CN110182928A - A kind of integrated waste-water treater, method and system - Google Patents
A kind of integrated waste-water treater, method and system Download PDFInfo
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- CN110182928A CN110182928A CN201910427827.3A CN201910427827A CN110182928A CN 110182928 A CN110182928 A CN 110182928A CN 201910427827 A CN201910427827 A CN 201910427827A CN 110182928 A CN110182928 A CN 110182928A
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- zero
- accommodating cavity
- valent iron
- ions
- persulfate
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- 239000002351 wastewater Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 105
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 61
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 55
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 5
- 231100000719 pollutant Toxicity 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 48
- 229960004887 ferric hydroxide Drugs 0.000 claims description 35
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 ruthenium ions Chemical class 0.000 claims description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 16
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 13
- 239000010865 sewage Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000000149 penetrating effect Effects 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 48
- 230000003647 oxidation Effects 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 16
- 150000003254 radicals Chemical class 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 238000009285 membrane fouling Methods 0.000 abstract 1
- 239000011797 cavity material Substances 0.000 description 53
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 238000000926 separation method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 238000005276 aerator Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- 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)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of integrated waste-water treater, method and system, on the one hand since UF membrane and persulfate advanced oxidation reaction are integrated, the free radical that persulfate advanced oxidation reaction is formed being capable of oxidation of organic compounds, metal complex and inorganic matter, metal hydroxides wadding body is due to absorption, the effects of complexing is with co-precipitation, it is removed while realizing multiple pollutant, these features can greatly reduce the irreversible membrane fouling through filter membrane, reduce the stifled probability of filter membrane dirt, and filter membrane is in accommodating chamber, the disturbance of mixer bring can make the iron hydroxide wadding body gathered on filter membrane constantly disturb simultaneously, zero-valent iron particle is disturbed in filter membrane surface, it can play the role of online Membrane cleaning in conjunction with generated in-situ free-radical oxidation agent, and then further mitigate the burden of filter membrane, further prevent filter membrane dirt stifled , compared to persulfate advanced oxidation reaction and UF membrane non-integral device, the stifled phenomenon of filter membrane dirt is dramatically reduced, can be used for serialization wastewater treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an integrated wastewater treatment device, method and system.
Background
The persulfate advanced oxidation uses transition metal ions as an activator and uses persulfate (S)2O8 2-) The wastewater treatment method for chemical oxidation generates sulfate radical through the reaction of transition metal ions and persulfate, and the sulfate radical can destroy organic matters in the wastewater or complexes of the organic matters and heavy metals, thereby achieving the purpose of wastewater degradation. The existing wastewater treatment technology based on persulfate advanced oxidation still has a plurality of defects, and the improvement space exists.
Disclosure of Invention
In order to solve the defects, the application improves the wastewater treatment technology of persulfate advanced oxidation or persulfate-like advanced oxidation, and combines the persulfate advanced oxidation or persulfate-like advanced oxidation with the membrane separation technology to form an integrated wastewater treatment device, method and system.
An embodiment of an aspect of the present invention provides an integrated wastewater treatment apparatus, including:
a device body having a receiving cavity;
the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity;
a second charging device for charging zero-valent iron particles into the accommodating chamber;
a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles;
the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide flocs;
the filtering membrane assembly comprises a filtering membrane arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and
and the zero-valent iron particle separator is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, is used for separating and discharging zero-valent iron particles in the ferric hydroxide flocs, and throws the separated zero-valent iron particles into the accommodating cavity again.
In a preferred embodiment, the first investor includes:
a persulfate liquid storage tank for storing the persulfate solution;
a wastewater tank for storing the wastewater to be treated; and
the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity; or,
the first throw-in device includes:
a persulfate liquid storage tank for storing the persulfate solution;
a wastewater communication pipeline communicated with a wastewater discharge port of a production system; and
and the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity.
In a preferred embodiment, the first injector further comprises:
and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions.
In a preferred embodiment, the filter membrane is a ceramic membrane.
In a preferred embodiment, further comprising: a sewage draining device;
the sewage draining device comprises: the sewage pump and the sludge collector are used for collecting ferric hydroxide flocs and pollutants settled in the accommodating cavity.
In a second aspect, an embodiment of the present invention provides an integrated wastewater treatment method, including:
putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;
mixing the persulfate solution, the wastewater to be treated and the zero-valent iron particles in the containing cavity;
adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range within a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;
adjusting the pH value of the reaction environment in the containing cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;
collecting liquid penetrating through a filter membrane arranged in the accommodating cavity by suction, wherein the filter membrane is provided with a plurality of pore channels capable of preventing the ferric hydroxide flocs from penetrating;
separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and throwing the separated zero-valent iron particles into the accommodating cavity again;
the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity.
In a preferred embodiment, further comprising:
premixing the persulfate solution and the wastewater to be treated;
mixing persulfate solution in the holding chamber, the wastewater to be treated and the zero-valent iron particles, comprising:
and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.
In a preferred embodiment, further comprising:
and collecting ferric hydroxide floc settled in the containing cavity.
In a preferred embodiment, further comprising:
and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.
In a third aspect, the embodiment of the invention provides an integrated wastewater treatment system, which comprises the integrated wastewater treatment device.
The invention has the beneficial effects that:
the invention provides an integrated wastewater treatment device, a method and a system, which are formed by combining a persulfate advanced oxidation reaction and a membrane separation technology and integrating the membrane separation technology into the same accommodating cavity in which the persulfate advanced oxidation reaction occurs. On one hand, the membrane separation and the persulfate advanced oxidation reaction are integrated, free radicals formed by the persulfate advanced oxidation reaction can oxidize organic matters, metal complexes and inorganic matters, metal hydroxide flocs can remove various pollutants simultaneously due to the adsorption, complexation, codeposition and other actions, the irreversible pollution penetrating through the filter membrane can be greatly reduced, the probability of fouling and blocking of the filter membrane is reduced, the filter membrane is positioned in the accommodating cavity, and the ferric hydroxide flocs accumulated on the filter membrane can be continuously disturbed by disturbance brought by the mixer, so that the fouling and blocking of the filter membrane are further prevented; on the other hand, zero-valent iron particles in the transition metal are selected, the zero-valent iron particles can be converted into ferrous ions under the aerobic or anaerobic condition, further persulfate advanced oxidation reaction is carried out, the zero-valent iron is in a flowing state, active sites are updated in time, and the reaction activity is improved compared with that of the traditional heterogeneous persulfate advanced oxidation; furthermore, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the on-line membrane cleaning effect can be realized by combining with the free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced; in addition, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view showing the structure of an integrated wastewater treatment apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic flow diagram of an integrated wastewater treatment process according to an embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Various schematic diagrams in accordance with the disclosed embodiments of the invention are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, as actually required.
The process of the higher oxidation of persulfates is persulfate (S)2O8 2-) Mixing with zero-valent iron, persulfate can be decomposed to generate sulfate radical (SO) at normal temperature4 -Sulfuric acid radical (SO)4 2-) Furthermore, the oxidation reaction of many known organic compounds such as carboxylic acid, alcohol and ester into inorganic state has the capability of efficiently mineralizing refractory organic pollutants, oxidizing low-valence inorganic matters and destroying heavy metal complexes, and has wide application in the treatment of printing and dyeing wastewater, oily wastewater, phenolic wastewater, coking wastewater, nitrobenzene-containing wastewater, diphenylamine wastewater and other wastewater.
Zero-valent iron can be converted to divalent iron ions, either under aerobic or anaerobic regulation, the principle of which can be expressed by the following formula:
aerobic conditions: fe0+H2O+1/2O2→Fe2++2OH-
Anaerobic condition: : fe0+2H2O→Fe2++2OH-+H2
Then reacts with persulfate in persulfate to produce sulfate radical, the principle of which can be expressed by the following formula:
Fe2++S2O8 2-→Fe3++SO4 -(free radical) + SO4 2-
It is the presence of sulfate radicals which confer a strong oxidizing power. But the prior advanced oxidation based on persulfate simply utilizes persulfate advanced oxidation, and a deep wastewater treatment technology based on persulfate advanced oxidation, namely a deep coupling treatment technology based on persulfate advanced oxidation and a reliable deep coupling multistage wastewater treatment technology are lacked.
Based on this, this application has improved current persulfate advanced oxidation, the degree of depth has coupled persulfate advanced oxidation and membrane separation technique, through combining persulfate advanced oxidation or class persulfate advanced oxidation and membrane separation technique, and with the membrane separation technique integration in taking place the same chamber that holds of persulfate advanced oxidation, and then form integrated effluent treatment plant, and then formed the second grade waste water treatment integration technique of reliable degree of depth coupling, the efficiency of waste water treatment has been improved greatly, and the coupling degree is higher.
FIG. 1 illustrates an integrated wastewater treatment plant provided by an embodiment of an aspect of the present application, as shown in FIG. 1, comprising: a device body 1 having a housing chamber; the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity; a second charging device for charging zero-valent iron particles into the accommodating chamber; a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles; the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide flocs; the filtering membrane component comprises a filtering membrane 8 arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane 8, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and a zero-valent iron particle separator 21 which is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, and is used for separating and discharging zero-valent iron particles in the ferric hydroxide flocs and throwing the separated zero-valent iron particles into the accommodating cavity again.
In the integrated wastewater treatment device, on one hand, because the membrane separation and the persulfate advanced oxidation are integrated, the ferric hydroxide floc formed by the persulfate advanced oxidation can greatly reduce the pressure drop of the ferric hydroxide floc passing through the filtering membrane when the ferric hydroxide floc is accumulated on the filtering membrane due to larger molecular gap, the probability of fouling and blocking of the filtering membrane is reduced, and the filtering membrane is positioned in the accommodating cavity; on the other hand, the zero-valent iron is in a flowing state, the active sites are updated in time, and the reaction activity is improved compared with the traditional heterogeneous persulfate advanced oxidation; furthermore, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the on-line membrane cleaning effect can be realized by combining with the free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced; in addition, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.
This application adopts zero-valent iron as the iron source, compare in throwing into ferrous salt, because ferrous salt is not normal position production ferrous iron, directly dissolve when ferrous salt gets into solution, can't be at filtration membrane surface disturbance, directly dissolve simultaneously and can't bring the renewal of looks interface, can't play online membrane abluent effect, in addition, compare in the ferrous oxide particle, because the strong reducibility of zero-valent iron under the acid condition, the speed that zero-valent iron dissolves in water is faster, the reaction is more thorough, and ferrous oxide itself is insoluble in water, it dissolves to need the strong acid, the degree of difficulty of dissolving is great, the dissolving speed is slower, can't satisfy timely renewal and the replenishment of ferrous particle concentration, the wastewater treatment speed has been reduced.
In the embodiment shown in fig. 1, the first investor includes: a persulfate liquid storage tank 3 for storing the persulfate solution; a wastewater communication pipeline 2 communicated with a wastewater discharge port of a production system; and a premixer 4 for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating chamber. The embodiment directly communicates the device with a wastewater discharge port of a production system, and further can realize continuous online wastewater treatment.
In an embodiment not shown in fig. 1, the first investor comprises: a persulfate liquid storage tank for storing the persulfate solution; a wastewater tank for storing the wastewater to be treated; and the premixer is used for premixing the persulfate solution and the wastewater to be treated, and the premixed mixed solution can be pumped into the accommodating cavity.
Depending on the throughput, pumps of different sizes may be selected, such as micro pumps, peristaltic pumps, plunger pumps, etc., and the application is not limited thereto.
The mixer may be a paddle type mixer or may be a mixer that uses gas not participating in the reaction to create agitation, such as an aerator 16, in this embodiment, the mixer includes: an aerator 16, an air pipeline 15 communicated with the aerator, and an air compressor 14 connected to the air pipeline 15, or an air blower, so as to suck the external air or prepared inert gas (such as nitrogen) into the accommodating cavity, wherein the air or the inert gas forms a plurality of bubbles 23 in the reaction liquid, thereby forming an agitation and disturbance environment.
Further, in order to improve the efficiency of the persulfate advanced oxidation, the first injector further comprises: and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions. Thereby forming a persulfate-like advanced oxidation system, and the persulfate-like advanced oxidation system further strengthens the oxidation effect of persulfate advanced oxidation.
The ph adjuster can adjust the ph by adding an acidic substance and a basic substance, and in the embodiment shown in fig. 1, the ph adjuster includes: an acid adding pipeline (not shown in the figure), an alkali adding pipeline (not shown in the figure), an acid liquid tank 5 and a corresponding power pump (not shown in the figure) which are connected to the acid adding pipeline, an alkali liquid tank 6 and a corresponding power pump (not shown in the figure) which are connected to the alkali adding pipeline, and an acid-alkali detector 7, wherein the flow controllers (not shown in the figure) are correspondingly connected to the acid adding pipeline and the alkali adding pipeline.
The filtering membrane 8 in the filtering membrane module can be a ceramic membrane with a set aperture, and the ceramic membrane has various excellent material properties such as high temperature resistance, acid and alkali resistance, high mechanical strength and the like, and is increasingly applied to the field of water treatment. And with the continuous maturity and perfection of the ceramic membrane preparation process, the preparation cost of the ceramic membrane can be continuously reduced, and the ceramic membrane is developed in the field of water treatment. The ceramic membrane can remove colloidal suspended matters, macromolecular organic matters and the like, thereby ensuring the stability of the effluent quality. In the oil gas field, the ceramic membrane also can have better removal effect to grease waste water.
The ceramic membrane is easy to block, the ferric hydroxide floc formed in the embodiment of the invention can reduce transmembrane pressure drop and increase membrane flux, the ferric hydroxide floc can complex and adsorb heavy metal ions, silicon, phosphorus and the like in sewage, and meanwhile, the mixer can continuously disturb the floc accumulated on the ceramic membrane, so that the blocking is further prevented; furthermore, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the on-line membrane cleaning effect can be realized by combining with the free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced.
The ceramic membrane may be fixed by the membrane holder 9, and may be fixed obliquely or vertically, but the present invention is not limited thereto.
The filtering membrane component further comprises a water outlet pipeline 10, a pressure gauge 11, a vacuum pump 12 and a collector 13, the vacuum pump 12 creates suction force, so that liquid in the accommodating cavity penetrates through the filtering membrane 8, the ferric hydroxide floc is blocked by the filtering membrane 8, and the filtering membrane 8 has sewage filtering capacity and is matched with the ferric hydroxide floc to achieve the purpose of two-stage deep treatment. Experiments prove that the transmembrane pressure difference of the device is reduced by 50 percent, and the device is stable for a long time; membrane flux can be increased; the COD removal rate can reach more than 50 percent, and the turbidity is lower than 1 NTU.
In one embodiment, a heat exchanger (not shown) is disposed on the outer side wall or the inner side wall of the apparatus body 1 for adjusting the temperature of the whole reaction system, so that the reaction can be performed at a preferred temperature.
Further, in some embodiments, in order to collect the ferric hydroxide flocs after adsorbing the heavy metal ions, silicon and phosphorus in the wastewater, fig. 1 shows an embodiment in which the apparatus further comprises a sewage draining device, and the sewage draining device comprises: a dredge pump 22 and a sludge collector for collecting ferric hydroxide flocs and pollutants settled in the containing chamber.
Sludge collector is a long-pending mud fill 20, and long-pending mud fill 20 is the back taper, can make the ferric hydroxide floc can concentrate the pipeline entrance under the effect of gravity like this, and then draws out through dredge pump 22 and holds the chamber outside.
In one embodiment, the zero-valent iron particle separator 21 is disposed outside the receiving chamber.
The device is in the use process, firstly, required persulfate solution and waste water to be treated are respectively put into a containing cavity through a first input device and a second input device, zero-valent iron particles are put into the containing cavity, the zero-valent iron is in a flowing state, active sites are updated in time, the reaction activity is improved compared with the traditional heterogeneous persulfate advanced oxidation, after the zero-valent iron forms ferrous iron, persulfate is decomposed to generate sulfate radicals under the catalytic action of ferrous ions, the sulfate radicals are mixed with the waste water to destroy organic matters which are difficult to degrade in the waste water/waste water, or complex formed by heavy metal and the organic matters, organic phosphorus and organic arsenic are destroyed, meanwhile, ferrous ions are converted to form ferric ions in the process of generating the sulfate radicals, after the ferrous ions are mixed for a period of time, the pH value is regulated to 6-7.5 through a pH value regulator (part of the system is regulated to 9.5-10.5, can provide enough OH-So far) to provide sufficient OH-Reacting with ferric iron in solution to generate ferric hydroxide floc, complexing and adsorbing heavy metal ions, silicon, phosphorus and the like in sewage, and because the whole reaction is in the same accommodating cavity, hydrogen and oxygen are generatedThe iron oxide flocs have small density and large gaps among particles, so that transmembrane pressure drop is reduced, membrane flux is improved, iron particles can perform an online membrane cleaning effect on the surface of a ceramic membrane and a free radical oxidant generated in situ, the pollution blockage of a filtering membrane can be effectively reduced, continuous disturbance is performed under the action of a mixer, the possibility of pollution blockage is further reduced, and a deep-coupled secondary wastewater treatment technology of persulfate advanced oxidation and membrane separation technology is further formed. Adopt zero-valent iron as the iron source, compare in throwing the ferrite, because the ferrite is not normal position produces ferrous iron, directly dissolve when the ferrite gets into solution, can't be at filtration membrane surface disturbance, directly dissolve simultaneously and can't bring the renewal of phase interface, can't play online membrane abluent effect, in addition, compare in the ferrous oxide particle, because the strong reducibility of zero-valent iron under the acidic condition, the speed that zero-valent iron dissolves in water is faster, the reaction is more thorough, and the ferrous oxide itself is insoluble in water, it needs the strong acid to dissolve, the degree of difficulty of dissolving is great, the dissolving speed is slower, can't satisfy timely renewal and the replenishment of ferrous particle concentration, waste water treatment speed has been reduced.
Based on the same reason as the above embodiment, the second aspect of the present invention provides an integrated wastewater treatment method, specifically as shown in fig. 2, comprising:
s100, putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;
s200, mixing persulfate solution, the wastewater to be treated and the zero-valent iron particles in the accommodating cavity;
s300, adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range in a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;
s400, adjusting the pH value of the reaction environment in the accommodating cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;
and S500, collecting liquid penetrating through a filtering membrane arranged in the accommodating cavity by suction, wherein the filtering membrane is provided with a pore passage capable of preventing the ferric hydroxide flocs from penetrating.
S600, separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and adding the separated zero-valent iron particles into the accommodating cavity again;
the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity. According to the integrated wastewater treatment method provided by the aspect, the persulfate advanced oxidation or persulfate-like advanced oxidation and the membrane separation technology are combined, and the membrane separation technology is integrated in the same accommodating cavity in which the persulfate advanced oxidation occurs, so that the integrated wastewater treatment device is formed. On one hand, the membrane separation and the persulfate advanced oxidation are integrated, iron hydroxide floc formed by the persulfate advanced oxidation has larger molecular gap, so that the pressure drop of the iron hydroxide floc passing through the filtering membrane can be greatly reduced when the iron hydroxide floc is accumulated on the filtering membrane, the probability of fouling and blocking of the filtering membrane is reduced, the filtering membrane is positioned in the accommodating cavity, and the iron hydroxide floc accumulated on the filtering membrane can be continuously disturbed by disturbance brought by the mixer, so that the fouling and blocking of the filtering membrane are further prevented; on the other hand, the zero-valent iron is in a flowing state, the active sites are updated in time, and the reaction activity is improved compared with the traditional heterogeneous persulfate advanced oxidation; furthermore, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the on-line membrane cleaning effect can be realized by combining with the free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced; in addition, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.
This application adopts zero-valent iron as the iron source, compare in throwing into ferrous salt, because ferrous salt is not normal position production ferrous iron, directly dissolve when ferrous salt gets into solution, can't be at filtration membrane surface disturbance, directly dissolve simultaneously and can't bring the renewal of looks interface, can't play online membrane abluent effect, in addition, compare in the ferrous oxide particle, because the strong reducibility of zero-valent iron under the acid condition, the speed that zero-valent iron dissolves in water is faster, the reaction is more thorough, and ferrous oxide itself is insoluble in water, it dissolves to need the strong acid, the degree of difficulty of dissolving is great, the dissolving speed is slower, can't satisfy timely renewal and the replenishment of ferrous particle concentration, the wastewater treatment speed has been reduced.
For the same reason, the method further comprises:
s001, premixing the persulfate solution and the wastewater to be treated;
in this embodiment, step S100 includes: and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.
Based on the foregoing embodiments, it can be known that the method further includes:
and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.
In addition, in some embodiments, in order to collect iron hydroxide flocs after adsorbing heavy metal ions, silicon, and phosphorus in the wastewater, the wastewater treatment method of the present aspect further includes:
and S700, collecting ferric hydroxide flocs settled in the accommodating cavity.
The invention further provides an integrated wastewater treatment system, which comprises the integrated wastewater treatment device and a wastewater or sewage discharge device, wherein a wastewater discharge port of the wastewater or sewage discharge device is communicated with the integrated wastewater treatment device, so that the online continuous wastewater treatment is realized.
The wastewater discharge device can be a sub-device in the complete industrial production system, such as a printing and dyeing wastewater discharge device of a printing and dyeing system, so that the integrated wastewater treatment device is directly integrated in the production process, and the process flow of wastewater treatment is simplified.
The above embodiments of the present application will be described in detail with reference to several specific scenarios.
Scene one: the organophosphorus waste water has COD 1120mg/L and total phosphorus 89 mg/L. Preparing a persulfate advanced oxidation reagent, wherein the amount of persulfate is 800-1000mg/L, the input amount of iron is 5g/L, adjusting the pH value to 6.5-7.5 after mixing for 120 minutes, starting ceramic membrane filtration, reducing the COD of effluent to be within 500mg/L, and reducing the total phosphorus to be less than 20 mg/L.
Scene two: the electroplating waste water has COD 500mg/L, copper ion concentration 30mg/L and nickel ion content 10 mg/L. Preparing a persulfate high-grade oxidation reagent, wherein the amount of persulfate is 250-500mg/L, the input amount of iron is 3g/L, reacting for 60 minutes, raising the pH value of the wastewater to 6.5-7.5, and adjusting the pH value to 9.5-10.5; the ceramic membrane filtration is started, the COD of the effluent is reduced to be within 120mg/L, the concentration of copper ions is lower than 0.5mg/L, and the concentration of nickel ions is lower than 0.3 mg/L.
Scene three: printing and dyeing wastewater with COD of 320 mg/L. Preparing a persulfate high-grade oxidation reagent, wherein the amount of persulfate is 150-400mg/L, the input amount of iron is 3g/L, the reaction lasts for 60 minutes, and the pH value of the wastewater is raised to 6.5-7.5; the ceramic membrane filtration is started, and the COD of the effluent is reduced to be within 90 mg/L.
According to the scene, the integrated wastewater treatment device, the method and the system provided by the invention are not easy to block, can further improve the wastewater treatment efficiency, and have important guiding significance, and the COD removal rate can reach more than 50%.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An integrated wastewater treatment device, comprising:
a device body having a receiving cavity;
the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity;
a second charging device for charging zero-valent iron particles into the accommodating chamber;
a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles;
the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide flocs;
the filtering membrane assembly comprises a filtering membrane arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and
and the zero-valent iron particle separator is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, is used for separating and discharging zero-valent iron particles in the ferric hydroxide flocs, and throws the separated zero-valent iron particles into the accommodating cavity again.
2. The integrated wastewater treatment apparatus according to claim 1, wherein the first throw-in device comprises:
a persulfate liquid storage tank for storing the persulfate solution;
a wastewater tank for storing the wastewater to be treated; and
the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity; or,
the first throw-in device includes:
a persulfate liquid storage tank for storing the persulfate solution;
a wastewater communication pipeline communicated with a wastewater discharge port of a production system; and
and the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity.
3. The integrated wastewater treatment plant of claim 2, wherein the first feeder further comprises:
and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions.
4. The integrated wastewater treatment apparatus according to claim 1, wherein the filtration membrane is a ceramic membrane.
5. The integrated wastewater treatment plant according to claim 1, further comprising: a sewage draining device;
the sewage draining device comprises: the sewage pump and the sludge collector are used for collecting ferric hydroxide flocs and pollutants settled in the accommodating cavity.
6. An integrated wastewater treatment method, comprising:
putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;
mixing the persulfate solution, the wastewater to be treated and the zero-valent iron particles in the containing cavity;
adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range within a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;
adjusting the pH value of the reaction environment in the containing cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;
collecting liquid permeating a filter membrane arranged in the accommodating cavity by suction, wherein the filter membrane is provided with a pore passage capable of preventing ferric hydroxide flocs from permeating;
separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and throwing the separated zero-valent iron particles into the accommodating cavity again;
the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity.
7. The integrated wastewater treatment method according to claim 6, further comprising:
premixing the persulfate solution and the wastewater to be treated;
mixing persulfate solution in the holding chamber, the wastewater to be treated and the zero-valent iron particles, comprising:
and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.
8. The integrated wastewater treatment method according to claim 6, further comprising:
and collecting ferric hydroxide floc settled in the containing cavity.
9. The integrated wastewater treatment method according to claim 6, further comprising:
and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.
10. An integrated wastewater treatment system comprising the integrated wastewater treatment apparatus of any one of claims 1 to 5.
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