CN117263360A - Method for treating printing and dyeing wastewater through iron-spent bleaching clay-carbon coupling Fenton system - Google Patents
Method for treating printing and dyeing wastewater through iron-spent bleaching clay-carbon coupling Fenton system Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 64
- 238000004043 dyeing Methods 0.000 title claims abstract description 51
- 238000007639 printing Methods 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000004061 bleaching Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008878 coupling Effects 0.000 title claims abstract description 23
- 238000010168 coupling process Methods 0.000 title claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 34
- 231100000719 pollutant Toxicity 0.000 claims abstract description 34
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 32
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 27
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004927 clay Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002699 waste material Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 36
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 13
- 239000000356 contaminant Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005189 flocculation Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010918 textile wastewater Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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Abstract
A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupling Fenton system comprises the steps of adding hydrogen peroxide into an iron-carbon mixture formed by spent bleaching clay-carbon and iron, mixing to obtain the iron-spent bleaching clay-carbon micro-electrolysis coupling Fenton system, regulating the printing and dyeing wastewater to be acidic, and carrying out synergistic degradation on organic dye pollutants and heavy metal antimony in the printing and dyeing wastewater by the iron-spent bleaching clay-carbon micro-electrolysis coupling Fenton system. According to the method for treating the printing and dyeing wastewater by the iron-spent bleaching clay-carbon coupling Fenton system, the synergistic degradation of organic dye pollutants and heavy metal antimony is improved, so that the actual treatment capacity of the printing and dyeing wastewater is improved.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupling Fenton system.
Background
China is the largest textile production country worldwide, and the total amount of textile wastewater discharged per year is about 20 hundred million tons, wherein the printing and dyeing wastewater accounts for about 70 percent. Printing and dyeing wastewater contains a large amount of organic dye pollutants (such as azo type anionic organic dye pollutants (methyl orange), water-soluble mountain stings type anionic organic dye pollutants (eosin Y), water-soluble anthraquinone type anionic organic dye pollutants (alizarin red) and the like) and heavy metal antimony, wherein the organic dye pollutants contain chromogenic groups and polar groups, and the heavy metal antimony mainly exists in a form of high-toxicity pentavalent antimony. These components lead to high colour, high COD content, high toxicity and low degradability of the printing and dyeing wastewater. If the treatment is improper, the organic dye pollutants can react with other elements in the environment to generate harmful substances, so that the ecological environment is deteriorated, and the human health is threatened; the heavy metal antimony is easily absorbed by plant root systems, and has strong toxicological effects on root system growth and germination. Therefore, it is important to search for a method for effectively treating printing and dyeing wastewater.
Removal of the organic dye contaminant and heavy metal antimony is accomplished by separate reactions with the reactants, which are reduced if the organic dye contaminant consumes more of the reactants because the mass of the reactants is fixed during degradation, and vice versa. This allows antagonism between the organic dye contaminant and the heavy metal antimony, the presence of one species reducing the removal rate of the other. Therefore, aiming at the characteristic that the printing and dyeing wastewater contains a large amount of organic dye pollutants and heavy metal antimony, the existing method is usually aimed at removing single organic dye pollutants or heavy metal antimony, the application conditions are harsh, and the difficulty of removing the pollutants in the printing and dyeing wastewater is aggravated.
Disclosure of Invention
The invention aims to provide a method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupling Fenton system, which improves the actual treatment capacity of the printing and dyeing wastewater.
In order to solve the technical problems, the invention adopts the following specific scheme: a method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupling Fenton system comprises the steps of adding hydrogen peroxide into an iron-carbon mixture formed by spent bleaching clay-carbon and iron, mixing to obtain the iron-spent bleaching clay-carbon micro-electrolysis coupling Fenton system, regulating the printing and dyeing wastewater to be acidic, and carrying out synergistic degradation on organic dye pollutants and heavy metal antimony in the printing and dyeing wastewater by the iron-spent bleaching clay-carbon micro-electrolysis coupling Fenton system.
Preferably, the spent bleaching clay carbon is prepared by the following method:
1) Drying the spent bleaching clay at 60-130 ℃ for 12-72h;
2) Grinding or crushing the waste clay dried in the step 1) until the particle size is smaller than 5.0mm to obtain waste clay powder;
3) Pyrolyzing the waste clay powder obtained in the step 2) in an anoxic atmosphere at 400-1000 ℃ for 0.5-5h, and cooling to obtain the waste clay carbon.
Preferably, in step 3) a nitrogen blanket is performed, the nitrogen flow rate being 50-400ml/min.
Preferably, the temperature rising rate of the step 3) is 5-20 ℃/min.
Preferably, the pH of the printing and dyeing wastewater is regulated to 2.5-3.5, 70-80mmol/L hydrogen peroxide and 1.8-2.3g/L iron-carbon mixture are added, and the mixture is reacted for 0.5-12h at the temperature of 25-50 ℃.
Preferably, the pH of the printing and dyeing wastewater is regulated to 2.5-3.5, 70-80mmol/L hydrogen peroxide is added, the iron-carbon mixture is used as a filler to prepare a filling column, the filling column is put into the printing and dyeing wastewater with a filling amount of 1-2.8g/L, and the reaction is carried out for 0.5-12h at the temperature of 25-50 ℃.
Preferably, the proportion of waste clay carbon and iron in the iron-carbon mixture is 1: (2.5-3.5).
Preferably, the pH of the printing and dyeing wastewater is adjusted to 3, and 78.4mmol/L hydrogen peroxide and 2g/L iron-carbon mixture are added.
Preferably, after the reaction is finished, the iron-carbon mixture is recovered for reuse.
Preferably, the organic dye contaminants are one or more combinations of azo type anionic organic dye contaminants, water-soluble mountain stings type anionic organic dye contaminants, and water-soluble anthraquinone type anionic organic dye contaminants.
Advantageous effects
The iron-waste carclazyte carbon micro-electrolysis coupling Fenton system realizes the synergistic effect of removing organic dye pollutants and heavy metal antimony under certain specific conditions such as limiting pH, adding amount of iron carbon, adding amount of hydrogen peroxide and the like, namely the removing efficiency is higher than that of independently removing the organic dye pollutants or the heavy metal antimony, and the mechanism is that the degradation of the organic dye pollutants promotes the oxidation reaction in the system and accelerates the Fe 2+ And Fe (Fe) 3+ Form, absorb and remove pentavalent antimony by flocculation, and form the antimony-containing floccules to reduce Fe in the system 2+ And Fe (Fe) 3+ The reaction of the micro-electrolysis coupling Fenton system is promoted to generate more free radicals to degrade organic dye pollutants, so that the method can be applied to the treatment of printing and dyeing wastewater with complex components, and the defect that the prior art can only treat single pollutants is overcome. Experiments prove that in the micro-electrolysis coupling Fenton system, the removal efficiency of alizarin red which is a single pollutant organic dye is 71.72%, and the removal efficiency of Sb (V) which is a single pollutant is 73.66%; under the condition that organic dye pollutants and heavy metal antimony coexist, the removal rate is not only not reduced, but also obviously increasedThe most preferred embodiment has an organic dye contaminant removal of 90.94% and a pentavalent antimony removal of 98.73%.
The invention relates to an iron-spent bleaching clay carbon micro-electrolysis coupling Fenton system, which generates a nascent state [ H ] under the action of a micro-electric field](ii) OH and H 2 O 2 And Fe (Fe) 2+ Redox decomposes contaminants, which process generates Fe (OH) 2 And Fe (OH) 3 Realizes physical flocculation and pollutant adsorption, and electric field enrichment promotes charged pollutants in printing and dyeing wastewater to move to two ends of an electrode to generate flocculation precipitation, and Fe generated by iron-carbon micro-electrolysis 2+ Can be used as a reactant of Fenton reaction, and H 2 O 2 Fenton reaction is carried out under an acidic condition to generate OH, so that oxidation reduction of pollutants is accelerated, and the pollutant removal effect is enhanced.
The waste carclazyte carbon is a byproduct of oil refining, and can avoid generating oxygen-containing toxic gas through anoxic pyrolysis; meanwhile, the waste carclazyte carbon can be used as a carbon source for iron carbon micro-electrolysis, so that waste recycling is realized. The novel adsorbent is prepared by the method, and the pollutants are enriched on the surface of the adsorbent, so that the free radical site-directed attack of the pollutants and the iron simple substance reduction of the pentavalent antimony is facilitated.
The printing and dyeing wastewater is acidic or alkaline, and for acidic printing and dyeing wastewater, the iron-spent bleaching clay carbon micro-electrolysis coupling Fenton system can consume acid in the printing and dyeing wastewater, so that the use amount of the acid is reduced, and the difficulty in neutralizing organic acid in wastewater treatment is reduced.
The iron-spent bleaching clay carbon micro-electrolysis coupling Fenton system can be repeatedly used under the condition of no regeneration, and the reaction does not cause secondary pollution and is green and clean.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to specific embodiments:
example 1
Preparing waste carclazyte carbon: drying the spent bleaching clay in a 125 ℃ oven for 18 hours, grinding the spent bleaching clay in a mortar, sieving the ground spent bleaching clay by a 100-mesh sieve, putting the ground spent bleaching clay in a tubular furnace for pyrolysis, adjusting the flow rate of nitrogen to 120ml/min, heating the mixture at a rate of 10 ℃/min, and pyrolyzing the mixture at 800 ℃ for 2 hours. And after pyrolysis is finished, naturally cooling to 45 ℃ and taking out the material to prepare the waste carclazyte carbon.
Constructing an iron-spent bleaching clay carbon micro-electrolysis coupling Fenton system: mixing the reduced iron powder and the waste carclazyte carbon in a ratio of 3:1, taking an iron-carbon mixture according to the volume of sewage to be treated and 2g/L, and taking H according to 78.4mmol/L 2 O 2 And (5) uniformly mixing.
The method is applied to degradation of pollutants in the antimony-containing printing and dyeing wastewater: alizing dye with alizarin red as pollutant, preparing 1L of printing and dyeing wastewater containing 500mg/L alizarin red and 1mg/L antimonate, regulating pH to 3, adding the iron-spent bleaching clay carbon micro-electrolysis coupling Fenton system, and reacting at 25deg.C for 2 hr/min. After the reaction, the supernatant was filtered through a 0.45 μm filter membrane, and the removal rates of alizarin red and heavy metal antimony after adsorption were measured as shown in Table 1 below.
Example 2
The only difference from example 1 is that: in this example, iron-carbon mixtures were added at 1g/L, based on the volume of wastewater to be treated.
Example 3
The only difference from example 1 is that: in this example, iron-carbon mixtures were added at 2.8g/L, based on the volume of wastewater to be treated.
Example 4
The only difference from example 1 is that: in this example, iron-carbon mixtures were added at 3.5g/L, based on the volume of wastewater to be treated.
Example 5
The only difference from example 1 is that: in this example, the iron-carbon mixture was added at 8g/L, based on the volume of wastewater to be treated.
Example 6
The only difference from example 1 is that: the pH of the wastewater was adjusted to 1 in this example.
Example 7
The only difference from example 1 is that: the pH of the wastewater was adjusted to 2.5 in this example.
Example 8
The only difference from example 1 is that: the pH of the wastewater was adjusted to 3.5 in this example.
Example 9
The only difference from example 1 is that: the pH of the wastewater was adjusted to 4 in this example.
Example 10
The only difference from example 1 is that: in this example, H was added at a rate of 70mmol/L based on the volume of wastewater to be treated 2 O 2 。
Example 11
The only difference from example 1 is that: in this example, H was added at 80mmol/L based on the volume of wastewater to be treated 2 O 2 。
Example 12
The only difference from example 1 is that: in this example, H was added at 100mmol/L based on the volume of wastewater to be treated 2 O 2 。
Example 13
The only difference from example 1 is that: in this example, a test was conducted by preparing 1L of composite printing and dyeing wastewater of 166.7mg/L methyl orange, 500mg/L eosin Y, 500mg/L alizarin red and 1mg/L antimonate.
Example 14
The only difference from example 1 is that: in the embodiment, the iron-carbon mixture is used as a filler to prepare a filling column, and the filling column is put into printing and dyeing wastewater for degradation reaction.
Example 15
The only difference from example 1 is that: in this example, 1L of printing and dyeing wastewater containing 500mg/L alizarin red without heavy metal antimony was prepared for the test.
Example 16
The only difference from example 1 is that: in this example, 1L of printing and dyeing wastewater containing 1mg/L antimonate was prepared and tested without organic dye contaminants.
TABLE 1 removal rates of organic dye pollutants and heavy metal antimony for various examples in the present invention
As can be seen from table 1 above:
example 1 according to the invention, at a rate of 2g/L iron-carbon mixture, 78.4mmol/L H was taken 2 O 2 And when the pH value of the wastewater is regulated to 3, the highest removal rate of alizarin red and heavy metal antimony is achieved to 90.94% and 98.73% respectively. In examples 15 and 16, the removal rates for alizarin red and heavy metal antimony single contaminants were only 71.72% and 73.66%, respectively, at the same dosage addition. Therefore, the embodiment has a synergistic effect on the degradation of organic dye pollutants and heavy metal antimony, and overcomes the defect that the prior art can only treat single pollutants.
In examples 1 to 3, 7, 8, 10, 11, 13 and 14, the iron-carbon addition amount was 1 to 2.8g/L at pH 2.5 to 3.5, H 2 O 2 When the addition amount is 70-80mmol/L, the removal rates of alizarin red and heavy metal antimony are respectively higher than 71.72% and 73.66%, so that the above embodiment has obvious synergistic effect on alizarin red and heavy metal antimony. In examples 4 to 6, 9 and 12, the pH, the iron-carbon addition amount and H were as follows 2 O 2 When the addition amount is not limited any more, the removal rate of alizarin red and heavy metal antimony is mostly lower than 71.72% and 73.66%, so that the synergistic effect in the embodiment is not obvious.
Based on the above data analysis, the reason that pH 3 is optimal may be: although the initial pH value is raised, fe 2+ And Fe (Fe) 3+ Separating out to form floccules, enhancing adsorption and flocculation, and removing organic dye by adsorption; however, under alkaline conditions, iron can rapidly form hydroxide precipitates to cover the surface of the material, which prevents the progress of micro-electrolysis and Fenton reaction. The removal efficiency of Sb (V) decreases with increasing pH, since under acidic conditions the organic dye is mainly removed by oxidative degradation, whereas the antimony is mainly removed by adsorption flocculation; with the increase of the initial pH value, the oxidative degradation of the organic dye is inhibited, the removal of the organic dye and the antimony are dominant by adsorption flocculation, and the high-concentration organic dye occupies part of attachment sites, so that the removal efficiency of the antimony is obviously reduced. If the initial pH value is high, a passivation film is formed on the surface of the material, which is unfavorable for the iron-carbon micro-electrolysis coupling Fenton reaction. But at acidic pH, H + Has effect in promoting iron corrosion and Fe 2+ Thereby promoting Fenton reaction and Fe 2+ And Fe (Fe) 3+ And precipitate to form floccules. It is apparent that when the pH is below 3, too much H + Can inhibit Fe (OH) 2 And Fe (OH) 3 The formation of floccules has a negative effect on the adsorption removal of organic dyes and heavy metal antimony.
The optimal addition amount of the iron-carbon mixture is 2g/L, which is probably as follows: because the addition amount is low, the number of primary cells is reduced, and Fe provided for Fenton system is reduced 2+ The concentration is very limited, the micro-electrolysis reaction and the Fenton reaction are weak, and the pollutant removing capability is limited. Along with the increase of the addition amount, the micro-electrolysis reaction is gradually enhanced, meanwhile, the Fenton reaction is promoted, and the removal rate is increased. However, when the addition amount is too high, the micro-electrolysis reaction rapidly occurs, and the generated ferrous iron excites H 2 O 2 A large amount of OH is generated, which is not timely combined with organic matters, side reaction (2) occurs, the concentration of OH is reduced, and the removal rate is reduced.
H 2 O 2 +·OH→H 2 O+·O 2 H (1)
·OH+·OH→H 2 O 2 (2)
H 2 O 2 The optimal addition amount of 78.4mmol/L may be: when H is 2 O 2 The concentration is too low, the generated OH number is insufficient, and the Fenton reaction is limited. With H 2 O 2 The Fenton reaction is gradually enhanced when the concentration is increased, and when H 2 O 2 When the concentration is too high, side reactions (1) and (2) occur, resulting in a decrease in the removal rate.
In addition, the following recycling experiments were also performed for the iron-spent bleaching clay carbon micro-electrolysis coupled Fenton system of example 1: after the primary reaction is finished, filtering the waste water recovery material, and adding 1L of printing and dyeing wastewater containing 500mg/L alizarin red and 1mg/L antimonate again for adsorption. After the first repeated use, the removal rate of the organic dye is 78.14 percent, and the removal rate of the heavy metal antimony is 90.84 percent; after the second repeated use, the removal rate of the organic dye is 76.07 percent, and the removal rate of the heavy metal antimony is 88.08 percent; after the third repeated use, the removal rate of the organic dye is 72.61%, and the removal rate of heavy metal antimony is 46.91%.
Claims (10)
1. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupling Fenton system is characterized by comprising the following steps: adding hydrogen peroxide into an iron-carbon mixture composed of waste clay carbon and iron, mixing to obtain an iron-waste clay carbon micro-electrolysis coupling Fenton system, regulating the printing and dyeing wastewater to be acidic, and carrying out synergistic degradation on organic dye pollutants and heavy metal antimony in the printing and dyeing wastewater through the iron-waste clay carbon micro-electrolysis coupling Fenton system.
2. The method for treating printing and dyeing wastewater by using an iron-spent bleaching clay-carbon coupled Fenton system according to claim 1, wherein the method comprises the following steps of: the waste clay carbon is prepared by the following steps:
1) Drying the spent bleaching clay at 60-130 ℃ for 12-72h;
2) Grinding or crushing the waste clay dried in the step 1) until the particle size is smaller than 5.0mm to obtain waste clay powder;
3) Pyrolyzing the waste clay powder obtained in the step 2) in an anoxic atmosphere at 400-1000 ℃ for 0.5-5h, and cooling to obtain the waste clay carbon.
3. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-coupled Fenton system according to claim 2, wherein: and 3) nitrogen protection is carried out in the step 3), and the flow rate of the nitrogen is 50-400ml/min.
4. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-coupled Fenton system according to claim 2, wherein: the temperature rising rate of the step 3) is 5-20 ℃/min.
5. The method for treating printing and dyeing wastewater by using an iron-spent bleaching clay-carbon coupled Fenton system according to claim 1, wherein the method comprises the following steps of: adjusting the pH of the printing and dyeing wastewater to 2.5-3.5, adding 70-80mmol/L hydrogen peroxide and 1.8-2.3g/L iron-carbon mixture, and reacting for 0.5-12h at 25-50 ℃.
6. The method for treating printing and dyeing wastewater by using an iron-spent bleaching clay-carbon coupled Fenton system according to claim 1, wherein the method comprises the following steps of: adjusting the pH of the printing and dyeing wastewater to 2.5-3.5, adding 70-90mmol/L hydrogen peroxide, preparing the iron-carbon mixture as a filler into a filling column, putting the filling column into the printing and dyeing wastewater with a filling amount of 1-2.8g/L, and reacting for 0.5-12h at 25-50 ℃.
7. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-coupled Fenton system according to claim 5 or 6, wherein: in the iron-carbon mixture, the proportion of the waste carclazyte carbon to the iron is 1: (1-4).
8. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-coupled Fenton system according to claim 5 or 6, wherein: adjusting the pH of the printing and dyeing wastewater to 3, and adding 78.4mmol/L hydrogen peroxide and 2g/L iron-carbon mixture.
9. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-coupled Fenton system according to claim 5 or 6, wherein: and after the reaction is finished, recovering the iron-carbon mixture for reuse.
10. A method for treating printing and dyeing wastewater by an iron-spent bleaching clay-carbon coupled Fenton system according to any one of claims 1-6, wherein: the organic dye pollutant is one or a combination of more of azo type anionic dye, water-soluble mountain stings type anionic dye and water-soluble anthraquinone type anionic dye.
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