CN115925086B - A method for degrading organic matter in wastewater - Google Patents
A method for degrading organic matter in wastewater Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000000593 degrading effect Effects 0.000 title claims abstract description 19
- 239000002351 wastewater Substances 0.000 title claims abstract description 19
- 239000005416 organic matter Substances 0.000 title claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 89
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- -1 sulfide ions Chemical class 0.000 claims abstract description 11
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 2
- 235000010261 calcium sulphite Nutrition 0.000 claims description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 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 description 85
- 229940043267 rhodamine b Drugs 0.000 description 85
- 230000015556 catabolic process Effects 0.000 description 46
- 238000006731 degradation reaction Methods 0.000 description 46
- 239000000243 solution Substances 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000001994 activation Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- KMZJRCPGGAQHGC-UHFFFAOYSA-N trisodium boric acid borate Chemical compound [Na+].[Na+].[Na+].OB(O)O.[O-]B([O-])[O-] KMZJRCPGGAQHGC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001412 inorganic anion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种降解废水中有机物的方法，属于废水处理技术领域，该方案通过在废水中形成二价锰离子/金属配合物体系，利用二价锰离子/金属配合物体系激活四价硫离子形成硫酸根自由基，通过硫酸根自由基对有机物进行降解。该方法可有效解决现有技术中采用二价锰激活四价硫离子时存在的激活效率低的问题。The invention provides a method for degrading organic matter in wastewater, belonging to the technical field of wastewater treatment. The scheme forms a divalent manganese ion/metal complex system in wastewater, uses the divalent manganese ion/metal complex system to activate tetravalent sulfide ions to form sulfate radicals, and degrades organic matter through sulfate radicals. The method can effectively solve the problem of low activation efficiency when using divalent manganese to activate tetravalent sulfide ions in the prior art.
Description
Technical Field
The invention belongs to the technical field of organic matter degradation, and particularly relates to a method for degrading organic matters in wastewater.
Background
Advanced oxidation processes (SR-AOPs) based on SO4 ·- radicals have been widely studied and developed with a wider pH range of application, a higher redox potential (SO 4 ·- radicals of 2.5-3.1V, OH · radicals of 1.8-2.7V) and a longer half-life (SO 4 ·- radicals of 30-40 μs, OH · radicals of 1 μs) than the hydroxyl radicals of conventional Fenton oxidation processes. In SR-AOPs, persulfates (peroxodisulfates (PDS) and Peroxomonosulfates (PMS)) are often used as precursors for the generation of SO4 ·- radicals. However, the use of persulfates still suffers from the disadvantages of high cost, high acidity and residual biotoxicity. Sulfite (S (IV)) is a common industrial byproduct derived from sulfur dioxide, and because of its environmental friendliness, low cost and also the ability to be activated to form SO4 ·- free radicals, how to efficiently activate S (IV) to form SO4 ·- free radicals is becoming an increasingly important issue for research.
Common methods of activating S (IV) mainly include thermal activation, photoactivation, electro-activation and transition metal activation. Manganese (Mn) is a common transition metal and has the characteristics of low toxicity, rich natural reserves and the like. Mn is commonly used for SR-AOPs and is considered to be an excellent metal catalyst. The current research is directed to combining permanganate, single or complex manganese oxides with S (IV). However, since Mn (II) activates S (IV) with conversion between Mn (II) and Mn (III), mn (III) in a medium alkaline solution is very unstable, disproportionation reaction occurs to form Mn (II) and MnO 2 (equilibrium constant log K=7 to 9), resulting in limited research and application of Mn (II) activation S (IV) in an aqueous solution.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for degrading organic matters in wastewater, which can effectively solve the problem of low activation efficiency in the prior art when tetravalent sulfide ions are activated by divalent manganese.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
A method for degrading organic matters in wastewater is characterized in that a divalent manganese/metal complex system is formed in the wastewater, tetravalent sulfur is activated by the divalent manganese/metal complex system to form sulfate radical, and the organic matters are degraded by the sulfate radical.
Further, the specific operation process is as follows: mixing water containing organic matters, divalent manganese salt and metal complexing agent to obtain a mixed solution, regulating the pH value of the mixed solution to 4-10, adding sulfite into the mixed solution, and stirring for reaction.
Further, the molar ratio of the divalent manganese salt to the metal complexing agent in the mixed solution is 1:1-10.
Further, the concentration of the divalent manganese salt in the mixed solution is 10 to 100. Mu.M.
Further, the concentration of tetravalent sulfur ions in the mixed solution is 100 to 800. Mu.M.
Further, the pH value of the mixed solution is regulated to be 6-7.5.
Further, the reaction is carried out at 25-35 ℃.
Further, the divalent manganese salt includes at least one of manganese sulfate monohydrate, manganese chloride, and manganese nitrate.
Further, the metal complexing agent is sodium nitrilotriacetate.
Further, the sulfite includes at least one of anhydrous sodium sulfite, potassium sulfite, calcium sulfite, sodium bisulfite, and potassium bisulfite.
The beneficial effects of the invention are as follows:
1. In the method, divalent manganese (Mn (II)) and a metal complex (NTA) are added into wastewater, in the presence of NTA, mn (II) forms a stable coordination form, SO that hydrolysis disproportionation reaction is not easy to occur, mn (II) in the coordination form excites and activates tetravalent sulfur (S (IV)) to form sulfate radical (SO 4 ·-), and organic matters in water are degraded by utilizing the strong oxidizing property of SO 4 ·-; due to the existence of the metal complex, the stable state of Mn (II) in the water body can be greatly improved, so that the excitation effect on S (IV) is improved, and the degradation effect of organic matters is improved.
2. According to the method, the sulfite is used as a raw material to degrade organic pollutants in the water body, the sulfite is stable in property, convenient to transport and store, low in price, wide in source, free of biological toxic effects and greatly improved in use safety.
3. In the application, the divalent manganese is taken as the raw material, and the divalent manganese is widely existing in underground water and natural water and uniformly distributed in the water body, so that the use of the raw material can be reduced; the divalent manganese has wide sources and low price, and can reduce the treatment cost; the divalent manganese can activate sulfite rapidly and fully, and the theoretical gap of the divalent manganese ion for efficiently activating sulfite is made up.
Drawings
FIG. 1 is a statistical graph of degradation effects of organic matters in different reaction systems;
FIG. 2 is an ultraviolet-visible spectrum plot of Mn (III) -NTA and Mn (II)/NTA/S (IV) systems at t=1 min;
FIG. 3 is a graph showing the degradation statistics of RhB in Mn (III) -NTA and Mn (III) -NTA/S (IV) systems;
FIG. 4 a is a statistical plot of EtOH and TBA versus RhB degradation in Mn (II)/NTA/S (IV) systems; b is a statistical graph of EtOH and TBA versus RhB degradation in Mn (III) -NTA/RhB systems;
FIG. 5 a is a statistical plot of variation of Mn (II) concentration versus RhB degradation; b is a statistical graph of RhB degradation after changing the ratio of [ Mn (II) ] to [ NTA ];
FIG. 6 is a statistical plot of S (IV) dosage versus degradation of RhB in Mn (II)/NTA/S (IV) systems;
FIG. 7 a is a statistical plot of pH versus degradation of RhB by Mn (II)/NTA/S (IV) systems; b is a graph of the percent content of Mn (II) -NTA and NTA species in solution as a function of pH;
FIG. 8 is a statistical plot of inorganic anions versus degradation of RhB by Mn (II)/NTA/S (IV) systems.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the drawings.
Example 1
A method for degrading organic matters in wastewater comprises the following specific operation processes: mixing a water body containing organic matters, mnSO 4·H2 O and NTA to obtain a mixed solution, wherein the mol ratio of MnSO 4·H2 O to NTA in the mixed solution is 1:3, the concentration of MnSO 4·H2 O in the mixed solution is 50 mu M, adjusting the pH value of the mixed solution to 7.5 by using a boric acid-sodium borate buffer solution, and then adding anhydrous sodium sulfite (S (IV)) to the mixed solution to ensure that the concentration of the mixed solution is 500 mu M, and stirring and reacting at the temperature of 30 ℃ at the speed of 2000 r/min.
Example 2
A method for degrading organic matters in wastewater comprises the following specific operation processes: mixing water containing organic matters, manganese chloride and NTA to obtain a mixed solution, wherein the molar ratio of the manganese chloride to the NTA in the mixed solution is 1:5, the concentration of the manganese chloride in the mixed solution is 30 mu M, the pH value of the mixed solution is regulated to be 6 by using boric acid-sodium borate, and then anhydrous sodium sulfite (S (IV)) is added to the mixed solution to ensure that the concentration of the anhydrous sodium sulfite in the mixed solution is 300 mu M, and stirring and reacting are carried out at the temperature of 25 ℃ at the speed of 2000 r/min.
Example 3
A method for degrading organic matters in wastewater comprises the following specific operation processes: mixing water containing organic matters, manganese nitrate and NTA to obtain a mixed solution, wherein the molar ratio of the manganese nitrate to the NTA in the mixed solution is 1:1, the concentration of the manganese nitrate in the mixed solution is 20 mu M, adjusting the pH value of the mixed solution to 7 by using boric acid-sodium borate buffer solution, and then adding anhydrous sodium sulfite (S (IV)) into the mixed solution to ensure that the concentration of the anhydrous sodium sulfite (S (IV)) in the mixed solution is 200 mu M, and stirring and reacting at the temperature of 35 ℃ at the speed of 2000 r/min.
Example 4
A method for degrading organic matters in wastewater comprises the following specific operation processes: mixing a water body containing organic matters, mnSO 4·H2 O and NTA to obtain a mixed solution, wherein the mol ratio of MnSO 4·H2 O to NTA in the mixed solution is 1:10, the concentration of MnSO 4·H2 O in the mixed solution is 100 mu M, adjusting the pH value of the mixed solution to 6.5 by using boric acid-sodium borate or acetic acid-sodium acetate buffer solution, and then adding anhydrous sodium sulfite (S (IV)) to the mixed solution to ensure that the concentration of the anhydrous sodium sulfite (S (IV)) in the mixed solution is 800 mu M, and stirring and reacting at the temperature of 30 ℃ at the speed of 2000 r/min.
Test examples
1. Preparing organic matter solution
Rhodamine B (RhB) is a common artificial dye, and because the rhodamine B has a similar structure to most organic pollutants, has benzene rings and various active sites, and the detection method is convenient, rhB is taken as a model organic pollutant, and is added into water to prepare RhB solution with the RhB concentration of 1mM for later use.
2. Test
2.1 Control experiments
Taking a RhB solution, and degrading RhB in the solution by adopting the method in the example 1, wherein the RhB solution is used as an experimental group;
Taking a RhB solution, adding MnSO 4·H2 O (Mn (II)) into the RhB solution to degrade RhB in the solution, wherein the RhB solution is used as a control group 1;
Taking a RhB solution, adding a metal complexing agent (NTA) into the RhB solution to degrade RhB in the solution, wherein the RhB solution is used as a control group 2;
Taking a RhB solution, adding anhydrous sodium sulfite (S (IV)) into the RhB solution to degrade RhB in the solution, wherein the RhB solution is used as a control group 3;
Taking a RhB solution, adding MnSO 4·H2 O (Mn (II)) and anhydrous sodium sulfite (S (IV)) into the RhB solution, and carrying out degradation treatment on the RhB in the solution, wherein the RhB solution is used as a control group 4;
Taking a RhB solution, adding MnSO 4·H2 O (Mn (II)) and a metal complexing agent (NTA) into the RhB solution to carry out degradation treatment on the RhB in the solution, wherein the RhB solution is used as a control group 5;
Taking a RhB solution, adding a metal complexing agent (NTA) and anhydrous sodium sulfite (S (IV)) into the RhB solution, and carrying out degradation treatment on the RhB in the solution, wherein the RhB solution is used as a control group 6;
Samples were taken at 0, 1, 2, 3, 4,5, 7, 10, and 15min after the administration of the reagent, and immediately added to a cuvette containing 1mL 200mM Na 2S2O3 solution. The effect of the Na 2S2O3 solution is to quench the active species that may be present in the system, thereby stopping further oxidation of the RhB. Measuring the absorbance of RhB at 554nm by using an ultraviolet-visible spectrophotometer, and measuring ultraviolet-visible light absorption spectrograms of different systems in the reaction process by using the ultraviolet-visible spectrophotometer; the content of RhB in the solution after the reaction is counted, and the specific result is shown in figure 1.
As can be seen from FIG. 1, there was no significant degradation of RhB in both the Mn (II), NTA and S (IV) single system and the Mn (II)/S (IV) binary systems. In the experimental group, i.e. the Mn (II)/NTA/S (IV) system of example 1, the degradation rate of RhB reached 86.05%. Thus, mn (II) -NTA formed by the introduction of ligand NTA with Mn (II) is able to react effectively with S (IV) and produce active oxidizing species degrading RhB.
2.2 Production of Mn (III)
Mn (II) can be oxidized into Mn (III) in the process of activating S (IV) to generate SO 4 ·- free radicals, mn (III) has strong oxidizing property, mn (III) is easy to disproportionate when meeting water (formula (1)), SO that the content of Mn (III) in the solution is very small, and the aim of degrading RhB can not be realized.
2Mn(III)+2H2O＝MnO2+Mn(II)+4H+ (1)
The Mn (III) -NTA system was prepared in situ by the reaction process in the following formula (2), and the uv-visible spectrum of the Mn (III) -NTA system prepared in situ and the Mn (II)/NTA/S (IV) system in example 1 at t=1 min was scanned using a uv-visible spectrophotometer, and the result is shown in fig. 2.
As can be seen from FIG. 2, a characteristic absorption peak appears at about 280mm in the in-situ prepared Mn (III) -NTA spectrum, which is consistent with the absorption peak of Mn (III) in the coordinated form. The results show that Mn (III) -NTA prepared in situ by formula (2) can exist stably in the presence of NTA. Meanwhile, in the spectrogram of the Mn (II)/NTA/S (IV) system, characteristic absorption peaks of Mn (III) -NTA were observed at the same positions, and thus it was confirmed that Mn (III) -NTA was produced in the Mn (II)/NTA/S (IV) system.
The Mn (II)/NTA/S (IV) system, the in-situ prepared Mn (III) -NTA system and the Mn (III) -NTA/S (IV) system in example 1 were directly reacted with RhB, rhB in the Mn (III) -NTA system was not significantly degraded, and RhB in the Mn (III) -NTA/S (IV) system was degraded, and the specific results are shown in FIG. 3.
As can be seen from FIG. 3, in the Mn (III) -NTA/S (IV) system, rhB is rapidly degraded, and even the degradation efficiency is higher than that of the Mn (II)/NTA/S (IV) system, which reaches 95.72%. It is known that Mn (III) -NTA does not directly oxidize and degrade RhB, and that addition of S (IV) to Mn (III) -NTA may result in the formation of other reactive oxidizing species to degrade RhB. Presumably, mn (III) in a coordinated state with NTA is more stable and can activate S (IV) more rapidly than Mn (II) to cause degradation of RhB. Thus, stable Mn (III) -NTA has an important role in promoting the circulation of Mn species and in efficiently activating S (IV).
3. Investigation of reactive oxidizing species
It is presumed that sulfate radicals (SO 4 ·-) and hydroxyl radicals (OH ·) may be generated in the Mn (II)/NTA/S (IV) reaction system, and the radical scavenger reacts with SO 4 ·- radicals and OH radicals to have different second order rate constants, SO Tertiary Butanol (TBA) is used as a specific scavenger of OH · radicals (k (TBA,SO4·-)＝8.5×105M-1s-1,k(TBA,OH·)＝6.0×108M-1s-1). Whereas absolute ethanol (EtOH) can quench both SO 4 ·- and OH · radicals (k(EtOH,SO4·-)＝(1.6～7.7)×107M-1s-1,k(EtOH,OH·)＝(1.2～2.8)×109M-1s-1),, the specific results are shown in fig. 4.
As shown in FIGS. 4a and 4b, when 20mM TBA was added to Mn (II)/NTA/S (IV) and Mn (III) -NTA/S (IV) systems, the degradation rate of RhB was reduced by only 6.13% and 5.18%, respectively, indicating that OH · radicals were not the major active oxidized species. However, when 20mM EtOH was added as radical scavenger to both systems, rhB degradation was almost completely inhibited, thus confirming that SO 4 ·- radical was the decisive oxidizing species in both systems.
4. Effect of Mn (II) and NTA concentration
Fixing [ Mn (II) ], [ NTA ] =1:3, when the concentration of Mn (II) is gradually increased, the degradation rate of RhB is gradually increased as shown in FIG. 5a, but when the concentration of Mn (II) is increased to 100. Mu.M, the degradation efficiency is drastically reduced to 53.27%. Presumably, this is because an increase in Mn (II) concentration increases the subsequent Mn-NTA complex concentration, facilitating the activation of S (IV) and thus degradation of RhB. However, as Mn (II) concentration continues to increase to 100. Mu.M, the large amount of ligand introduced competes with RhB for consumption of SO 4 ·- free radicals, resulting in inhibition of RhB degradation.
When the concentration of Mn (II) is controlled to be 50 mu M and [ Mn (II) ] [ NTA ] =1:1-1:10 is changed, the degradation rate of RhB is changed as shown in figure 5b, and when the ratio of the two is reduced from 1:1 to 1:3, the degradation rate of RhB is increased from 64.23% to 86.04%. And when [ Mn (II) ], [ NTA ] is 1:5 and 1:10, the degradation rate of the RhB is 86.3 percent and 85.66 percent respectively, and the degradation of the RhB is influenced in a negligible way. When [ Mn (II) ], [ NTA ] = 1:1, it is probably due to the fact that in the case of insufficient NTA, the generated Mn (II) -NTA and Mn (III) -NTA are low in concentration, and the activation efficiency of S (IV) is not high, so that RhB cannot be effectively degraded. When the ratio of the two is 1:3-1:10, the concentration of the generated Mn species can be kept sufficient and stable under the condition of proper excess NTA, and the subsequent activation of S (IV) is facilitated.
5. Influence of the amount of S (IV) added
As shown in FIG. 6, the degradation rates of RhB were 13.79%,56.36%,83.88% and 86.24% when the S (IV) concentrations were 100, 200, 300 and 500. Mu.M, respectively. However, when the S (IV) concentration reached 800. Mu.M, the degradation rate of RhB was instead drastically reduced to 16.89%. S (IV) is closely related to the formation of SO 4 ·- radicals and Mn (III), and sufficient S (IV) can be activated to generate a large amount of SO 4 ·- radicals to participate in RhB degradation. However, an excessive amount of S (IV) may compete with the RhB for the SO 4 ·- radical (formula (3)), thereby causing internal consumption of the radical, reducing the utilization rate of the SO 4 ·- radical, and resulting in a decrease in the degradation rate of the RhB. Furthermore, the addition of excess S (IV) results in a substantial consumption of dissolved oxygen, thereby reducing the yield of SO 5 ·- and SO 4 ·- radicals (formulas (4) and (5)) and limiting the formation of subsequent reactive oxidizing species.
SO4 ·-+SO3 2-→SO3 ·-+SO4 2-(3)
SO3 ·-+O2-----→SO5 ·-(4)
SO5 ·-+SO3 2-→SO4 ·-+SO4 2-(5)
6. Influence of pH
The effect of pH on degradation of RhB by Mn (II)/NTA/S (IV) system is shown in fig. 7, and it can be seen from fig. 7a that when the pH of the solution is=4, the degradation rate of RhB is only 11.79%. When the pH of the solution was=6, the degradation rate of RhB increased significantly to 99.31%. When the pH of the solution=7.5, the degradation rate of RhB was 86.05%, but at ph=9, the degradation rate of RhB was reduced to 49.33 again, and the pH had a great influence on the ionization balance of the substances in the solution. FIG. 7b is a graph of the percentage of Mn (II) -NTA and NTA components in solution as a function of pH plotted by a specialized chemical equilibration software Medusa. The molecular structure of NTA is (CH 2COOH)3 N, at lower pH, a large amount of NTA in aqueous solution exists in the form of tribasic acid, SO that at ph=4, only a small amount of Mn (II) -NTA is formed, the subsequent S (IV) activation reaction is difficult to carry out, resulting in low degradation efficiency of RhB, and as the pH increases, the content of Mn (II) -NTA gradually increases, S (IV) can be effectively activated to generate SO 4 ·- free radical to degrade RhB.
7. Influence of inorganic anions
FIG. 8 shows the effect of common inorganic anions on degradation of RhB by Mn (II)/NTA/S (IV) systems. Even in the presence of 1-10 mM Cl -, rhB degradation was hardly affected, but slightly enhanced. This is probably due to the fact that Cl - captures the SO 4 ·- radical, and thus active chlorine species such as Cl ·、Cl2 ·- and HOCl are generated and may participate in the oxidation process of RhB.
HCO 3 - is generally considered as an interfering ion in the S (IV) activation system, Since SO 4 ·- can react with HCO 3 - to form CO 3 ·- (formula (6)) which is less reactive. the presence of HCO 3 - at high concentrations does not only have an interfering effect on degradation of RhB, but rather slightly promotes degradation of RhB. This is probably because the reaction rate constant of SO 4 ·- with RhB is 2 orders of magnitude higher (k (RhB,SO4·-)＝3.02×108M-1s-1,k(HCO3-,SO4·-)＝2.8×106M-1s-1) than that of SO 4 ·- with HCO 3 -, Therefore HCO 3 - had no significant effect on RhB degradation. The degradation effect of the RhB is slightly improved under the existence of HCO 3 -, Probably because the HSO 5 - existing in the Mn (II)/NTA/S (IV) system reacts with HCO 3 - to produce HCO 4 -, thereby oxidizing part of the organic matters (formula (7)).SO4 ·-+HCO3 -→H++SO4 2-+CO3 ·- (6)
HSO5 -+HCO3 -→SO4 2-+HCO4 -+H+ (7)
The addition of NO 3 - to the system slightly inhibits the degradation effect and reaction rate of RhB, probably because NO 3 - reacts with SO 4 ·- to form NO 3 · (formula (8)) with a lower oxidation-reduction potential, thereby inhibiting the degradation of part of RhB.
SO4 ·-+NO3 -→SO4 2-+NO3 · (8)。
Claims (5)
1. A method for degrading organic matters in wastewater is characterized in that,
The specific operation process is as follows: mixing a water body containing organic matters, divalent manganese salt and a metal complexing agent, forming a divalent manganese/metal complex system in wastewater to obtain a mixed solution, regulating the pH value of the mixed solution to be 6-7.5, adding sulfite into the mixed solution, stirring for reaction, activating tetravalent sulfide ions by using the divalent manganese/metal complex system to form sulfate radical, and degrading the organic matters by the sulfate radical;
the metal complexing agent is nitrilotriacetic acid sodium salt;
The molar ratio of the divalent manganese salt to the metal complexing agent in the mixed solution is 1:1-10; the concentration of the divalent manganese salt in the mixed solution is 10-100 mu M.
2. The method for degrading organic matter in wastewater according to claim 1, wherein a concentration of said tetravalent sulfide ion in the mixed solution is 100 to 800 μm.
3. The method for degrading organic matter in wastewater as claimed in claim 1, wherein the reaction is performed at 25-35 ℃.
4. The method of degrading organic matter in wastewater according to claim 1, wherein the divalent manganese salt includes at least one of manganese sulfate monohydrate, manganese chloride, and manganese nitrate.
5. The method of degrading organic matter in wastewater according to claim 1, wherein the sulfite comprises at least one of anhydrous sodium sulfite, potassium sulfite, calcium sulfite, sodium bisulfite, and potassium bisulfite.
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