CN104445576B - A kind of organic pollutant oxidation treatment method based on sulphur oxyradical - Google Patents
A kind of organic pollutant oxidation treatment method based on sulphur oxyradical Download PDFInfo
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- CN104445576B CN104445576B CN201410790241.0A CN201410790241A CN104445576B CN 104445576 B CN104445576 B CN 104445576B CN 201410790241 A CN201410790241 A CN 201410790241A CN 104445576 B CN104445576 B CN 104445576B
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- organic pollutant
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000005864 Sulphur Substances 0.000 title claims abstract description 17
- -1 persulfuric acid free radical Chemical class 0.000 claims abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 34
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 9
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- MLVYOYVMOZFHIU-UHFFFAOYSA-M sodium;4-[(4-anilinophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1N=NC(C=C1)=CC=C1NC1=CC=CC=C1 MLVYOYVMOZFHIU-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000001117 sulphuric acid Substances 0.000 abstract description 7
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 abstract description 5
- 239000005750 Copper hydroxide Substances 0.000 abstract description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000003403 water pollutant Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 229950011260 betanaphthol Drugs 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PVLIWNWMRNQALM-UHFFFAOYSA-L O.O.S(=O)([O-])[O-].[Cu+2] Chemical compound O.O.S(=O)([O-])[O-].[Cu+2] PVLIWNWMRNQALM-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type 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
- C02F1/725—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (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)
- Removal Of Specific Substances (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of organic pollutant oxidation treatment method based on sulphur oxyradical, (comprise Na with cupric ion or the cuprous ion copper hydroxide colloidal catalytic sulphite that (pH value 8 ~ 11) is formed in the basic conditions
2sO
3, K
2sO
3, (NH
4)
2sO
3, NaHSO
3, MgSO
3, Al
2(SO
3)
3, Fe
2(SO
3)
3, ZnSO
3) reaction produces sulphur oxyradical and (comprise persulfuric acid free radical (SO
5 -), sulphuric acid free radical (SO
4 -) and sulfurous acid free radical (SO
3 -)), wherein sulphuric acid free radical and hydroxide ion (OH
-) reaction generation hydroxyl radical free radical (HO
.), then utilize these sulphur oxyradicals and hydroxyl radical free radical to be oxidized water pollutant.The present invention is without the need to the oxygenant such as hydrogen peroxide or persulphate, easy and simple to handle, and oxidation efficiency is high, speed is fast, and can be oxidized pollutent under anoxic conditions.Therefore, be widely used prospect.
Description
Technical field
The invention belongs to environmental technology field, particularly a kind of organic pollutant oxidation treatment method based on sulphur oxyradical.
Background technology
Along with the development of China's economy, the kind of trade effluent constantly increases, especially the waste water that produces of DYE PRODUCTION and textile printing and dyeing industry, and the harm of various pollution substance to environment increasingly sharpens.Because waste water from dyestuff colourity is high, chemical stability is strong, and complicated component, if it is directly drained into environment, by serious threat environmental quality and human health.Therefore the organic pollutant removed in water body has great theoretical and practical significance.
At present, domestic waste water from dyestuff often adopts to carry out a biological disposal upon as master, then is aided with the process for comprehensively treating of physical chemistry treatment process.Wherein, biological process is the metabolism utilizing microorganism, using the nutrition source of the organic pollutant in waste water from dyestuff as microorganism, to its constantly absorption, flocculation, oxidation, decomposes, thus reaches the object of decolored degradation; And chemical rule is mainly by principle and the method Separation and Recovery pollutent of chemical reaction or change its character to reach innoxious.But due to chemical stability and the bio-refractory of dyestuff, Conventional waste water treatment technology can not effective dye wastewater treatment.Therefore the high-level oxidation technology (AOP) occurred in recent years, can not only overcome the shortcomings such as the selective oxidation of conventional chemical oxidation style, percent of decolourization are low, Recalcitrant chemicals of also can directly removing or degrade, and becomes the strong effective means of process organic waste water.High-level oxidation technology mainly produces free radical by different approaches, the reactions such as these free radicals can replace with the Recalcitrant chemicals in waste water, electrophilic addition, transfer transport, open loop, scission of link, make its oxidative degradation become the intermediate product of the low harmful readily biodegradable of low toxicity, be even directly degraded to water and carbonic acid gas and mineral ion.In high-level oxidation technology, most important two kinds of methods are exactly Fenton and Fenton-like method, and these two kinds of methods are also the study hotspots in high-level oxidation technology.
Traditional high-level oxidation technology is mainly with hydroxyl radical free radical (HO
.) carry out degradation of contaminant for active specy, but up-to-date research finds, has the sulphuric acid free radical (SO of lone-pair electron
4 -) comparatively HO
., the pH value scope of application is wider, and oxidizing potential is high, and the organic pollutant category be oxidized in theory is more, and can carry out oxidative degradation to organic pollutant in the basic conditions.This with sulphuric acid free radical (SO
4 -) be the AOPs of chief active group, belong to Fenton-like method.The SO produced in the method
4 -have oxidizing potential high, oxidisability is strong, and steady time compares HO
.long, applicable pH range is wide, can also be oxidized some HO
.inoxidizable organic pollutant, has broad prospects in the process of the organic waste waters such as dyestuff.
At present, sulphuric acid free radical (SO is produced
4 -) mainly react by Potassium Persulphate and permonosulphuric acid potassium and generate, but when utilizing this two kinds of oxygenants, need the effect that the ratio of oxygenant and catalyzer very large (being generally greater than 100) just can be got, therefore cost is very high.So the technique producing sulphur oxyradical needs to be improved.The technique ability degradation of organic substances in slant acidity situation producing sulphuric acid free radical with Fe-sulphite system then proposed.On this background, we have proposed in alkaline environment, produce with colloid copper hydroxide-sulphite reaction a kind of novel high-level oxidation technology that sulphur oxyradical is disposed of sewage.This technology is without the need to additionally adding the oxygenant such as hydrogen peroxide or persulphate, easy and simple to handle, and oxidation efficiency is high, speed is fast, and can be oxidized pollutent under anoxic conditions.Therefore, the technology that the present invention is applied to has very large development prospect.
Summary of the invention
The object of this invention is to provide a kind of without the need to illumination, easy and simple to handle, oxidation efficiency is high, speed is fast, and can under anoxic conditions to the method for a kind of fast degradation organic pollutant that pollutent is oxidized.
Technical scheme provided by the present invention is specific as follows:
Based on an organic pollutant oxidation treatment method for sulphur oxyradical, comprise the steps:
A () gets the solution containing organic pollutant, the concentration recording organic pollutant is xmol/L;
B () prepares sulfite solution, copper salt solution respectively, for subsequent use;
C sulfite solution adds in the solution containing organic pollutant by (), form mixed liquor A, the concentration of mixed liquor A sulfite salt is 10xmol/L ~ 250xmol/L; Regulate pH value to 10.0 ~ 11.4 of mixed liquor A immediately, then add copper salt solution rapidly, form mixed liquid B, in mixed liquid B, the concentration of mantoquita is 1xmol/L ~ 17xmol/L, and the pH of mixed liquid B is 8.0 ~ 11.0; Stir or aeration mixed liquid B degradable to organic pollutant.The pH of described mixed liquid B is preferably 11.0.
Described organic pollutant is one or more in dihydroxyphenyl propane, orange II, Congo red, activated red X-3B, orange IV, alkaline bright yellow, erie black.
Described sulphite is Na
2sO
3, K
2sO
3, (NH
4)
2sO
3, NaHSO
3, MgSO
3, Al
2(SO
3)
3, Fe
2(SO
3)
3, ZnSO
3in one or more.
Described mantoquita is Cu (NO
3)
2, CuCl
2, CuSO
4, CuSO
3, one or more in CuCl.
In treatment process as above, the pH value of cupric salt solution is 2.
In treatment process as above, the manner of formulation of CuCl solution is: first dissolved completely by CuCl solid with concentrated hydrochloric acid, then adds deionized water and regulates Cu
+to desired concn.
In reaction involved in the present invention, contingent principal reaction is following flow process:
In this system, after copper salt solution joins and regulates pH in organic pollutant wastewater, Cu
2+form the colloid of copper hydroxide; If what add is cuprous salt solution, then cuprous salt solution joins in organic pollutant wastewater after overregulating pH and the oxidation of water oxygen gas, the colloid of cuprous formation copper hydroxide.The reaction of copper hydroxide colloidal catalytic sulphite produces multiple free radical as SO
3 -, SO
5 -, SO
4 -, HO, these free radicals all can react with pollutent.
Tool of the present invention has the following advantages and beneficial effect:
1. the present invention obtains free radical by sulphite and copper hydroxide colloid reaction, and without the need to illumination, speed of response is fast, and oxidation effectiveness is good, simple and easy to do.
2. the sulphur oxyradical that the present invention produces (comprises persulfuric acid free radical (SO
5 -), sulphuric acid free radical (SO
4 -) and sulfurous acid free radical (SO
3 -)) oxidisability is strong, more more active than general free radical (as hydroxyl radical free radical).
Accompanying drawing explanation
Fig. 1 is Cu under different pH in embodiment 1
2+-MgSO
3to 8.6 μMs of (2mgL
-1) the degraded situation of dihydroxyphenyl propane;
Fig. 2 is when in embodiment 2, pH is 11, Cu
2+-NaHSO
3to 28.6 μMs of (10mgL
-1) the degraded situation of orange beta-naphthol;
Fig. 3 is when in embodiment 3, pH is 11, Cu
2+-ZnSO
3to 16.2 μMs of (10mgL
-1) the degraded situation of erie black;
Fig. 4 is when in embodiment 4, pH is 11, Cu
+-(NH
4)
2sO
3to 28.6 μMs of (10mgL
-1) the degraded situation of orange beta-naphthol;
Fig. 5 is pH when being 11, Cu
+-K
2sO
3respectively to Congo red 14.4 μMs of (10mgL
-1), activated red X-3B 16.3 μMs of (10mgL
-1), orange IV 26.6 μMs of (10mgL
-1), alkaline bright yellow 30.9 μMs of (10mgL
-1) degraded situation.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition or replacement, all belong to scope of the present invention.Embodiment is carried out under experimental conditions, and organic contamination solution used is prepared voluntarily.
Embodiment 1
Preparation 400mL concentration is 8.6 μMs of (2mgL
-1) dihydroxyphenyl propane solution, add the MgSO that concentration is 50mM
3solution, forms mixed liquor A, makes MgSO in mixed liquor A
3concentration be 1mM; Regulate rapidly about the pH to 11.4 of mixed liquor A by NaOH solution, add magneton, open magneton agitator.Afterwards, Cu is added rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.1mM, now the pH of mixed liquid B is 11.0.Under magneton stirring, reaction 2 hours, reacts previous hour that starts, and at interval of sampling in 10 minutes, react latter one hour that starts, sampling at interval of 20 minutes, is 83% with the degradation efficiency of liquid chromatogram measuring dihydroxyphenyl propane.
In like manner regulate the pH to 10.0 of mixed liquid B, 9.0,8.0, be respectively 45.4%, 13.1%, 9.2% with the degradation rate of liquid chromatogram measuring now dihydroxyphenyl propane.When it should be noted that the pH>12 when mixed liquor A, in solution now, precipitation can be produced.
Embodiment 2
Degraded orange beta-naphthol is micro-reaction, and preparation 50mL concentration is 28.6 μMs of (10mgL
-1) acid orangeⅡ solution, add the NaHSO that concentration is 50mM
3solution, forms mixed liquor A, makes NaHSO in mixed liquor A
3concentration be 1mM; About the pH to 11.4 of mixed liquor A is regulated by NaOH solution; Then get 3mL mixed liquor A in cuvette, add Cu rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.1mM, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of orange beta-naphthol is 84%.
Embodiment 3
Degraded erie black is micro-reaction, and preparation 50mL concentration is 16.2 μMs of (10mgL
-1) erie black solution, add the ZnSO that concentration is 50mM
3solution, forms mixed liquor A, makes ZnSO in mixed liquor A
3concentration be 1mM, regulate about the pH to 11.4 of mixed liquor A by NaOH solution; Then get 3mL mixed liquor A in cuvette, add Cu rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.1mM, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of erie black is 90%.
Embodiment 4
First with concentrated hydrochloric acid, CuCl solid is dissolved completely, then add deionized water and be adjusted to Cu
+concentration be 30mM, be mixed with Cu
+solution.Preparation 50mL concentration is 28.6 μMs of (10mgL
-1) acid orangeⅡ solution, add (the NH that concentration is 50mM
4)
2sO
3solution, forms mixed liquor A, makes (NH in mixed liquor A
4)
2sO
3concentration be 1mM, regulate about the pH to 11.4 of mixed liquor A by NaOH solution.Add Cu rapidly
+solution, forms mixed liquid B, makes Cu in mixed liquid B
+concentration be 0.1mM, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of orange beta-naphthol is 89.8%.
Embodiment 5
Prepare the Congo red 14.4 μMs of (10mgL of 50mL respectively
-1), activated red X-3B 16.3 μMs of (10mgL
-1), orange IV 26.6 μMs of (10mgL
-1), alkaline bright yellow 30.9 μMs of (10mgL
-1) solution, add the K that concentration is 50mM respectively
2sO
3solution, makes K in each reaction solution
2sO
3concentration be 1mM, regulate reaction solution about pH to 11.4 with NaOH.Get 3mL reaction solution respectively and be placed in different cuvettes, add Cu rapidly
2+solution (30mM, pH=2), makes the Cu in reaction solution
2+concentration is 0.1mM, and now reaction solution pH is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, recording its degradation rate is respectively: Congo red 88%, activated red X-3B 57%, orange IV 28%, alkaline bright yellow 28%.
Embodiment 6
Preparation 50mL activated red X-3B concentration is 8.2 μMs of (5mgL
-1), orange beta-naphthol concentration is 14.3 μMs of (5mgL
-1) mixing solutions, add the Na that concentration is 50mM
2sO
3solution, forms mixed liquor A, makes Na in mixed liquor A
2sO
3concentration be 1mM, regulate about the pH to 11.4 of mixed liquor A with NaOH.Get 3mL mixed liquor A in cuvette, add Cu rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.1mM, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of mixed liquor A is 67%.As the Na added
2sO
3in the mixed liquor A that solution is formed, Na
2sO
3concentration when being 0.3mM, add the Cu of 0.1mM
2+solution, the degradation rate of mixed liquor A is 29.4%; As the Na added
2sO
3in the mixed liquor A that solution is formed, Na
2sO
3concentration when being 6mM, add the Cu of 0.1mM
2+solution, the degradation rate of mixed liquor A is 68.1%.
Embodiment 7
Preparation 50mL concentration is 28.6 μMs of (10mgL
-1) acid orangeⅡ solution, add the Na that concentration is 50mM
2sO
3solution, forms mixed liquor A, makes Na in mixed liquor A
2sO
3concentration be 1mM, regulate about the pH to 11.2 of mixed liquor A by NaOH solution.Add Cu rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 28.6 μMs, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of orange beta-naphthol is 34.4%.
In like manner regulate about the pH to 11.5 of mixed liquor A, add Cu rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.5mM, now the pH of mixed liquid B is 11.0.Carry out METHOD FOR CONTINUOUS DETERMINATION with fiber spectrometer, react after 30 minutes, the degradation rate of orange beta-naphthol is 90.3%.
Embodiment 8
Preparation 400mL concentration is 8.6 μMs of (2mgL
-1) dihydroxyphenyl propane solution, add the Na that concentration is 50mM
2sO
3solution, forms mixed liquor A, makes Na in mixed liquor A
2sO
3concentration be 1mM, regulate rapidly about the pH to 4 of mixed liquor A by NaOH solution, add magneton, open magneton agitator.Afterwards, Cu is added rapidly
2+solution (30mM, pH=2), forms mixed liquid B, makes Cu in mixed liquid B
2+concentration be 0.1mM, now the pH of mixed liquid B is 4.0.Under magneton stirring, reaction 2 hours, reacts previous hour that starts, and at interval of sampling in 10 minutes, react latter one hour that starts, sampling at interval of 20 minutes, is 1% with the degradation efficiency of liquid chromatogram measuring dihydroxyphenyl propane.In like manner regulating the pH to 6.0 of mixed liquor A, is 5.3% with the degradation rate of liquid chromatogram measuring now dihydroxyphenyl propane.
Embodiment 9
Preparing 2 parts of 400mL concentration is respectively 8.6 μMs of (2mgL
-1) dihydroxyphenyl propane solution, a copy of it dihydroxyphenyl propane solution only adds the Na that concentration is 50mM
2sO
3solution, makes Na
2sO
3concentration is 1mM, regulates about pH to 11 rapidly by NaOH solution, adds magneton, opens magneton agitator.Only Cu is added in another part of dihydroxyphenyl propane solution
2+solution (30mM, pH=2), makes Cu
2+concentration is 0.1mM, regulates about pH to 11 rapidly with NaOH, adds magneton, opens magneton agitator.Under magneton stirring, reaction 2 hours, reacts previous hour that starts, and at interval of sampling in 10 minutes, reacts latter one hour that starts, samples at interval of 20 minutes; Now obtain with liquid chromatogram measuring, the degradation efficiency of the two dihydroxyphenyl propane is all almost 0.
Claims (7)
1., based on an organic pollutant oxidation treatment method for sulphur oxyradical, it is characterized in that, comprise the steps:
A () gets the solution containing organic pollutant, the concentration recording organic pollutant is xmol/L;
B () prepares sulfite solution, copper salt solution respectively, for subsequent use;
C sulfite solution adds in the solution containing organic pollutant by (), form mixed liquor A, the concentration of mixed liquor A sulfite salt is 10xmol/L ~ 250xmol/L; Regulate pH value to 10.0 ~ 11.4 of mixed liquor A immediately, then add copper salt solution rapidly, form mixed liquid B, in mixed liquid B, the concentration of mantoquita is 1xmol/L ~ 17xmol/L, and the pH of mixed liquid B is 8.0 ~ 11.0; Stir or aeration mixed liquid B degradable to organic pollutant.
2. as claimed in claim 1 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: described organic pollutant is one or more in dihydroxyphenyl propane, orange II, Congo red, activated red X-3B, orange IV, alkaline bright yellow, erie black.
3., as claimed in claim 1 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: described sulphite is Na
2sO
3, K
2sO
3, (NH
4)
2sO
3, NaHSO
3, MgSO
3, Al
2(SO
3)
3, Fe
2(SO
3)
3, ZnSO
3in one or more.
4., as claimed in claim 1 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: described mantoquita is Cu (NO
3)
2, CuCl
2, CuSO
4, CuSO
3, one or more in CuCl.
5., as claimed in claim 4 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: the pH value of cupric salt solution is 2.
6. as claimed in claim 4 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: the manner of formulation of CuCl solution is: first with concentrated hydrochloric acid, CuCl solid is dissolved completely, then add deionized water and regulate Cu
+to desired concn.
7., as claimed in claim 1 based on the organic pollutant oxidation treatment method of sulphur oxyradical, it is characterized in that: the pH of described mixed liquid B is 11.0.
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