CN114477607A - Treatment system and treatment method for industrial wastewater - Google Patents
Treatment system and treatment method for industrial wastewater Download PDFInfo
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- CN114477607A CN114477607A CN202210290592.XA CN202210290592A CN114477607A CN 114477607 A CN114477607 A CN 114477607A CN 202210290592 A CN202210290592 A CN 202210290592A CN 114477607 A CN114477607 A CN 114477607A
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 118
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 97
- 230000003647 oxidation Effects 0.000 claims abstract description 94
- 238000005189 flocculation Methods 0.000 claims abstract description 91
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- 238000001914 filtration Methods 0.000 claims abstract description 77
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 76
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- 239000002245 particle Substances 0.000 claims abstract description 24
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 22
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- 239000004576 sand Substances 0.000 claims description 56
- 239000010802 sludge Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000000835 fiber Substances 0.000 claims description 24
- 238000006385 ozonation reaction Methods 0.000 claims description 22
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- 239000000463 material Substances 0.000 claims description 16
- 238000010008 shearing Methods 0.000 claims description 11
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- 238000011084 recovery Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 239000002159 nanocrystal Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 238000003672 processing method Methods 0.000 claims 2
- 239000002352 surface water Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
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- -1 suspended flocs Substances 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a treatment system and a treatment method of industrial wastewater, wherein the treatment system comprises a magnetic flocculation unit, a filtering unit and an ozone catalytic oxidation unit which are sequentially connected, wherein the magnetic flocculation unit is used for removing inorganic pollutants in an ionic state and suspended solid particles in the industrial wastewater to obtain primary flocculated effluent and primary precipitates; the filtering unit is used for removing solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent; and the ozone catalytic oxidation unit is used for removing organic pollutants and ammonia nitrogen in the filtered water. By applying the technical scheme of the invention, the industrial wastewater II-grade biochemical water is subjected to advanced treatment sequentially through the magnetic flocculation unit, the filtering unit and the ozone catalytic oxidation unit, so that the quality of the treated effluent is excellent and can reach the standard of 'surface water environment quality standard' (GB3838-2002) surface III-class water in China.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a treatment system and a treatment method for industrial wastewater.
Background
With the increasingly prominent problem of water pollution in China, the improvement of the discharge standard of industrial wastewater treatment is a great trend. After the secondary biochemical treatment, most of suspended solids and organic matters in the existing industrial wastewater are removed, and the COD concentration of the effluent is relatively low, but the effluent still has the characteristics of complex components, more characteristic pollutants and poorer biodegradability, and the water quality is discharged into the urban water environment basically without self-purification capacity, so that the urban water is not repaired but polluted. Therefore, the industrial wastewater II-grade biochemical water is urgently required to be discharged after being subjected to standard extraction to the surface III-class water, but the current fresh process can meet the standard improvement requirement of the surface III-class water.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention mainly aims to provide a system and a method for treating industrial wastewater, which aim to solve the problem of incomplete treatment of the industrial wastewater in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided an industrial wastewater treatment system, comprising a magnetic flocculation unit for removing inorganic contaminants in an ionic state and solid particles in a suspended state from industrial wastewater to obtain a primary flocculated effluent and a primary precipitate, the flocculation unit having a primary flocculation water outlet; the filtering unit is used for removing solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent, and is provided with an inlet to be filtered and a filtered effluent port, and the inlet to be filtered is connected with the primary flocculated effluent port; the ozone catalytic oxidation unit is used for removing organic pollutants and ammonia nitrogen in the filtered water and is provided with a catalytic oxidation water inlet and a purified water outlet, and the catalytic oxidation water inlet is connected with the filtered water outlet.
Further, the magnetic flocculation unit comprises: the magnetic flocculation reactor is provided with a magnetic sludge outlet, a feed inlet and a primary flocculation water outlet; the magnetic sludge shearing machine is provided with a magnetic sludge inlet and a floccule outlet, and the magnetic sludge inlet is connected with the magnetic sludge outlet; the magnetic seed separator is provided with a floccule inlet and a magnetic seed outlet, wherein the floccule inlet is connected with the floccule outlet, and the magnetic seed outlet is connected with the feeding port.
Further, this magnetism flocculation reaction ware includes that mutual intercommunication thoughtlessly congeals pond and flocculation basin, and magnetism mud export and one-level flocculation delivery port set up on the flocculation basin.
Further, the filter unit includes: the active sand filter is provided with an inlet to be filtered and a primary filtering water outlet, the active sand filter is provided with a sand bed, and the particle size of active sand in the sand bed is preferably 0.8-1.2 mm; the fiber ball filter is provided with a primary filtering water inlet and a filtering water outlet, the primary filtering water outlet is connected with the primary filtering water inlet, a filter material layer is arranged in the fiber ball filter, and the layer height of the filter material layer is preferably 1200-1800 m.
Furthermore, the ozone catalytic oxidation unit comprises a primary ozone catalytic oxidation device and a secondary ozone catalytic oxidation device which are connected in sequence, wherein a catalytic oxidation water inlet is arranged on the primary ozone catalytic oxidation device, and a purified water outlet is arranged on the secondary ozone catalytic oxidation device; the first-stage ozone catalytic oxidation device is filled with a first catalyst, and the active component of the first catalyst comprises at least one of Mn, Cu, Fe or Ce; and/or the secondary ozone catalytic oxidation device is filled with a second catalyst, and the active component of the second catalyst comprises at least one of Co or Ni.
According to another aspect of the present invention, there is provided a method for treating industrial wastewater, the method comprising: step S1, performing magnetic flocculation treatment on the industrial wastewater to remove inorganic pollutants in an ionic state, inorganic pollutants in an ionic state and solid particles in a suspended state in the industrial wastewater to obtain primary flocculation effluent and primary precipitates; step S2, filtering the primary flocculated effluent to remove solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent; and step S3, performing odor sample catalytic oxidation treatment on the filtered water to remove organic pollutants and ammonia nitrogen in the filtered water, and obtaining purified water.
Further, step S1 includes adding magnetic seeds and water treatment agents to the industrial wastewater to perform magnetic flocculation, wherein the time of the magnetic flocculation is preferably 4-6min, and the magnetic seeds preferably include at least one of ferroferric oxide or ferrosilicon nanocrystals; the water treatment agent preferably comprises a coagulant, preferably at least one of polyaluminum chloride (PAC) or polyferric sulfate (PFS), and a flocculant, preferably Polyacrylamide (PAM).
Further, step S1 includes performing a magnetic seed recovery process on the primary precipitate, where the magnetic seed recovery process includes: shearing the primary precipitate into flocculent sludge, separating magnetic seeds from the flocculent sludge to obtain recovered magnetic seeds, preferably separating the magnetic seeds for 3-5 min; the recovered magnetic seeds are returned to step S1 for reuse.
Further, step S2 includes: performing primary filtration on the primary flocculated effluent to remove solid suspended matters to obtain primary filtered effluent; and performing secondary filtration on the primary filtered water to remove suspended flocs to obtain filtered water.
Further, an active sand filter is adopted for primary filtration, the active sand filter is provided with a sand bed, the particle size of active sand in the sand bed is preferably 0.8-1.2mm, and the filtration speed of the primary filtration is preferably 8-12 m/h.
Further, a fiber ball filter is adopted for secondary filtration, a filter material layer is arranged in the fiber ball filter, the layer height of the filter material layer is preferably 1200-1800mm, and the filtration speed of the secondary filtration is preferably 25-40 m/h.
Further, step S3 includes: performing primary ozone catalytic oxidation treatment on the filtered water to remove organic pollutants in the filtered water to obtain primary ozone catalytic oxidation water; and carrying out secondary ozone catalytic oxidation treatment on the primary ozone catalytic water to remove ammonia nitrogen in the primary ozone catalytic oxidation water, thereby obtaining purified water.
Further, the primary ozone catalytic oxidation treatment is carried out under the catalysis of a first catalyst, the active component of the first catalyst is selected from at least one of Mn, Cu, Fe or Ce, and the treatment time is preferably 30-60 min;
further, the secondary ozone catalytic oxidation treatment is carried out under the catalytic action of a second catalyst, the active component of the second catalyst is at least one of Co or Ni, and the treatment time is preferably 60-90 min.
By applying the technical scheme of the invention, the industrial wastewater II-grade biochemical water is subjected to advanced treatment sequentially through the magnetic flocculation unit, the filtering unit and the ozone catalytic oxidation unit, and inorganic pollutants in an ionic state, suspended solid particles, suspended solids, suspended flocs, organic pollutants and ammonia nitrogen in the industrial wastewater II-grade biochemical water are removed, so that the treated effluent has excellent water quality, can reach the national Standard for Water environmental quality on the surface (GB3838-2002) and the Standard for class III water on the surface, can not cause pollution after being directly discharged into a city river, and can effectively restore the city water body.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a block diagram showing the construction of an industrial wastewater treatment system provided in accordance with embodiment 1 of the present invention.
Wherein the figures include the following reference numerals:
10. a flocculation reactor; 20. an active sand filter; 30. a fiber ball filter; 40. a first-stage ozone catalytic oxidation tower; 50. a secondary ozone catalytic oxidation tower.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As the background art of the application analyzes, the existing industrial wastewater still has the characteristics of complex components, more characteristic pollutants and poorer biodegradability after secondary treatment, and the water quality is discharged into the urban water environment without self-purification capacity basically, so that the urban water is polluted. In order to solve the problem, the application provides a treatment system and a treatment method of industrial wastewater.
In the present application, "industrial wastewater" in "treatment system and treatment method of industrial wastewater" refers to industrial wastewater grade II biochemical water subjected to secondary biochemical treatment.
In an exemplary embodiment of the present application, there is provided an industrial wastewater treatment system, including: the system comprises a magnetic flocculation unit, a filtering unit and an ozone catalytic oxidation unit, wherein the magnetic flocculation unit is used for removing inorganic pollutants in an ionic state and solid particles in a suspended state in industrial wastewater to obtain primary flocculation water and primary sediments, and is provided with a primary flocculation water outlet;
the filtering unit is used for removing solid suspended matters and suspended flocs in the primary flocculated water to obtain filtered water, and is provided with a water inlet to be filtered and a filtered water outlet, and the water inlet to be filtered is connected with the primary flocculated water outlet;
the ozone catalytic oxidation unit is used for removing organic pollutants and ammonia nitrogen in the filtered water and is provided with a catalytic oxidation water inlet and a purified water outlet, and the catalytic oxidation water inlet is connected with the filtered water outlet.
According to the industrial wastewater treatment system, industrial wastewater II-grade biochemical water is subjected to advanced treatment sequentially through the magnetic flocculation unit, the filtering unit and the ozone catalytic oxidation unit, inorganic pollutants in an ionic state and suspended solid particles in the industrial wastewater II-grade biochemical water are subjected to flocculation treatment by the magnetic flocculation unit to generate a first-grade precipitate, and the obtained first-grade suspended matters and suspended flocs in the first-grade flocculated water are effectively removed through the filtering unit; after solid pollution is removed, organic pollutants and ammonia nitrogen in the wastewater can be effectively removed by catalytic oxidation of ozone, so that the treated effluent has excellent water quality, can reach the standard of 'surface water environment quality standard' (GB3838-2002) surface III water standard in China, cannot cause pollution after being directly discharged into urban rivers, and can effectively restore urban water bodies.
In some embodiments of the present application, the magnetic flocculation unit comprises a magnetic flocculation reactor, a magnetic mud shear, and a magnetic seed separator. The magnetic flocculation reactor is provided with a magnetic sludge outlet, a feed inlet and a primary flocculation water outlet, the industrial wastewater is subjected to magnetic flocculation reaction in the magnetic flocculation reactor, inorganic pollutants in an ionic state and suspended solid particles are subjected to magnetic flocculation reaction to generate primary precipitates which are then precipitated to obtain primary flocculation effluent, and the primary flocculation effluent is conveyed to the filtering unit for filtering. The magnetic flocculation reactor can remove 50-75% of organic pollutants (COD) in industrial wastewater.
The magnetic sludge shearing machine is provided with a magnetic sludge inlet and a floccule outlet, wherein the magnetic sludge inlet is communicated with the magnetic sludge outlet of the magnetic flocculation reactor, so that the magnetic sludge enters the magnetic sludge shearing machine to be sheared into floccule sludge, and then the floccule sludge is discharged out of the magnetic sludge shearing machine through the floccule outlet.
The magnetic seed separator is provided with a floccule inlet and a magnetic seed outlet, the floccule inlet is connected with the floccule outlet of the magnetic mud shearing machine so as to be beneficial to separating floccule mud into recovered magnetic seeds and flocculent mud in the magnetic seed separator by entering the floccule inlet, and the recovered magnetic seeds are discharged from the magnetic seed separator by the magnetic seed outlet. Preferably link to each other this magnetic seed export with flocculation reactor's charge door to do benefit to and retrieve the magnetic seed and pass through the charge door and get into in the magnetic flocculation reactor and continue to carry out the magnetic flocculation reaction, realize the recycle of magnetic seed, reduce the energy waste, reduce cost.
In order to avoid direct discharge of the flocculated sludge to pollute the environment, in some embodiments, the industrial wastewater treatment system further comprises a sludge dewatering system for dewatering the flocculated sludge discharged from the magnetic seed separator, preferably the magnetic seed separator further comprises a flocculated sludge outlet, and the flocculated sludge is connected to the sludge dewatering system.
In order to do benefit to the more abundant that magnetic flocculation reaction goes on, one-level precipitate and one-level flocculation delivery water more do benefit to the separation, in some embodiments, above-mentioned magnetic flocculation reactor includes coagulating basin and the flocculation basin of mutual intercommunication, the charge door sets up on coagulating basin, magnetic sludge outlet and one-level flocculation delivery port set up on the flocculation basin, industrial waste water carries out magnetic flocculation reaction in the coagulating basin at first, then deposit in getting into the flocculation basin again, in order to do benefit to the one-level precipitate to precipitate in the flocculation basin and appear through magnetic sludge outlet discharge flocculation basin, it obtains one-level flocculation delivery water and carries out subsequent filtration through one-level flocculation delivery port discharge flocculation basin to separate one-level precipitate.
In some embodiments of the present application, a filtration unit comprises: the filter comprises an active sand filter and a fiber ball filter, wherein the active sand filter is provided with a water inlet to be filtered and a primary filtering water outlet, the water inlet to be filtered is connected with the primary flocculation water outlet, and the active sand filter is provided with a sand bed so as to filter and remove solid suspended matters in the water to be filtered through the sand bed. The activated sand filter can clean sand and filter at the same time, a backwashing system is not required to be additionally arranged, and the removal effect on suspended matters is very good, for example, when the inlet water turbidity is less than 2NTU, the outlet water is less than 1 NTU. The removal rate of the turbidity of the water to be filtered by the active sand filter is more than or equal to 50 percent. The particle size of the active sand in the sand bed is preferably 0.8-1.2mm, so as to be beneficial to more fully removing solid suspended substances in the primary flocculated effluent in the filtering process. The fiber ball filter is provided with a primary filtering water inlet and a filtering water outlet, the primary filtering water outlet is connected with the primary filtering water inlet, and a filter material layer is arranged in the fiber ball filter, so that suspended flocs (such as colloid and biological sludge and other sticky substances) in primary filtering water are filtered and removed through the filter material layer, and the subsequent catalytic oxidation reaction is prevented from being influenced by the suspended flocs. Preferably, the height of the filter material layer is 1200-1800mm, so as to facilitate more sufficient removal of suspended flocs in the filtering process.
Typically, but not by way of limitation, the particle size of the active sand in the sand bed in the active sand filter is, for example, 0.8mm, 0.9mm, 1.0mm, 1.1mm, or 1.2 mm; the height of the filter material layer in the fiber ball filter is 1200mm, 1300mm, 1400mm, 1500mm, 1600mm, 1700mm or 1800 mm.
In some embodiments of the present application, the catalytic ozonation unit includes a primary catalytic ozonation device and a secondary catalytic ozonation device connected in sequence, the catalytic ozonation water inlet is disposed on the primary catalytic ozonation device, and the purified water outlet is disposed on the secondary catalytic ozonation device. The first catalyst is filled in the first-stage ozone catalytic oxidation device, so that organic pollutants in the filtered water are oxidized under the catalytic action of the first catalyst to remove and reduce COD, and then the organic pollutants enter the second-stage ozone catalytic oxidation device to oxidize ammonia nitrogen under the catalytic action of the second catalyst, so that the ammonia nitrogen is further treated, and the water outlet index is improved.
The first catalyst is used for catalyzing the oxidation of organic pollutants (COD), and the active component of the first catalyst comprises one or more of Mn, Cu, Fe or Ce.
The second catalyst is used for catalyzing ammonia nitrogen oxidation, and the active ingredients of the second catalyst include but are not limited to one or two of Co and Ni.
In some embodiments of the present application, in order to further improve the convenience of loading the first catalyst and the second catalyst in the primary ozone catalytic oxidation device and the secondary ozone catalytic oxidation device respectively, the first catalyst and the second catalyst are independently present in a spherical form, including but not limited to, the active ingredient is loaded on a spherical support, and the spherical support may be an active metal, such as an alumina molecular sieve, and the like. The active ingredient to be loaded on the spherical carrier may be one kind or plural kinds. The diameter of the spherical carrier is preferably 3 to 5mm to facilitate loading.
The structures of the primary ozone catalytic oxidation device and the secondary ozone catalytic oxidation device are not limited, and any device can be used for loading a catalyst and performing catalytic oxidation treatment on wastewater, such as an oxidation tower and the like, and the height of the oxidation tower is not limited, preferably 7-11 m.
The organic pollutants and ammonia nitrogen in the filtered water are removed by sequentially adopting the primary ozonation catalytic device and the secondary ozonation catalytic oxidation device, preferably, the removal rate of COD in the filtered water by the primary ozonation catalytic device is 40-65%, and the removal rate of ammonia nitrogen by the secondary ozonation catalytic device is more than or equal to 90%.
In another exemplary embodiment of the present application, there is provided a method for treating industrial wastewater, the method comprising:
step S1, performing magnetic flocculation treatment on the industrial wastewater to remove sludge pollutants in an ionic state and suspended solid particles in the industrial wastewater to obtain primary flocculation effluent and primary sediments;
step S2, filtering the primary flocculated effluent to remove solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent;
and step S3, carrying out ozone catalytic oxidation treatment on the filtered water to remove organic pollutants and ammonia nitrogen in the filtered water, and obtaining purified water.
According to the industrial wastewater treatment method, the industrial wastewater II-level biochemical water is sequentially subjected to magnetic flocculation treatment, filtration treatment and ozone catalytic oxidation treatment, so that inorganic pollutants in an ionic state, suspended solid particles, suspended solids, suspended flocs, organic pollutants and ammonia nitrogen in the industrial wastewater II-level biochemical water are removed, the quality of the treated effluent water is excellent, the standard of the national 'surface water environment quality standard' (GB3838-2002) surface III-class water standard can be reached, the industrial wastewater can not only be polluted after being directly discharged into a city river, but also the city water body can be effectively repaired.
In some embodiments of the present application, step S1 includes adding a magnetic seed and a water treatment agent to the industrial wastewater to perform magnetic flocculation treatment, reacting the inorganic pollutant in an ionic state with the treatment agent to generate a water-insoluble or water-insoluble compound, forming flocs by using the magnetic seed as a crystal nucleus between the suspended solid particles and the water-insoluble or water-insoluble compound, forming a primary precipitate from the industrial wastewater by the flocs under the action of gravity, and removing the primary precipitate from the industrial wastewater to obtain a primary flocculated effluent.
In order to improve the magnetic flocculation treatment efficiency, the magnetic flocculation reaction time is preferably controlled to be 4-6min, so that the treatment efficiency of the industrial wastewater is further improved on the basis of ensuring that inorganic pollutants and suspended particles fully form primary precipitates for precipitation.
Typical but non-limiting magnetic flocculation reaction times are e.g. 4min, 4.5min, 5min, 5.5min or 6 min.
The type of the above-mentioned water treatment agent is not limited as long as it can react with the inorganic contaminant in an ionic state to form a water-insoluble or hardly water-soluble compound, and includes, but is not limited to, one or more of a coagulant or a flocculant. Coagulant such as PAC (polyaluminium chloride) or PFS (polyferric sulfate), and flocculant such as PAM (polyacrylamide).
The type of the magnetic species is not limited, as long as the magnetic species can be used as a crystal nucleus to form a floccule with suspended solid particles and water-insoluble or water-insoluble compounds, and the material includes but is not limited to one or more of ferroferric oxide, iron-silicon nanocrystals or neodymium-iron-boron.
In one embodiment of the application, in order to remove inorganic pollutants in an ionic state and solid particles in a suspended state in industrial wastewater more fully, ferroferric oxide is added into the industrial wastewater as a magnetic seed, the adding amount is 35-45mg/L, the water treatment agent comprises a flocculating agent and a coagulating agent, the coagulating agent is polyaluminium chloride (PAC), the adding amount is 25-35mg/L, the flocculating agent is Polyacrylamide (PAM), and the adding amount is 0.8-1.2 mg/L.
In order to reduce the energy waste and improve the utilization rate of magnetic seeds, the first-stage precipitate is preferably subjected to magnetic seed recovery treatment, and the magnetic seed recovery treatment comprises the following steps: the primary precipitate is sheared into flocculent sludge, so that magnetic seeds can be separated from the flocculent sludge, the recovery of the magnetic seeds is more sufficient, and the influence on the recovery rate of the magnetic seeds due to the wrapping of the precipitate is avoided; separating the magnetic seeds from the flocculent sludge to obtain recovered magnetic seeds, and returning the recovered magnetic seeds to the step S1 for recycling.
The flocculent slurry obtained after the flocculent sludge is separated from the magnetic seeds is preferably dehydrated to avoid environmental pollution caused by direct discharge.
In order to further improve the magnetic seed separation efficiency on the basis of ensuring the sufficient recovery of the magnetic seeds, the time for separating the magnetic seeds from the flocculent sludge is 3-5 min.
Typically, but not by way of limitation, the flocculent sludge is separated from the magnetic species for a period of time, such as 3min, 3.5min, 4min, 4.5min, or 5 min.
In some embodiments of the present application, the step S2 includes: performing primary filtration on the primary flocculated effluent to remove solid suspended matters to obtain primary filtered effluent; and performing secondary filtration on the primary filtered water to remove suspended flocs to obtain filtered water, so as to be beneficial to more completely removing solid suspended matters and suspended flocs in the primary flocculated water.
In some embodiments, in order to improve the filtering effect, the first-stage filtering is performed by using an active sand filter, so that the active sand is cleaned at the same time of filtering without additionally arranging a backwashing system. The above-mentioned active sand filter is provided with a sand bed, and the primary filtration is preferably performed in the active sand filter to filter out solid suspended substances through the sand bed in the active sand filter. It is further preferable that the particle size of the active sand in the sand bed is 0.8 to 1.2 mm. In order to further improve the efficiency of the first-stage filtration, the preferred filtration speed is 8-12m/h, the movement speed of the sand bed is 7-9mm/min, and the compressed air for lifting the active sand in the sand bed is 5-7kg/cm2。
In some embodiments, a fiber ball filter is used for secondary filtration to further remove some suspended flocs (such as sticky sludge) and the like in the primary filtered water through the fiber ball filter. The fiber ball filter is provided with a filter material layer, and the layer height of the filter material layer is further preferably 1200-1800mm, so that suspended flocs in the primary filtered water can be filtered and removed through the fiber ball filter. In order to improve the filtration efficiency on the basis of ensuring the sufficient removal of suspended flocs, the filtration speed of the secondary filtration is preferably 25-40 m/h.
Typically but not limitatively, when the activated sand filter is used for primary filtration, the filtration speed is 8m/h, 9m/h, 10m/h, 11m/h or 12m/h, the moving speed of the sand bed is 7mm/min, 7.5mm/min, 8mm/min, 8.5mm/min or 9mm/min, and the compressed air for lifting the activated sand in the sand bed is 5mm/min, 5.5mm/min, 6mm/min, 6.5mm/min or 7 mm/min; the height of the filter material layer is 1200mm, 1300mm, 1400mm, 1500mm, 1600mm, 1700mm or 1800 mm; when the fiber ball filter is used for secondary filtration, the filtration speed is 25m/h, 28m/h, 30m/h, 32m/h, 35m/h, 38m/h or 40 m/h.
In some embodiments of the present application, step S3 includes: performing primary ozone catalytic oxidation treatment on the filtered water to remove organic pollutants in the filtered water to obtain primary ozone catalytic oxidation water; and carrying out secondary ozone catalytic oxidation treatment on the primary ozone catalytic oxidation water to remove ammonia nitrogen in the primary ozone catalytic oxidation water to obtain purified water, so that organic pollutants and ammonia nitrogen in the filtered water can be more completely removed.
In order to improve the efficiency of the primary catalytic ozonation treatment, the primary catalytic ozonation treatment is carried out under the catalysis of a first catalyst, the type of the active component of the first catalyst is not limited, and the first catalyst can catalyze organic pollutants (COD) to carry out oxidation reaction, including but not limited to one or more of Mn, Cu, Fe or Ce.
In order to improve the efficiency of the secondary ozone catalytic oxidation treatment, the secondary ozone catalytic oxidation treatment is carried out under the catalysis of a second catalyst, the type of the active component of the first catalyst is not limited, and the active component can catalyze ammonia nitrogen to carry out oxidation reaction, including but not limited to one or more of Co or Ni.
In some embodiments of the present application, the time of the first-stage ozone catalytic oxidation treatment is 30-60min, and the time of the second-stage ozone catalytic oxidation treatment is 60-90min, so as to further improve the ozone catalytic oxidation treatment efficiency on the basis of ensuring that the organic pollutants and ammonia nitrogen are removed sufficiently.
Typically, but not by way of limitation, the time of the first-stage ozone catalytic oxidation treatment is, for example, 30min, 35min, 40min, 45min, 50min, 55min or 60 min; the time of the secondary ozone catalytic oxidation treatment is 60min, 65min, 70min, 75min, 80min, 85min or 90 min.
The following examples will further illustrate the advantageous effects of the present application.
Example 1
The embodiment provides an industrial wastewater treatment system, as shown in fig. 1, the industrial wastewater treatment system comprises a magnetic flocculation reactor 10, an active sand filter 20, a fiber ball filter 30, a primary ozone catalytic oxidation tower 40 and a secondary ozone catalytic oxidation tower 50 which are connected in sequence, wherein the magnetic flocculation reactor 10 comprises a coagulation tank and a flocculation tank which are communicated with each other, a magnetic sludge outlet and a primary flocculation water outlet are arranged on the flocculation tank, the coagulation tank and the flocculation tank are respectively provided with a feed inlet, the active sand filter 20 is provided with a to-be-filtered water inlet and a primary filtered water outlet, and the to-be-filtered water inlet is connected with the primary flocculation water outlet through a pipeline; the fiber ball filter 30 has a first-stage filtered water inlet and a filtered water outlet, the first-stage filtered water inlet and the first-stage filtered water outlet are connected by a pipeline; the first-stage ozone catalytic oxidation tower 40 is provided with a catalytic oxidation water inlet and a first-stage catalytic oxidation water outlet, and the catalytic oxidation water inlet is connected with the first-stage filtered water outlet through a pipeline; the second-stage ozone catalytic oxidation tower 50 is provided with a first-stage catalytic oxidation water inlet and a purified water outlet, and the first-stage catalytic oxidation water inlet is connected with the first-stage catalytic oxidation water outlet through a pipeline; the first-stage ozone catalytic oxidation tower is filled with a first catalyst, and the second-stage ozone catalytic oxidation tower is filled with a second catalyst.
The magnetic flocculation reactor 10 is connected with a magnetic mud shearing machine through a pipeline, the magnetic mud shearing machine is connected with a magnetic seed separator through a pipeline, and the magnetic seed separator is connected with the magnetic flocculation reactor through a pipeline so as to realize the cyclic utilization of magnetic seeds.
In this embodiment, the industrial wastewater is industrial wastewater grade II biochemical water, and the water quality index is as follows: COD is 70mg/L, ammonia nitrogen is 4.5mg/L, and the pH value is 8.2.
The industrial wastewater treatment method comprises the following steps:
(1) adding magnetic seeds, a coagulant and a flocculating agent into the industrial wastewater to perform magnetic flocculation reaction, wherein the magnetic seeds are ferroferric oxide, and the addition amount is 40 mg/L; the coagulant is polyaluminium chloride (PAC), and the addition amount is 30 mg/L; the flocculating agent is Polyacrylamide (PAM), the adding amount is 1mg/L, and the magnetic flocculation reaction is carried out for 5min to obtain a first-level precipitate and first-level flocculation effluent; shearing the primary precipitate into flocculent sludge, and recovering magnetic seeds from the flocculent sludge to continue the magnetic flocculation reaction;
(2) conveying the primary flocculated effluent to an active sand filter for primary filtration, wherein the particle size of active sand in the active sand filter is 0.8-1.2mm, the filtration speed of the primary filtration is 10m/h, the moving speed of a sand bed is 8mm/min, and the air for lifting the active sand is 6kg/cm2The first-stage flocculated effluent is subjected to first-stage filtration to obtain first-stage filtered effluent;
(3) conveying the primary filtered water to a fiber ball filter for secondary filtration, wherein the height of a filter layer in the fiber ball filter is 1500mm, the filtration speed of the secondary filtration is 32m/h, and the primary filtered water is subjected to secondary filtration to obtain filtered water;
(4) carrying out primary ozone catalytic oxidation treatment on the filtered water under the catalysis of a first catalyst for 45min, wherein the first catalyst is spherical alumina loaded with Mn, and the diameter of the spherical alumina is 5mm, so as to obtain primary ozone catalytic oxidation water;
(5) and performing secondary ozone catalytic oxidation treatment on the primary ozone catalytic oxidation water under the catalytic action of a second catalyst for 75min, wherein the second catalyst is spherical alumina loaded with Co, and the diameter of the spherical alumina is 5mm, so as to obtain the purified water.
Example 2
This example is different from example 1 in that, in the first catalyst used in step (4), the spherical alumina-supported active ingredient is Cu.
Example 3 this example differs from example 1 in that in the first catalyst used in step (4), the active ingredient supported on spherical alumina is Fe.
Example 4
This example differs from example 1 in that in the first catalyst used in step (4), the active components supported on spherical alumina are Mn and Ce in a molar mass ratio of 4: 1.
Example 5
This example is different from example 1 in that in the second catalyst used in step (5), the active ingredient supported on spherical alumina is Ni.
Example 6
The difference between this example and example 1 is that in step (4), the time for performing the primary ozone catalytic oxidation treatment was 30 min.
Example 7
The difference between this example and example 1 is that in step (4), the time for performing the primary catalytic ozonation treatment was 60 min.
Example 8
The difference between this example and example 1 is that in step (5), the time for performing the secondary ozone catalytic oxidation treatment was 60 min.
Example 9
The difference between this example and example 1 is that in step (5), the time for performing the secondary ozone catalytic oxidation treatment was 90 min.
Example 10
The present example is different from example 1 in that the time for performing the primary catalytic ozonation treatment in step (4) is 15 min.
Example 11
The difference between this example and example 1 is that the time for performing the primary catalytic ozonation treatment in step (4) is 90 min.
Example 12
The difference between this example and example 1 is that in step (5), the time for performing the secondary ozone catalytic oxidation treatment was 30 min.
Example 13
The difference between this example and example 1 is that in step (5), the time for performing the secondary ozone catalytic oxidation treatment was 120 min.
Comparative example 1
This comparative example is different from example 1 in that step (5) was not carried out and the first-order ozone catalytic oxidation water was directly used as purified water.
Comparative example 2
This comparative example is different from example 1 in that step (4) is not performed, and the filtered water is directly subjected to the secondary catalytic ozonation treatment under the action of the second catalyst to obtain purified water.
Test examples
The quality of the purified water provided in examples and comparative examples was measured, respectively, and the results are shown in table 1 below.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: according to the industrial wastewater treatment system, industrial wastewater II-grade biochemical water is subjected to advanced treatment sequentially through the magnetic flocculation reactor, the active sand filter, the fiber ball filter, the primary ozone catalytic oxygen tower and the secondary ozone catalytic oxidation tower, inorganic pollutants in an ionic state and suspended solid particles in the industrial wastewater II-grade biochemical water are subjected to flocculation treatment by the magnetic flocculation reactor to generate primary precipitates to be removed, and solid suspended matters and suspended flocs in the obtained primary flocculated water are effectively removed sequentially through the active sand filter and the fiber ball filter; after solid pollution is removed, organic pollutants and ammonia nitrogen in the wastewater are further effectively removed by using the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower, so that the treated effluent has excellent water quality, can reach the national standard of 'surface water environment quality (GB 3838-2002)' surface III-class water standard, cannot cause pollution after being directly discharged into urban rivers, and can effectively repair urban water.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A system for treating industrial wastewater, comprising:
the magnetic flocculation unit is used for removing inorganic pollutants in an ionic state and solid particles in a suspended state in the industrial wastewater to obtain primary flocculation effluent and primary sediments, and is provided with a primary flocculation water outlet;
the filtering unit is used for removing solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent, and is provided with a water inlet to be filtered and a filtered water outlet, and the water inlet to be filtered is connected with the primary flocculated water outlet;
the ozone catalytic oxidation unit is used for removing organic pollutants and ammonia nitrogen in the filtered water, and is provided with a catalytic oxidation water inlet and a purified water outlet, and the catalytic oxidation water inlet is connected with the filtered water outlet.
2. The treatment system of claim 1, wherein the magnetic flocculation unit comprises:
the magnetic flocculation reactor is provided with a magnetic sludge outlet, a feed inlet and the primary flocculation water outlet;
the magnetic sludge shearing machine is provided with a magnetic sludge inlet and a floccule outlet, and the magnetic sludge inlet is connected with the magnetic sludge outlet;
the magnetic seed separator is provided with a floccule inlet and a magnetic seed outlet, the floccule inlet is connected with the floccule outlet, and the magnetic seed outlet is connected with the feeding port.
3. The treatment system according to claim 1 or 2, wherein the magnetic flocculation reactor comprises a coagulation tank and a flocculation tank which are communicated with each other, and the magnetic sludge outlet and the primary flocculation water outlet are arranged on the flocculation tank.
4. The treatment system of claim 1, wherein the filtration unit comprises:
the active sand filter is provided with the water inlet to be filtered and a primary filtering water outlet, the active sand filter is provided with a sand bed, and the particle size of active sand in the sand bed is preferably 0.8-1.2 mm;
the fiber ball filter is provided with a primary filtering water inlet and the filtering water outlet, the primary filtering water outlet is connected with the primary filtering water inlet, a filter material layer is arranged in the fiber ball filter, and the layer height of the filter material layer is preferably 1200-1800 mm.
5. The treatment system of claim 1, wherein the catalytic ozonation unit comprises a primary catalytic ozonation device and a secondary catalytic ozonation device which are connected in sequence, the catalytic ozonation water inlet is arranged on the primary catalytic ozonation device, and the purified water outlet is arranged on the secondary catalytic ozonation device;
the primary ozone catalytic oxidation device is filled with a first catalyst, and the active component of the first catalyst comprises at least one of Mn, Cu, Fe or Ce;
and/or the secondary ozone catalytic oxidation device is filled with a second catalyst, and the active component of the second catalyst comprises at least one of Co or Ni.
6. A method for treating industrial wastewater, which is characterized by comprising the following steps:
step S1, performing magnetic flocculation treatment on the industrial wastewater to remove inorganic pollutants in an ionic state and suspended solid particles in the industrial wastewater to obtain primary flocculation effluent and primary precipitates;
step S2, filtering the primary flocculated effluent to remove solid suspended matters and suspended flocs in the primary flocculated effluent to obtain filtered effluent;
and step S3, carrying out ozone catalytic oxidation treatment on the filtered water to remove organic pollutants and ammonia nitrogen in the filtered water, and obtaining purified water.
7. The treatment method according to claim 6, wherein the step S1 includes adding a magnetic seed and a water treatment agent to the industrial wastewater to perform the magnetic flocculation treatment,
preferably, the time of the magnetic flocculation reaction is 4-6 min;
preferably, the magnetic seeds comprise at least one of ferroferric oxide, ferrosilicon nanocrystals or neodymium iron boron;
preferably, the water treatment agent comprises a coagulant and a flocculant, the coagulant comprises at least one of polyaluminium chloride or polyferric sulfate, and the flocculant comprises polyacrylamide.
8. The process of claim 6 or 7, wherein the step S1 further comprises subjecting the primary precipitate to a magnetic seed recovery process, the magnetic seed recovery process comprising:
shearing the primary precipitate into flocculent sludge, and separating magnetic seeds from the flocculent sludge to obtain recovered magnetic seeds, wherein the time for separating the magnetic seeds is preferably 3-5 min;
and returning the recovered magnetic seeds to the step S1 for reuse.
9. The processing method according to claim 6, wherein the step S2 includes:
performing primary filtration on the primary flocculated effluent to remove the solid suspended matters to obtain primary filtered effluent;
performing secondary filtration on the primary filtered water to remove suspended flocs to obtain the filtered water;
preferably, the primary filtration is carried out by adopting an active sand filter, the active sand filter is provided with a sand bed, the particle size of active sand in the sand bed is further preferably 0.8-1.2mm, and the filtration speed of the primary filtration is preferably 8-12 m/h;
preferably, a fiber ball filter is adopted for the secondary filtration, a filter material layer is arranged in the fiber ball filter, the layer height of the filter material layer is further preferably 1200-1800mm, and the filtration speed of the secondary filtration is preferably 25-40 m/h.
10. The processing method according to any one of claims 6 to 9, wherein the step S3 includes:
carrying out primary ozone catalytic oxidation treatment on the filtered water to remove organic pollutants in the filtered water to obtain primary ozone catalytic oxidation water;
performing secondary ozone catalytic oxidation treatment on the primary ozone catalytic oxidation water to remove ammonia nitrogen in the primary ozone catalytic oxidation water to obtain purified water;
preferably, the primary ozone catalytic oxidation treatment is carried out under the catalysis of a first catalyst, the active ingredient of the first catalyst is selected from at least one of Mn, Cu, Fe or Ce, and the treatment time is preferably 30-60 min;
preferably, the secondary ozone catalytic oxidation treatment is carried out under the catalysis of a second catalyst, the active component of the second catalyst is at least one of Co or Ni, and the treatment time is preferably 60-90 min.
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