CN110330166B - High-efficient environmental protection industrial waste water treatment system - Google Patents
High-efficient environmental protection industrial waste water treatment system Download PDFInfo
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- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 27
- 230000007613 environmental effect Effects 0.000 title claims description 3
- 238000004065 wastewater treatment Methods 0.000 title abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 238000001962 electrophoresis Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000005345 coagulation Methods 0.000 claims abstract description 12
- 230000015271 coagulation Effects 0.000 claims abstract description 12
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims description 41
- 229910052567 struvite Inorganic materials 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 38
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- 238000007711 solidification Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000008023 solidification Effects 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
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- 150000002500 ions Chemical class 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 75
- 230000008569 process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000001174 ascending effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910017917 NH4 Cl Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012070 reactive reagent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 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
- 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
- C02F1/30—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
- C02F1/46—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
-
- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4696—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrophoresis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a high-efficiency environment-friendly industrial wastewater treatment system, which relates to the technical field of organic wastewater treatment, and comprises the following components: the collecting tank, the first separating device, the first electrophoresis reactor, the second crystallization coagulation reactor, the third crystallization coagulation reactor and the fourth photoelectrochemistry reactor are solidified through two-stage crystallization, nitrogen and phosphorus in industrial wastewater can be effectively removed, and pollutants in the industrial wastewater can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of organic wastewater treatment. More particularly, the present invention relates to an efficient and environmentally friendly industrial wastewater treatment system.
Background
Industrial waste water from food processing and paper making contains organic substances such as carbohydrates, proteins, fats and oils, and lignin. These substances are present in the sewage in a suspended or dissolved state and can be decomposed by biochemical action of microorganisms. Oxygen is consumed in its decomposition process and is therefore referred to as an oxygen-consuming contaminant. Such contaminants can cause a reduction in dissolved oxygen in the water, affecting the growth of fish and other aquatic organisms. After the dissolved oxygen in water is exhausted, the organic matter is anaerobically decomposed to generate hydrogen sulfide, ammonia, mercaptan and other bad smells, which deteriorates the water quality. The organic matter components in the water body are very complex, and the concentration of the oxygen-consuming organic matter is usually expressed by the oxygen consumption in the biochemical decomposition process of the oxygen-consuming substance in unit volume of water.
The physical and chemical method is usually used as a pretreatment means for organic wastewater treatment, and the purpose of pretreatment is to remove organic matters, improve biochemical property, reduce biochemical treatment load and improve treatment efficiency by recovering useful components in wastewater or treating some difficultly biodegradable matters. The physical and chemical methods generally used include extraction, adsorption, concentration, ultrasonic degradation and the like.
In recent years, a great deal of research has been conducted to evaluate the possibility of using struvite as a fertilizer. Struvite is a poorly water-soluble white crystal whose main component is magnesium ammonium phosphate hexahydrate (MgNH4PO4#6H 2O). By forming the struvite, the removal and the recycling of nitrogen and phosphorus in the industrial wastewater can be realized. However, the prior struvite production efficiency is low, and ammonia and phosphate are lost more in the production process.
Disclosure of Invention
In order to solve the defect of removing nitrogen and phosphorus in industrial wastewater by using struvite in the prior art, the invention provides a high-efficiency environment-friendly industrial wastewater treatment system.
An efficient and environmentally friendly industrial wastewater treatment system, the system comprising: the device comprises a collecting tank, a first separation device, a first electrophoresis reactor, a second crystallization solidification reactor, a third crystallization solidification reactor and a fourth photoelectrochemistry reactor;
wherein the collection tank stores the industrial wastewater;
a first separation device for extracting solid organic components from the industrial wastewater to obtain waste liquid containing nitrogen ammonium (NH4+) and phosphate (HPO 42-);
a first electrophoresis reactor for introducing the waste liquid and separating cations and anions by using an electric field to form a first concentrated ammonia solution, a second concentrated phosphate solution and a third organic liquid;
a second crystallization-solidification reactor, wherein the first concentrated ammonia solution S1, the second concentrated phosphate solution S2, and the solution containing magnesium S4 are introduced in a predetermined stoichiometric ratio, wherein the solutions S1, S2, S4 are mixed in a first intermediate solution S5 by incoming air, to obtain crystals and granules of struvite and a first purified solution S6;
a third crystallization solidification reactor, wherein the first purified solution S6 and the sodium hydroxide solution S9 extracted from the second reactor, wherein the solutions S6, S9 are mixed in a second intermediate solution S7 by incoming air to obtain further residual crystals and granular struvite and a second purified solution S8;
a fourth photoelectrochemical reactor having the second purified solution extracted from the third reactor, wherein all nitrogen is extracted from the third purified solution by a photoelectric process and a purified liquid wastewater is obtained.
Further, the system comprises a first tank and a second tank for receiving the first ammonia solution and the second phosphate solution extracted from the first electrophoresis reactor, respectively, a third tank for containing a solution containing magnesium for providing the second crystallising coagulation reactor and a delivery device for delivering the solutions S1, S2, S4 to the second crystallising coagulation reactor in a controlled manner.
Further, the system further comprises an extraction device for extracting the crystallized and coagulated struvite from the second and third crystallizing and coagulating reactors; a second separation device for separating the struvite from a residual liquid; and a drying device for drying the struvite.
Further, the system also supplies the residual liquid separated by the second separation device to the second reactor.
Further, the system also extracts the third organic liquid from the first electrophoresis reactor and supplies the third organic liquid to the fourth photoelectrochemical reactor.
Further, the system wherein the second and third crystallizing and solidifying reactors comprise:
an air inflow device disposed at a reaction zone of the crystallization and solidification reactor, the first intermediate solution S5 and the second intermediate solution S7 crystallizing and solidifying the struvite;
a heat exchange device arranged in a mixing zone of the crystallization solidification reactor and used for adjusting the temperature of the first intermediate solution S5 and the second intermediate solution S7;
a temperature detection device;
a pH value detection device for detecting and controlling the pH values of the first intermediate solution S5 and the second intermediate solution S7.
Further, in the system, the second and third crystallizing and solidifying reactors include respective outer tanks having a conical shape with a conical bottom.
Further, in the system, wherein the heat exchange means comprise tubular heat exchangers open at both ends and cylindrical, said heat exchangers being coaxially placed in respective outer tanks, comprising an inner mixing zone and an outer recirculation zone delimited by said outer tanks.
Further, in the system, a downward flow of liquid passes through the mixing zone and an upward flow of liquid passes through the recirculation zone.
Further, in the system, wherein the second and third crystallizing coagulation reactors include respective collecting devices, the first purified solution S6 and the second purified solution S8 are collected from an external storage tank.
Further, in the system, wherein the fourth photoelectrochemical reactor comprises an anode and a cathode, the direct current is supplied by a power supply; and an ultraviolet emitting device disposed between the anode and the cathode.
The invention has the advantages that: the treatment system optimizes the struvite crystallization rate by adjusting basic variables such as pH, temperature and concentration of the reactant solution, can effectively remove nitrogen and phosphorus in the industrial wastewater R, and produces struvite. Through one-stage separation and two-stage crystallization and solidification, nitrogen and phosphorus in the industrial wastewater can be effectively removed, and pollutants in the industrial wastewater can be effectively reduced.
Drawings
FIG. 1 is a schematic view of a high efficiency, environmentally friendly industrial wastewater treatment system of the present invention;
FIG. 2 is a schematic of a second and third crystallization and solidification reactor;
fig. 3 is a schematic view of a fourth photobioreactor.
Detailed Description
Referring to fig. 1 to 3, the high-efficiency and environment-friendly industrial wastewater treatment system 1 of the present invention comprises a collection tank 2 and a first separation device 3, and extracts solid organic components from the industrial wastewater to obtain a waste liquid L containing nitrogen ammonium (NH4+) and phosphate (HPO 42-).
The first separating device 3 is used for screening and filtering from a liquid flow particles capable of a size greater than 250 microns.
The first separation device 3 causes, by means of the solid/liquid separation step carried out, a significant change in the composition of the industrial waste water R, in particular a reduction in COD (chemical oxygen demand), an increase in the percentage of ammonia and a reduction in phosphorus.
The treatment system 1 comprises a first electrophoresis reactor 4 for treating the wastewater L produced by the first separation device 3. Performing electrophoresis treatment, and separating cations from anions to form a first concentrated ammonia solution S1, a second concentrated phosphate solution S2 and a third organic solution S3;
the first electrophoresis reactor 4 comprises a first tank 40 having a cylindrical shape, both ends of which are respectively provided with an anode 41 made of platinum and a cathode 42 made of graphite, and a cathode made of graphite, and an electric field is generated by a continuous current, and through electrophoresis treatment, nitrogen-rich ammonium (NH4+) in the waste liquid L migrates toward the cathode 42 and phosphate-rich ammonium (HPO42-) migrates toward the anode 41, wherein two ionic membranes are provided for separating a first concentrated ammonia solution S1 and a second concentrated phosphate solution S2.
Electrophoresis is an electrokinetic phenomenon very similar to electrolysis. Wherein in the fluid the charged particles migrate to influence the applied electric field generated by the pair of electrodes. This particle, if positively charged, will move towards the cathode. If they are negatively charged, they face the anode. In the first reactor 4 the ions NH4+ move towards the cathode 41 distribution, thus producing a first concentrated ammonia solution S1, while the ions HPO 42-towards the anode 42 thus produces a second concentrated phosphate solution S2.
During the electrophoresis process, the biogas generated from the waste liquid L can be eliminated by the prior art.
The treatment system 1 further comprises a second crystallization coagulation reactor 5, wherein said first concentrated ammonia solution S1, said second concentrated phosphate solution S2 and a solution containing magnesium S4 are introduced in a predetermined stoichiometric ratio, wherein said solutions S1, S2, S4 are mixed in a first intermediate solution S5 by incoming air to obtain struvite ST in crystals and granules/flocs and a first purified solution S6.
The stoichiometric ratio between the three solutions (N: P: Mg) included a minimum value equal to 1: 1 (in kg by weight, ratio 1: 2.2: 1), a maximum value equal to 1: 1.5, and a percentage of recoverable ammonia between 95 and 98%.
The fourth solution S4 is one of magnesium chloride (MgCl2) \ magnesium hydroxide (mg (oh)2), magnesium oxide (MgO), and brine.
The chemical reaction, carried out by mixing the three solutions (NH4 Cl; Na2HPO 4; MgCl 2.6H2O) with air, results in the formation of crystalline and solidified struvite, which can affect the content of ammonia present in the solution and can recover approximately 90% of the phosphorus.
The treatment system 1 further comprises a third crystallization solidification reactor 6, wherein the first purified solution S6 and the sodium hydroxide solution S9 extracted from said second reactor 5, wherein said solutions S6, S9 are mixed in a second intermediate solution S7 by incoming air to obtain further residual crystals and solidified struvite ST and a second purified solution S8.
The treatment system 1 also comprises a fourth photoelectrochemical reactor 7 having said second purification solution S8 extracted from said third reactor 6, wherein all nitrogen is extracted from said third purification solution S8 and purified liquid wastewater S10 is obtained by means of a photoelectric process.
The treatment system 1 also comprises a first tank 11 for receiving the first concentrated ammonia solution S1 extracted from the first reactor 4 and a second tank 12 for receiving the second concentrated phosphate solution S2, respectively, a third tank 13 for containing a magnesium-containing solution S4 that provides the second reactor 5; the distribution and delivery device 14 delivers the solutions S1, S2, S4 to the second reactor 5 in a controlled manner. Wherein the desired stoichiometric ratio is determined according to the operating conditions.
The treatment system 1 further comprises extraction means 8, 9 for extracting said crystalline agglomerated struvite from said second reactor 5 and said third reactor 6; a second liquid/solid separation device 15 for separating the struvite from the residual liquid LR; and a drying device 16 for drying the struvite ST.
The extraction device comprises a first dryer associated with the second reactor 5 and a second dryer 9 associated with the second reactor 6 for recovering the crystals and the coagulum of struvite. The precipitate 52, 62 in each zone of the reactor 5, 6 is collected and sent to the second separation device 15.
The second separating means 15 comprises a screen with 250 μm apertures. The liquid residue LR recovered from the separation of struvite ST is returned in a recycle to the second reactor 5.
The fourth photoelectrochemical reactor 7 is also supplied with the third organic liquid S3 obtained from the first reactor 4.
Referring to fig. 2, the second and third reactors 5 and 6 respectively include air introduction means 17, 18 disposed in reaction zones 51, 61, the reaction zones 51, 61 having a suitable shape and volume to ensure a proper residence time, and precipitation or accumulation zones 52, 62 to collect the precipitated struvite starting from the first and second intermediate solutions S5 and S7 respectively.
The second reactor 5 and the third reactor 6 comprise respective reservoirs 50, 60 having a form suitable for ensuring the recirculation of the fluidized bed produced therein, and corresponding collecting means, comprising an overflow channel provided at the top of the reactors. In particular, the reactors 5, 6 have a corresponding height to ensure an upward velocity of 0.50m/h of liquid flow and sedimentation and thus the achievement of all crystals and clots at the bottom of the reactors.
Each heat exchange device 19, 20 is provided in correspondence with the center of the mixing zone 52, 62 of the reactor 5, 6 to adjust the temperature of the first intermediate solution S5 and the second intermediate solution S7, respectively, and to promote the struvite crystallization and coagulation process.
The second reactor 5 and the third reactor 6 are also provided with means for detecting the temperature of the solution, means for measuring and adjusting the flow rate at the input of the solution, and means for detecting and controlling the pH of the first intermediate solution S5 and the second intermediate solution S7.
The second reactor 5 comprises a second outer tank 50 of cylindrical shape, the outer tank 50 being of conical configuration, the first concentrated ammonia solution S1 being introduced from the top of the outer tank 50, the second concentrated phosphate solution S2 and the solution S4 containing magnesium being introduced in a radial direction of the reaction zone 51. The temperature of the solution flowing into the reactor is controlled at 45-50 deg.C, preferably 50 deg.C.
The second reactor 5 comprises a first heat exchange means 19 comprising a first tube-in-tube shaped heat exchanger open at both ends and having a cylindrical shape, located coaxially to the outer tank 50.
A hot fluid is introduced inside the tube bundle of the heat exchange device 19, for example hot water, for regulating the temperature of the first intermediate S5. A thermostat may be provided to regulate the flow of hot water to control the precise process temperature.
The first exchange means 19 has a mixing zone 53 in its interior and cooperates with the outer tank 50 with an annular recirculation zone 54.
In operation, a descending liquid stream is produced in the first exchanger 19 through the mixing zone 53 and an ascending liquid stream of partially removed struvite and reagent in the annulus or recirculation zone 54 is produced which allows for expansion of the crystalline particles.
In order to adjust the pH of the first intermediate solution S5 and to ensure mixing of the air provided by the first means for introducing air 17, the first means for introducing air 17 comprises a micro bubble diffuser having a supply from the compressor 30. The introduction of air is controlled by a turbidimeter and a pH meter, respectively. The pH meter is located in the reaction zone 51 and the turbidimeter is located in the precipitation zone 52. From the readings of these two instruments, the flow rates can be adjusted to intervene to ensure that the flows of the solutions S1, S2, S4 react with each other to obtain the struvite precipitation process with maximum efficiency.
The rising liquid flow from the first purified solution S6 was collected in the top channel of the second reactor 5 and sent to the third reactor 6 for crystallization.
The third reactor 6 is substantially identical to the second reactor 5 and comprises a third external tank 60, the external tank 50 having a conical configuration, the first purification solution S6 being introduced from the internal top of the third external tank 60, the sodium hydroxide solution S9 being introduced in the reaction zone 61. The two solutions S6, S9 were introduced with air and mixed to form a second intermediate solution S7.
The third reactor 6 comprises second heat exchange means 20 comprising a second tube-in-tube exchanger open at both ends and having a cylindrical shape, in a coaxial position inside a second outer tank 60. The second heat exchanger tube bundle is passed through 20 a hot fluid, in particular hot water, for conditioning the intermediate solution S6 in the second reactor 6. The thermostat regulates the flow of hot water and accurately controls the process temperature.
The second exchange means 20 has a mixing zone 63 in its interior and cooperates with the outer tank 60 with an annular recirculation zone 64.
Likewise, a descending liquid stream is produced in the second exchanger 20 through the mixing zone 63 and an ascending liquid stream of partially removed struvite and reagent in the annular or recirculation zone 64 which permits expansion of the crystalline particles.
In order to adjust the pH of the second intermediate solution S7 and to ensure mixing of the air provided by the second means for introducing air 18, the second means for introducing air 18 comprises a micro bubble diffuser having a supply from a compressor 19. The introduction of air is controlled by a turbidimeter and a pH meter, respectively. The flow rates and volumes of the second purification solution S8 and the sodium hydroxide solution S9 can be adjusted from the readings of these two instruments to obtain the struvite precipitation process with maximum efficiency. In particular, the pH of the sodium hydroxide solution is adjusted to a pH of 11 and 12, in particular 12.
The ascending liquid flow coming from the second purified solution S8 is collected in a corresponding channel at the top of the third reactor 6 and sent to the fourth photoelectrochemical reactor 7.
Referring to fig. 3, the fourth photoelectrochemical reactor 7 includes a can 71 having an anode 22 made of platinum and a cathode made of graphite, supplied with direct current at an intensity ranging from 0.3A to 1.9A by a power supply device 24, and an ultraviolet ray emitting device 25 disposed directly on the anode 22 and the cathode 23.
The ultraviolet ray emitting means 25 comprises one or more ultraviolet lamps, and is arranged side by side at one side of the anode 22 and the cathode 23 of the fourth reactor 7.
The driving means comprise a first pump 26 and a second pump 27, allowing to supply the fourth reactor 7 with the solutions S3, S8, and to recirculate the latter to ensure the retention time. The current intensity supplied by the anode and cathode is adjusted by appropriate control methods to adjust the initial pH.
The temperature in the fourth reactor 7 is controlled at 25 and 45 c, preferably 40 c. The fourth reactor 7 comprises an outer gap 28 with a circulating water of controlled temperature. The chlorine and sodium in solution in the fourth reactor 7 are treated according to the following formulas:
2Cl-＝Cl2+2e-
Cl2+H2O＝HOCl+HCl
2NH4+3HOCL＝N2+5H++3Cl-+3H2O
due to the influence of the charge, the photons generated by the ultraviolet light 25 act and the interacting ions in the ammonia molecules break.
In this process, the NH4 molecule is essentially broken, nitrogen and hydrogen are generated, nitrogen is in a free state, and hydrogen reacts with the hydroxyl group to form water. This process results from the presence of chloride, which is converted by electrochemical conversion into hypochlorite, a strong oxidizing compound and hydroxyl radicals which are capable of providing water generation.
After treatment, ammonium nitrate (NH4-N), nitrite (NO3-N, NO2-N) could not be detected, and any trace of nitrogen could be completely eliminated from the solution.
The purified liquid S10 obtained as a liquid after the discharge of the photoelectrolyte from the fourth reactor 7 was slightly contaminated.
The initial industrial waste water R is highly contaminated and has a COD content of approximately 13000mg/l, which is reduced to 8500mg/l after separation by the first separation device 3 and to 3500mg/l after the second and third crystallization and coagulation reactions.
Reactive reagents, such as sulfuric acid, can be introduced into the second reactor 5 to increase clot crystallization.
The treatment system optimizes the struvite crystallization rate by adjusting basic variables such as pH, temperature and concentration of the reactant solution, can effectively remove nitrogen and phosphorus in the industrial wastewater R, and produces struvite. Through one-stage separation and two-stage crystallization and solidification, nitrogen and phosphorus in the industrial wastewater can be effectively removed, and pollutants in the industrial wastewater can be effectively reduced.
Claims (1)
1. The utility model provides a high-efficient environmental protection industrial waste water processing system which characterized in that: the system (1) comprises: the device comprises a collecting tank (2), a first separating device (3), a first electrophoresis reactor (4), a second crystallization solidification reactor (5), a third crystallization solidification reactor (6) and a fourth photoelectrochemistry reactor (7);
wherein a collection tank (2) stores the industrial waste water (R);
a first separation device (3) for extracting solid organic components (F) from the industrial waste water (R) to obtain nitrogen-containing ammonium (NH)4 +) And Phosphates (HPO)4 2-) The waste liquid (L);
a first electrophoresis reactor (4) into which the waste liquid (L) is introduced, and which separates cations and anions using an electric field to form a first concentrated ammonia solution (S1), a second concentrated phosphate solution (S2), and a third organic liquid (S3);
a second crystallization-solidification reactor (5), wherein the first concentrated ammonia solution (S1), the second concentrated phosphate solution (S2) and the solution containing magnesium (S4) are introduced in a predetermined stoichiometric ratio, wherein the first concentrated ammonia solution (S1), the second concentrated phosphate solution (S2) and the solution containing magnesium (S4) are mixed in a first intermediate solution (S5) by incoming air, to obtain crystalline and granular Struvite (ST) and a first purified solution (S6);
a third crystallizing and coagulating reactor (6), wherein the first purified solution (S6) extracted from the second crystallizing and coagulating reactor (5) is mixed in a second intermediate solution (S7) by entering air with a sodium hydroxide solution (S9) introduced outside the third crystallizing and coagulating reactor (6) to obtain further residual crystals and granular Struvite (ST) and a second purified solution (S8);
a fourth photoelectrochemical reactor (7) having the second purified solution (S8) extracted from the third solidification reactor (6), wherein all nitrogen is extracted from the second purified solution (S8) by a photoelectric method and a purified liquid wastewater (S10) is obtained;
further comprising a first tank (11) and a second tank (12) for receiving respectively the first concentrated ammonia solution (S1) and the second concentrated phosphate solution (S2) extracted from the first electrophoresis reactor (4), a third tank (13) for containing a magnesium-containing solution (S4) for supplying the second crystallising coagulation reactor (5) and a delivery device (14) for delivering in a controlled manner the first concentrated ammonia solution (S1), the second concentrated phosphate solution (S2) and the magnesium-containing solution (S4) to the second crystallising coagulation reactor (5);
further comprising extraction means (8, 9) for extracting said crystallized and coagulated Struvite (ST) from said second crystallization and coagulation reactor (5) and said third crystallization and coagulation reactor (6);
-second separation means (15) for separating the struvite from a residual Liquid (LR);
and a drying device (16) for drying the Struvite (ST);
wherein the residual Liquor (LR) separated by the second separating device (15) is fed to the second crystallization solidification reactor (5);
wherein the third organic liquid (S3) is extracted from the first electrophoresis reactor (4) and is supplied to the fourth photoelectrochemical reactor (7);
wherein the second and third crystallization solidification reactors (5, 6) comprise:
an air inflow device (17, 18) provided at a reaction zone (51, 61) of the crystallization-solidification reactor (5, 6), the first intermediate solution (S5) and the second intermediate solution (S7) crystallizing-solidifying the Struvite (ST);
heat exchange means (19, 20) arranged in the mixing zone (53, 63) of the crystallization solidification reactor (5, 6) to regulate the temperature of the first intermediate solution (S5) and the second intermediate solution (S7);
the air inflow means (17, 18) comprise a diffuser with microbubbles fed by a compressor (19);
a temperature detection device;
pH value detection means for detecting and controlling pH values of the first intermediate solution (S5) and the second intermediate solution (S7);
the second (5) and third (6) crystallization solidification reactors comprise respective external tanks (50, 60) having conical-shaped tanks with a conical bottom;
wherein said heat exchange means (19, 20) comprise tubular heat exchangers open at both ends and cylindrical, placed coaxially in respective outer tanks (50, 60), comprising an inner mixing zone (53, 63) and an outer recirculation zone (54, 64) delimited from said outer tanks (50, 60);
wherein a downward liquid flow passes through the mixing zone (53, 63) and an upward liquid flow passes through the recirculation zone (54, 64);
wherein the fourth photoelectrochemical reactor (7) comprises an anode (22) and a cathode (23), the direct current being provided by a power supply means (24); and an ultraviolet emitting device (25) disposed between the anode (22) and the cathode (23);
the chlorine and sodium in solution in the fourth photoelectrochemical reactor (7) are treated according to the following formulae:
2Cl-＝Cl2+2e-
Cl2+H2O＝HOCl+HCl
2NH4+3HOCL＝N2+5H++3Cl-+3H2O
due to the influence of electric charges, photons generated by the ultraviolet ray emitting device (25) act, and interacting ions in ammonia molecules are broken;
the fourth photoelectrochemical reactor (7) is also supplied with the third organic liquid (S3) obtained from the first electrophoresis reactor (4).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001293482A (en) * | 2000-04-14 | 2001-10-23 | Ebara Corp | Dephosphorizing device |
| CN101298324A (en) * | 2008-04-11 | 2008-11-05 | 浙江大学 | Apparatus for reclaiming sewerage nitrogen and phosphor by ammoniomagnesium phosphate crystal method and method thereof |
| CN102139975A (en) * | 2011-02-22 | 2011-08-03 | 南京大学 | Method for recovering phosphorus in crystallization way from semiconductor industrial waste water |
| CN102690001A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for treating sewage with high ammonia, nitrogen and phosphorus contents in livestock and poultry farms by chemical precipitation |
| CN105481127A (en) * | 2016-01-05 | 2016-04-13 | 浙江大学 | System for treating cultivation recycled-water through electrolysis-ultraviolet combination |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001293482A (en) * | 2000-04-14 | 2001-10-23 | Ebara Corp | Dephosphorizing device |
| CN101298324A (en) * | 2008-04-11 | 2008-11-05 | 浙江大学 | Apparatus for reclaiming sewerage nitrogen and phosphor by ammoniomagnesium phosphate crystal method and method thereof |
| CN102139975A (en) * | 2011-02-22 | 2011-08-03 | 南京大学 | Method for recovering phosphorus in crystallization way from semiconductor industrial waste water |
| CN102690001A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for treating sewage with high ammonia, nitrogen and phosphorus contents in livestock and poultry farms by chemical precipitation |
| CN105481127A (en) * | 2016-01-05 | 2016-04-13 | 浙江大学 | System for treating cultivation recycled-water through electrolysis-ultraviolet combination |
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