iron mineral |
| CN108187723A (en) * | 2017-12-27 | 2018-06-22 | 浙江大学 | A kind of Fe-Im- carried catalysts, preparation method and application |
| US20190241452A1 (en) * | 2018-02-06 | 2019-08-08 | Oxytec Llc | Soil and water remediation method and apparatus for treatment of recalcitrant halogenated substances |
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