CN113264619A - Method for treating organic phosphate in landfill leachate membrane concentrated solution - Google Patents
Method for treating organic phosphate in landfill leachate membrane concentrated solution Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 62
- 239000010452 phosphate Substances 0.000 title claims abstract description 62
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 239000000149 chemical water pollutant Substances 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000002351 wastewater Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- -1 iron ions Chemical class 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000005192 partition Methods 0.000 claims abstract description 8
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 14
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000011001 backwashing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011574 phosphorus Substances 0.000 abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000009471 action Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- 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
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F2001/46152—Electrodes characterised by the shape or form
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention provides a method for treating organic phosphate in a landfill leachate membrane concentrated solution, which utilizes chloride ions contained in wastewater and added iron ions to degrade organic phosphate and synchronously recover phosphorus. The treatment method adopts a wastewater treatment device, and the wastewater treatment device comprises: the device comprises a water inlet pipe, an electrochemical oxidation reactor, a photochemical oxidation reactor, a stirrer, a partition plate, a filter layer, a water storage layer and a water outlet pipe. On one hand, under the action of a photoelectric oxidation reactor, chloride ions and iron ions efficiently generate hydroxyl radicals and chlorine radicals with extremely high reaction activity through a series of oxidation-reduction reactions, so that organic phosphate in wastewater is effectively degraded; on the other hand, the generated phosphate is combined with iron ions to generate iron phosphate precipitate or the ferrihydrite directly adsorbs the phosphate to precipitate on the bottom of the pool, thereby realizing the recovery of phosphorus.
Description
Technical Field
The invention relates to a wastewater treatment technology, in particular to a method for treating organic phosphate in a landfill leachate membrane concentrated solution.
Background
Organic phosphate is used as an artificially synthesized organic matter, and is often used as a flame retardant in the processing industries of textiles, electronic products, furniture, mattresses and the like due to the advantages of low price and good flame retardance, lubrication and plasticization. In addition, organophosphates may also be used as scale inhibitors to prevent or mitigate fouling of the membrane surface in reverse osmosis systems. However, researches show that the organic phosphate is not an environment-safe substance, most of the organic phosphate has toxicity, and after the organic phosphate is discharged into a water environment, the organic phosphate is easy to cause eutrophication of the water body and also harms human health. Meanwhile, phosphorus is used as a non-renewable strategic resource, which is related to agricultural development, grain safety and chemical industry development, and in order to maintain the normal use of phosphorus, the recovery and reuse of phosphorus in phosphorus-containing wastewater is necessary.
At present, the treatment method of organic phosphate mainly comprises three technologies of biological process, adsorption and advanced oxidation. The biological process is to degrade organic phosphorus in water into inorganic phosphorus by utilizing the decomposition of microorganisms, thereby purifying water quality. Biodegradation is not an effective method of treating phosphonate scale inhibitors, however, because high salinity in some wastewater can inhibit microbial growth, resulting in degradation rates of only 5% to 30% within 10 days. The adsorption method is characterized in that a large specific surface area provided by a porous solid adsorbent is utilized, and phosphorus-containing substances in the wastewater are left on the surface of the adsorbent through adsorption precipitation, ion exchange and other processes, so that the purpose of removing organic phosphate is achieved. However, the method is only the transfer of the organic phosphate, does not degrade the organic phosphate, and is not beneficial to the subsequent operation of recovering phosphorus resources. Advanced oxidation techniques, which involve ozone catalytic oxidation, electrochemical oxidation, fenton and photocatalytic processes, degrade organic materials by generating very reactive free radicals (typically hydroxyl radicals). Although they are all effective in degrading phosphonate to phosphate, the degradation time required is too long, the dosage of the agent is large, the degradation efficiency fluctuates greatly and it is also necessary to increase the processing unit for recovering phosphorus.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for treating organic phosphate in a landfill leachate membrane concentrated solution. The treatment method aims to improve the treatment efficiency of phosphate in the membrane concentrated solution and reduce the cost.
In order to solve the technical problem, the invention is realized by the following scheme: the invention relates to a method for treating organic phosphate in landfill leachate membrane concentrated solution, which comprises the following steps:
preparing a device, wherein the device is provided with a reaction kettle, a photoelectric reactor arranged in the reaction kettle, a water inlet pipe arranged at the upper part of the outer side of the reaction kettle, a water outlet pipe arranged at the bottom surface of the reaction kettle and a filtering system arranged in the lower region of an inner cavity of the reaction kettle, and the photoelectric reactor comprises an electrochemical oxidation reaction device and a photochemical oxidation reaction device; the electrochemical oxidation reaction device comprises an anode and a cathode which are arranged in the reaction chamber and are oppositely arranged; the photochemical oxidation reaction device comprises a ballast control system and a plurality of ultraviolet lamp tubes, wherein the ballast control system is arranged in the reaction chamber and controls the ultraviolet lamp tubes to work;
step two, the pretreated wastewater 2 containing the organic phosphate enters a reaction kettle through a water inlet pipe 1, and 1mol/L NaOH solution and H are used2SO4Adjusting the pH value of the wastewater 2 to 4.5-7.5;
secondly, adding iron ion solution;
starting the electrochemical oxidation device and the photochemical oxidation device, and simultaneously opening the stirrer 7 to enable the liquid in the reaction kettle to react;
fourthly, in the electrochemical oxidation device, oxidizing chloride ions in the wastewater 2 on the surface of an anode 3 to generate a plurality of active chlorine substances, wherein the plurality of active substances comprise chlorine gas, hypochlorous acid and sodium hypochlorite, and ferric ions generate ferrous ions on the surface of a cathode 6, in the active chlorine substances, the hypochlorous acid and the ferrous ions are combined to generate a Fenton-like reaction to generate hydroxyl radicals, and the hydroxyl radicals oxidize organic phosphate in the wastewater 2;
the ballast control system 4 is used for controlling the work of the ultraviolet lamp tube 5, and the ultraviolet light emitted by the ultraviolet lamp tube 5 can not only convert chlorine and sodium hypochlorite into chlorine free radicals under the catalytic action of the ultraviolet light, but also further accelerate the Fenton-like reaction;
fifthly, combining the generated phosphate with iron ions to generate iron phosphate precipitate or adsorbing the phosphate by ferrihydrite to precipitate at the bottom of a reaction chamber of the reaction kettle;
step six, after 2-3 hours, the reaction is finished, a partition plate 8 in the filtering system is unfolded, the wastewater after organic phosphate ester treatment is filtered through a filtering layer 9 in the filtering system, the filtrate flows into a water storage layer 10 below the filtering layer 9, and finally the filtrate is discharged through a water outlet pipe 11;
and seventhly, cleaning the filter membrane and collecting the precipitated substances by an automatic back washing device of the filter layer 9.
Further, the wavelength of ultraviolet light emitted by the ultraviolet lamp tube is 254 nm.
Further, in the second step, the pH value is adjusted to 6.5.
Compared with the prior art, the invention has the beneficial effects that: the device is used for treating organic phosphate in wastewater, the electrochemical oxidation device can oxidize chloride ions in the wastewater to generate active chlorine, such as chlorine, hypochlorous acid, hydrogen peroxide and other oxidants, and the oxidants generate chlorine free radicals and hydroxyl free radicals under the catalysis of ultraviolet light, so that the effect of degrading the organic phosphate is achieved.
And secondly, the added iron ions can be used as a catalyst under the action of an electric field to perform Fenton-like reaction with hypochlorous acid, so that the yield of hydroxyl radicals and chlorine radicals is greatly increased, and the degradation efficiency of the organic phosphate is further improved.
Finally, iron ions can react with phosphate to generate iron phosphate or generate iron hydroxide to adsorb the phosphate, so that the recovery of phosphorus is realized. The invention provides a device for treating organic phosphate in wastewater, which can degrade the organic phosphate and simultaneously realize the recovery of phosphorus without additionally increasing a phosphorus recovery process.
Drawings
FIG. 1 is a schematic block diagram of the treatment method of the present invention.
FIG. 2 is a schematic view of the structure of the apparatus used in the processing method of the present invention.
Each reference symbol name: 1 water inlet pipe, 2 organic phosphate wastewater, 3 anodes, 4 ballast control systems, 5 ultraviolet lamps, 6 cathodes, 7 stirrers, 8 partition plates, 9 filter layers, 10 water storage layers and 11 water outlet pipes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, so that the advantages and features of the present invention can be more easily understood by those skilled in the art, and thus the protection scope of the present invention is more clearly and clearly defined. It should be apparent that the described embodiments of the present invention are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; the two elements may be directly connected or indirectly connected through an intermediate medium, or may be communicated with each other inside the two elements, or may be wirelessly connected or wired connected. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1: the concrete structure of the invention is as follows:
referring to the attached fig. 1-2, the method for treating organic phosphate in the landfill leachate membrane concentrated solution of the present invention comprises the following steps:
preparing a device, wherein the device is provided with a reaction kettle, a photoelectric reactor arranged in the reaction kettle, a water inlet pipe 1 arranged at the upper part of the outer side of the reaction kettle, a water outlet pipe 11 arranged at the bottom surface of the reaction kettle and a filtering system arranged in the lower region of an inner cavity of the reaction kettle, and the photoelectric reactor comprises an electrochemical oxidation reaction device and a photochemical oxidation reaction device; the electrochemical oxidation reaction device comprises an anode 3 and a cathode 6 which are arranged in the reaction chamber and are oppositely arranged; the photochemical oxidation reaction device comprises a ballast control system 4 and a plurality of ultraviolet lamp tubes 5 which are arranged in the reaction chamber, wherein the ballast control system 4 controls the plurality of ultraviolet lamp tubes 5 to work;
step two, the pretreated wastewater 2 containing the organic phosphate enters a reaction kettle through a water inlet pipe 1, and 1mol/L NaOH solution and H are used2SO4Adjusting the pH value of the wastewater 2 to 4.5-7.5;
secondly, adding iron ion solution;
starting the electrochemical oxidation device and the photochemical oxidation device, and simultaneously opening the stirrer 7 to enable the liquid in the reaction kettle to react;
fourthly, in the electrochemical oxidation device, oxidizing chloride ions in the wastewater 2 on the surface of an anode 3 to generate a plurality of active chlorine substances, wherein the plurality of active substances comprise chlorine gas, hypochlorous acid and sodium hypochlorite, and ferric ions generate ferrous ions on the surface of a cathode 6, in the active chlorine substances, the hypochlorous acid and the ferrous ions are combined to generate a Fenton-like reaction to generate hydroxyl radicals, and the hydroxyl radicals oxidize organic phosphate in the wastewater 2;
the ballast control system 4 is used for controlling the work of the ultraviolet lamp tube 5, and the ultraviolet light emitted by the ultraviolet lamp tube 5 can not only convert chlorine and sodium hypochlorite into chlorine free radicals under the catalytic action of the ultraviolet light, but also further accelerate the Fenton-like reaction;
fifthly, combining the generated phosphate with iron ions to generate iron phosphate precipitate or adsorbing the phosphate by ferrihydrite to precipitate at the bottom of a reaction chamber of the reaction kettle;
step six, after 2-3 hours, the reaction is finished, a partition plate 8 in the filtering system is unfolded, the wastewater after organic phosphate ester treatment is filtered through a filtering layer 9 in the filtering system, the filtrate flows into a water storage layer 10 below the filtering layer 9, and finally the filtrate is discharged through a water outlet pipe 11;
and seventhly, cleaning the filter membrane and collecting the precipitated substances by an automatic back washing device of the filter layer 9.
A preferred technical solution of this embodiment: the wavelength of the ultraviolet light emitted by the ultraviolet lamp tube 5 is 254 nm.
A preferred technical solution of this embodiment: in step two, the pH value is adjusted to 6.5.
Example 2:
in the first step, the device has the following specific structure:
the device comprises:
the photoelectric reactor comprises a reaction kettle, an electrochemical oxidation reaction device and a photochemical oxidation reaction device which are arranged in the reaction kettle, wherein the reaction kettle is provided with a reaction chamber and a filtering system, the filtering system is arranged at the lower region of the reaction chamber and comprises a filtering layer 9 and a partition plate 8, the partition plate 8 can be unfolded to enable the reaction chamber to be communicated with the filtering layer 9, the partition plate 8 can cover the filtering layer 9 to enable the reaction chamber to be separated from the filtering layer 9, and a water storage layer 10 is formed between the filtering layer 9 and the inner bottom surface of the reaction kettle;
the water inlet pipe 1 is connected to the upper part of the outer side of the reaction kettle and is used for inputting liquid into the reaction chamber;
the water outlet pipe 11 is connected to the bottom surface of the reaction kettle and used for outputting the liquid in the water storage layer 10;
and the stirrer 7 is arranged in the reaction kettle and is used for stirring the liquid input into the reaction chamber.
The anode 3 and the cathode 6 are both plate electrodes or electrodes with a net structure.
The anode 3 is a ruthenium iridium titanium electrode capable of chlorine evolution, and the cathode 6 is a stainless steel electrode.
The filter layer 9 is an automatic backwashing filter.
The automatic backwashing filter adopts a screen filter, the filter screen of the screen filter is a duplex stainless steel filter screen, and the aperture of each mesh of the filter screen is 80-110 μm, preferably 100 μm.
The ultraviolet lamp tube 5 is arranged in a quartz sleeve, and is arranged in parallel with the anode 3 and the cathode 6.
Example 3:
the wastewater comprises landfill leachate, and the landfill leachate forms a membrane concentrated solution.
Through detection, the concentration of the organic phosphate in the membrane concentrated solution is 12.4mg/L, and the concentration of chloride ions is 6060 mg/L.
Introducing the membrane concentrated solution into the photoelectric reactor of the invention, adding 90mg/L ferric trichloride, and adding 1mol/L NaOH solution and H2SO4The pH of the wastewater was adjusted to 6.5. Wherein the working density of the electrochemical oxidation device is 50A/m2Electrochemical oxidation andthe photochemical oxidation is carried out simultaneously, after working for 1 hour, the recovery rate of the organic phosphate reaches 51.3 percent, and after working for 2.5 hours, the recovery rate of the organic phosphate reaches 93.6 percent.
Example 4:
the wastewater also includes printing and dyeing wastewater.
The concentration of the organophosphate contained in the printing and dyeing wastewater was 6.57mg/L, and the concentration of chloride ions was 3721 mg/L. Introducing the printing and dyeing wastewater into a photoelectric reactor, adding 60mg/L ferric trichloride, and adding 1mol/L NaOH solution and H2SO4The pH value of the wastewater is adjusted to 6.5, and the working density of the electrochemical oxidation device is 50A/m2And the electrochemical oxidation and the photochemical oxidation are carried out simultaneously, the recovery rate of the organic phosphate reaches 73.4 percent after working for 2 hours, and the recovery rate of the organic phosphate reaches 96.3 percent after working for 3 hours.
Example 5:
the wastewater also comprises chemical wastewater.
In the chemical wastewater, the phosphorus concentration of the organic phosphonate is 7.21mg/L, and the chloride ion concentration is 4356 mg/L. Introducing the wastewater into a photoelectric reactor, adding 65mg/L ferric trichloride, and adding 1mol/L NaOH solution and H2SO4The pH value of the wastewater is adjusted to 6.5, and the working density of the electrochemical oxidation device is 25A/m2The electrochemical oxidation and the photochemical oxidation are carried out simultaneously, the recovery rate of the organic phosphate reaches 71.3 percent after working for 2 hours, and the recovery rate of the organic phosphate reaches 94.1 percent after working for 3 hours.
In summary, the method for treating phosphate ester in membrane concentrate of the present invention is used for treating organic phosphate ester in wastewater, and in the method, the electrochemical oxidation apparatus can oxidize chloride ions in wastewater to generate active chlorine, such as chlorine, hypochlorous acid, hydrogen peroxide, and other oxidants, which generate chlorine radicals and hydroxyl radicals under the catalysis of ultraviolet light, thereby achieving the effect of degrading organic phosphate ester. And secondly, the added iron ions can be used as a catalyst under the action of an electric field to perform Fenton-like reaction with hypochlorous acid, so that the yield of hydroxyl radicals and chlorine radicals is greatly increased, and the degradation efficiency of the organic phosphate is further improved. Finally, iron ions can react with phosphate to generate iron phosphate or generate iron hydroxide to adsorb the phosphate, so that the recovery of phosphorus is realized. The invention provides a device for treating organic phosphate in wastewater, which can degrade the organic phosphate and simultaneously realize the recovery of phosphorus without additionally increasing a phosphorus recovery process.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (3)
1. A method for treating organic phosphate in landfill leachate membrane concentrated solution is characterized by comprising the following steps:
preparing a device, wherein the device is provided with a reaction kettle, a photoelectric reactor arranged in the reaction kettle, a water inlet pipe (1) arranged at the upper part of the outer side of the reaction kettle, a water outlet pipe (11) arranged at the bottom surface of the reaction kettle and a filtering system arranged in the lower area of an inner cavity of the reaction kettle, and the photoelectric reactor comprises an electrochemical oxidation reaction device and a photochemical oxidation reaction device; the electrochemical oxidation reaction device comprises an anode (3) and a cathode (6) which are arranged in the reaction chamber and are oppositely arranged; the photochemical oxidation reaction device comprises a ballast control system (4) and a plurality of ultraviolet lamp tubes (5) which are arranged in the reaction chamber, wherein the ballast control system (4) controls the plurality of ultraviolet lamp tubes (5) to work;
step two, the pretreated wastewater 2 containing the organic phosphate enters a reaction kettle through a water inlet pipe 1, and 1mol/L NaOH solution and H are used2SO4Adjusting the pH value of the wastewater 2 to 4.5-7.5;
secondly, adding iron ion solution;
starting the electrochemical oxidation device and the photochemical oxidation device, and simultaneously opening the stirrer 7 to enable the liquid in the reaction kettle to react;
fourthly, in the electrochemical oxidation device, oxidizing chloride ions in the wastewater 2 on the surface of an anode 3 to generate a plurality of active chlorine substances, wherein the plurality of active substances comprise chlorine gas, hypochlorous acid and sodium hypochlorite, and ferric ions generate ferrous ions on the surface of a cathode 6, in the active chlorine substances, the hypochlorous acid and the ferrous ions are combined to generate a Fenton-like reaction to generate hydroxyl radicals, and the hydroxyl radicals oxidize organic phosphate in the wastewater 2;
the ballast control system 4 is used for controlling the work of the ultraviolet lamp tube 5, and the ultraviolet light emitted by the ultraviolet lamp tube 5 can not only convert chlorine and sodium hypochlorite into chlorine free radicals under the catalytic action of the ultraviolet light, but also further accelerate the Fenton-like reaction;
fifthly, combining the generated phosphate with iron ions to generate iron phosphate precipitate or adsorbing the phosphate by ferrihydrite to precipitate at the bottom of a reaction chamber of the reaction kettle;
step six, after 2-3 hours, the reaction is finished, a partition plate 8 in the filtering system is unfolded, the wastewater after organic phosphate ester treatment is filtered through a filtering layer 9 in the filtering system, the filtrate flows into a water storage layer 10 below the filtering layer 9, and finally the filtrate is discharged through a water outlet pipe 11;
and seventhly, cleaning the filter membrane and collecting the precipitated substances by an automatic back washing device of the filter layer 9.
2. The method for treating organic phosphate in landfill leachate membrane concentrate of claim 1, wherein the wavelength of the ultraviolet light emitted by the ultraviolet lamp tube (5) is 254 nm.
3. The method according to claim 1, wherein in step two, the pH is adjusted to 6.5.
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| WO2024022192A1 (en) * | 2022-07-26 | 2024-02-01 | 苏州科技大学 | Method and system for treating aged landfill leachate |
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