CN111847570A - photo-Fe3+-Na2S2O8Method for deeply treating pulping and papermaking wastewater by system - Google Patents
photo-Fe3+-Na2S2O8Method for deeply treating pulping and papermaking wastewater by system Download PDFInfo
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- CN111847570A CN111847570A CN202010567090.8A CN202010567090A CN111847570A CN 111847570 A CN111847570 A CN 111847570A CN 202010567090 A CN202010567090 A CN 202010567090A CN 111847570 A CN111847570 A CN 111847570A
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- pulping
- papermaking wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 238000004537 pulping Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims abstract description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Images
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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- Chemical & Material Sciences (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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a light-Fe3+‑Na2S2O8The method for deeply treating pulping and papermaking wastewater by a system comprises the following operation steps: (1) taking the pulping and papermaking wastewater after the secondary biochemical treatment in a beaker; (2) adding FeCl into a beaker3·6H2O，FeCl3·6H2The concentration of O in the system is 1.0-2.0 mmol/L; (3) adding sodium persulfate into the beaker, wherein the concentration of the sodium persulfate in the system is 2-8 mmol/L; (4) adjusting the pH value to 2-3; (5) finally adding visible light, setting the reaction time to be 10-360min, and forming light-Fe after the reaction3+‑Na2S2O8And the system can degrade the papermaking wastewater. The method of the invention uses light-Fe3+‑Na2S2O8The system is applied to the degradation of complex papermaking wastewater, and can realize the high-efficiency, simple and convenient treatment of the secondary effluent of pulping and papermaking, so that the secondary effluent reaches the standard and is discharged.
Description
Technical Field
The invention belongs to the technical field of environmental protection and treatment, and particularly relates to light-Fe3+-Na2S2O8A method for deeply treating pulping and papermaking wastewater by a system.
Background
The paper making industry is a prop industry of China and is also a high water consumption industry, a large amount of water resources are consumed, and a large amount of paper making wastewater which is high in concentration and difficult to degrade is generated. According to 2016 annual report of the Chinese paper industry, in 2015, the total amount of water used in the paper-making and paper-product industry in China is 118.35 hundred million tons, wherein the fresh water accounts for 28.98 million tons, and accounts for 7.5 percent of the total fresh water consumption of 386.96 million tons in the industry; the total discharge of industrial wastewater in China is 181.55 hundred million tons, wherein 23.67 hundred million tons of wastewater account for 13.0 percent of the total discharge of industrial wastewater in China. The papermaking wastewater mainly comes from black liquor generated in a cooking working section, middle-stage water generated in a pulp washing and bleaching working procedure and white water generated in a papermaking working procedure. At present, most of papermaking enterprises in China often adopt traditional wastewater treatment technologies such as a physical and chemical treatment method and a biological treatment method to treat papermaking wastewater, and most of the papermaking enterprises can not reach the standard after secondary biochemical treatment according to the discharge standard of water pollutants for pulping and papermaking industries issued by the nation (GB3544-2008), and the CODcr value is higher. Therefore, an advanced treatment method capable of making the secondary biochemical effluent of papermaking reach the standard is urgently needed.
Advanced oxidation technologies (AOPs) are currently the most popular advanced wastewater treatment technologies, and have been widely used for wastewater treatment. The advanced oxidation technology comprises a Fenton reagent oxidation method, a quasi-Fenton oxidation method, an ozone oxidation method and the like. Currently, a Fenton reagent oxidation method is widely applied to actual wastewater treatment, but the Fenton reagent oxidation method has certain defects, such as narrow applicable pH range and general requirement under an acidic condition; h2O2The utilization rate is low, and the waste of the oxidant is easily caused; a large amount of iron mud is generated after the reaction, and the follow-up is increasedThe cost of the process.
Disclosure of Invention
The invention aims to provide light-Fe3+-Na2S2O8The method for deeply treating the pulping and papermaking wastewater by the system can efficiently, simply and conveniently treat the secondary effluent of pulping and papermaking, so that the secondary effluent reaches the standard and is discharged.
The invention solves the technical problems by the following technical scheme:
photo-Fe of the invention3+-Na2S2O8The method for deeply treating pulping and papermaking wastewater by the system comprises the following operation steps:
(1) taking the pulping and papermaking wastewater after the secondary biochemical treatment in a beaker;
(2) adding FeCl into a beaker3·6H2O，FeCl3·6H2The concentration of O in the system is 1.0-2.0 mmol/L;
(3) adding sodium persulfate into the beaker, wherein the concentration of the sodium persulfate in the system is 2-8 mmol/L;
(4) Adjusting the pH value to 2-3;
(5) finally adding visible light, setting the reaction time to be 10-360min, and forming light-Fe after the reaction3+-Na2S2O8And the system can degrade the papermaking wastewater.
In the step 1), the pulping and papermaking wastewater after the secondary biochemical treatment comprises the components of p-hydroxyphenylpropionic acid, glucose, anhydrous sodium sulfate and lactic acid.
In the step 5), the visible light is irradiated by a metal halide lamp, and the irradiation mode is internal irradiation.
Compared with the prior art, the invention has the following advantages:
1) the CODcr removing rate of the pulping and papermaking wastewater can reach 79.2 percent at most, the final effluent can be discharged up to the standard, and the defect that the papermaking wastewater cannot reach the standard when treated by the traditional wastewater treatment methods such as a physical treatment method, a biological treatment method and the like is overcome.
2) The invention adopts metal halide lamp to provide light source to catalyze Fe3+Conversion to Fe2+Promote Fe3+With Fe2+The redox cycle of (1) accelerates Fe2+Catalysis of sodium persulfate to SO4 -·The rate of the method improves the utilization rate of iron resources.
3) The invention adopts photo-Fe3+The method has the advantages of activating a sodium persulfate system, simple process, simple operation, wide sources of raw materials and reagents required by experiments, low price and easy purchase.
Drawings
FIG. 1 is a graph showing the analysis and measurement of the pulp and paper-making wastewater treated in example 1 of the present invention.
FIG. 2 is a graph showing the analysis and measurement of the pulp and paper wastewater treated in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
Example 1
Taking a proper amount of pulping and papermaking wastewater subjected to secondary biochemical treatment in a beaker (the concentration of CODcr of the wastewater in the system is 130mg/L), and sequentially adding 50mmol/L of FeCl3·6H2O stock solution 10, 20, 40, 100mL of solution was removed and added to the beaker (equivalent to FeCl)3·6H2The concentration of O in the system is: 0.5, 1.0, 2.0, 5.0mmol/L), and further 200mmol/L of sodium persulfate (Na)2S2O8) 10mL of the stock solution was transferred to the beaker (equivalent to Na)2S2O8The concentration in the system is 2mmol/L), and after the materials are fully mixed, the pH value is adjusted to 3; pouring the mixture into a metal halide lamplight catalytic reactor, and starting timing when the mixture is irradiated by light; CODcr measurements were performed on 5.0mL of water samples taken with a pipette at 0, 10, 30, 60, 120, 240, and 360min, and the results are shown in FIG. 1: it can be seen that the process of the present invention is in FeCl3·6H2O＝1.0mmol/L、Na2S2O8The CODcr removing rate of the pulping and papermaking wastewater can reach 41.7 percent at most when the reaction lasts for 360 min. According to GB 3544-2008, the discharge limit of CODcr of the pulping and papermaking combined production enterprise is 90mg/L, so that FeCl 3·6H2The O concentration range is 1.0-2.0mmol/L can realize the standard discharge of wastewater.
Example 2
Taking a proper amount of pulping and papermaking wastewater subjected to secondary biochemical treatment in a beaker (the concentration of CODcr of the wastewater in the system is 130mg/L), and adding 50mmol/L of FeCl3·6H220mL of the solution was transferred from the O stock solution and added to the beaker (corresponding to FeCl)3·6H2The concentration of O in the system is 1.0mmol/L), and then sodium persulfate (Na) of 200mmol/L is sequentially added2S2O8) 5, 10, 20, 40, 80mL of the stock solution were transferred to the beaker (equivalent to Na)2S2O8The concentration in the system is 1, 2, 4, 8, 16mmol/L), after fully mixing, the pH is adjusted to 2; pouring the mixture into a metal halide lamplight catalytic reactor, and starting timing when the mixture is irradiated by light; CODcr measurements were performed on 5.0mL of water samples taken with a pipette at 0, 10, 30, 60, 120, 240, and 360min, and the results are shown in FIG. 2: it can be seen that the process of the present invention is in FeCl3·6H2O＝1.0mmol/L、Na2S2O8The CODcr removal rate of the pulping and papermaking wastewater can reach 79.2 percent when the reaction time is 360 min. According to GB 3544-2008, the discharge limit of CODcr of the pulping and papermaking combined production enterprise is 90mg/L, so Na2S2O8The concentration range is 2-8mmol/L, and the wastewater can be discharged after reaching the standard.
Claims (3)
1. photo-Fe3+-Na2S2O8The method for deeply treating pulping and papermaking wastewater by a system is characterized by comprising the following operation steps:
(1) Taking the pulping and papermaking wastewater after the secondary biochemical treatment in a beaker;
(2) adding FeCl into a beaker3·6H2O，FeCl3·6H2The concentration of O in the system is 1.0-2.0 mmol/L;
(3) adding sodium persulfate into the beaker, wherein the concentration of the sodium persulfate in the system is 2-8 mmol/L;
(4) adjusting the pH value to 2-3;
(5) finally, visible light is added and the reaction is setThe time is 10-360min, and light-Fe is formed after the reaction3+-Na2S2O8And the system can degrade the papermaking wastewater.
2. photo-Fe according to claim 13+-Na2S2O8The method for deeply treating the pulping and papermaking wastewater by the system is characterized in that in the step 1), the pulping and papermaking wastewater after the secondary biochemical treatment comprises the components of p-hydroxyphenylpropionic acid, glucose, anhydrous sodium sulfate and lactic acid.
3. photo-Fe according to claim 1 or 23+-Na2S2O8The method for deeply treating the pulping and papermaking wastewater by the system is characterized in that in the step 5), the visible light is irradiated by a metal halide lamp, and the irradiation mode is internal irradiation.
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| CN202010567090.8A CN111847570A (en) | 2020-06-19 | 2020-06-19 | photo-Fe3+-Na2S2O8Method for deeply treating pulping and papermaking wastewater by system |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818993A (en) * | 2014-02-17 | 2014-05-28 | 华南理工大学 | Method for processing papermaking wastewater by advanced oxidation treatment of activating persulfate or monoperoxy-hydrosulfate with ferrous salt |
| US20140346124A1 (en) * | 2011-10-27 | 2014-11-27 | Universite D'aix Marseille | Reactor usable for decontamination of fluids and method of use |
| CN106517486A (en) * | 2016-12-27 | 2017-03-22 | 武汉纺织大学 | Method for processing organic wastewater through catalytic activation of peroxysulphate by means of visible light and FeOCl in synergetic mode |
| CN110745982A (en) * | 2019-09-12 | 2020-02-04 | 生态环境部华南环境科学研究所 | Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate |
-
2020
- 2020-06-19 CN CN202010567090.8A patent/CN111847570A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140346124A1 (en) * | 2011-10-27 | 2014-11-27 | Universite D'aix Marseille | Reactor usable for decontamination of fluids and method of use |
| CN103818993A (en) * | 2014-02-17 | 2014-05-28 | 华南理工大学 | Method for processing papermaking wastewater by advanced oxidation treatment of activating persulfate or monoperoxy-hydrosulfate with ferrous salt |
| CN106517486A (en) * | 2016-12-27 | 2017-03-22 | 武汉纺织大学 | Method for processing organic wastewater through catalytic activation of peroxysulphate by means of visible light and FeOCl in synergetic mode |
| CN110745982A (en) * | 2019-09-12 | 2020-02-04 | 生态环境部华南环境科学研究所 | Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate |
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