CN114180763A - Electrochemical advanced treatment device and process for perfluorinated compound wastewater - Google Patents
Electrochemical advanced treatment device and process for perfluorinated compound wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 26
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 53
- 238000005189 flocculation Methods 0.000 claims abstract description 45
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009297 electrocoagulation Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000005273 aeration Methods 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 230000016615 flocculation Effects 0.000 claims description 12
- -1 aluminum-iron-zinc Chemical compound 0.000 claims description 9
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- 238000004062 sedimentation Methods 0.000 claims description 7
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- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
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- 239000007788 liquid Substances 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides an electrochemical advanced treatment device for perfluorinated compound wastewater, which comprises an electrochemical unit and a filtering unit, wherein the electrochemical unit comprises an electro-catalysis tank and an electro-flocculation tank which are sequentially connected, a check valve is arranged between the electro-catalysis tank and the electro-flocculation tank, the electro-catalysis tank and the electro-flocculation tank are respectively and electrically connected with a first external power supply and a second external power supply through leads, the first external power supply is respectively connected with an anode electrode and a cathode electrode in the electro-catalysis tank through leads, the second external power supply is respectively connected with the anode electrode and the cathode electrode in the electro-flocculation tank through leads, and a water inlet pipe is arranged at the outer end of the electro-catalysis tank. The invention adopts the electrocatalysis tank and the electrocoagulation tank to coordinate with catalysis, reduction and adsorption, and removes fluoride in perfluorinated compound wastewater through each stage of filtering device.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an electrochemical advanced treatment device and process for perfluorinated compound wastewater.
Background
The perfluoro compound is an organic compound in which all hydrogen atoms linked to carbon atoms in a compound molecule are replaced by fluorine atoms. Is widely applied to the fields of textile, lubricant, surfactant, food package, electronic products and the like.
The perfluorinated compounds have very stable structures and are difficult to oxidize and lose electrons, and the treatment of wastewater, especially the advanced treatment of the wastewater is extremely difficult. The conventional water treatment method has difficulty in producing a rapid degradation effect on the water. At present, methods for removing perfluorinated compounds in wastewater mainly comprise biological methods, electrochemical methods, membrane separation technologies, adsorption methods, photocatalytic methods and the like. Wherein, the adsorption method and the membrane separation method remove the perfluorinated compounds in the wastewater by adsorption, separation and other modes, but have higher treatment cost and are easy to generate secondary pollution; the biological method has long degradation period and incomplete degradation; the photocatalysis method has long reaction time and low light energy utilization rate and is difficult to be applied in engineering; the electrochemical catalysis method has good treatment effect and higher energy consumption; the electric flocculation method has low energy consumption and high removal efficiency.
Therefore, it is very important to develop a technology for removing perfluoro compounds with good treatment effect and low cost by combining the synergistic effect of electrocatalysis and electrocoagulation adsorption.
Disclosure of Invention
The invention mainly aims to provide an electrochemical advanced treatment device and process for perfluorinated compound wastewater.
The invention provides an electrochemical advanced treatment device for perfluorinated compound wastewater, which comprises an electrochemical unit and a filtering unit, the electrochemical unit comprises an electro-catalysis tank and an electro-flocculation tank which are connected in sequence, a check valve is arranged between the electro-catalysis tank and the electro-flocculation tank, the electro-catalysis tank and the electro-flocculation tank are respectively and electrically connected with a first external power supply and a second external power supply through leads, the first external power supply is respectively connected with the anode electrode and the cathode electrode in the electro-catalysis cell through leads, the external power supply two-way is respectively connected with the anode electrode and the cathode electrode in the electric flocculation tank through leads, the outer end of the electro-catalysis tank is provided with a water inlet pipe, the outer end of the electro-flocculation tank is provided with a water outlet pipe, the inside of each of the electric flocculation tank and the electric catalysis tank is provided with a pH meter, and is respectively connected with an acid-base tank through an aeration pump, and the aeration pump is electrically connected with a PLC;
the filtering unit comprises an inclined tube sedimentation tank, a multi-media filter, a security filter and a resin adsorption tower which are connected in sequence.
Preferably, the anode electrode in the electrocoagulation cell is a metal sacrificial electrode, the metal sacrificial electrode is an aluminum metal, iron metal, zinc metal or aluminum-iron-zinc composite metal sacrificial electrode, and the cathode electrode in the electrocoagulation cell is a stainless steel plate electrode; the anode electrode in the electro-catalysis cell is a titanium-based coating electrode, the cathode electrode in the electro-catalysis cell is a stainless steel electrode or a carbon-based composite gas diffusion cathode, the titanium-based coating electrode is tubular or plate-shaped, and the metal sacrificial electrode is annular or plate-shaped.
Preferably, magnetic stirrers are arranged at the bottoms of the electric flocculation tank and the electric catalysis tank.
Preferably, the capacity of the acid-base pool is 5-20L, and the pH value range is 3-8.
Preferably, the aeration amount of the aeration pump is 10-200L/min.
Preferably, the size of the cathode electrode and the anode electrode of the electro-catalysis pool and the electro-flocculation pool is 0.4-2.0 m2/m3。
The invention also provides an electrochemical advanced treatment process of the perfluorinated compound wastewater, which adopts the electrochemical advanced treatment device of the perfluorinated compound wastewater and comprises the following steps: the method comprises the steps of enabling perfluorinated compound wastewater to enter an electro-catalysis tank through a water inlet pipe, measuring a result according to a pH meter, adjusting the pH value of the perfluorinated compound wastewater by using a PLC (programmable logic controller) and a peristaltic pump, enabling the perfluorinated compound wastewater to enter an electro-flocculation tank through a one-way valve after the electro-catalysis tank is electrified and continuously stirring, and enabling the perfluorinated compound wastewater to sequentially pass through an inclined tube sedimentation tank, a multi-media filter, a security filter and a resin adsorption tower after the electro-catalysis tank is electrified and reacted to obtain treated waste liquid.
Preferably, the voltage of the first external power supply of the electro-catalytic cell is 10V, the current is 500-800A, and the processing time is 4 h; the voltage of the second external power supply of the electric flocculation cell is 8V, the current is 400-700A, and the treatment time is 2 h.
Preferably, the filtering flow rate in the multi-media filter is 6-12 m/h, the filtering precision of the cartridge filter is less than or equal to 10 μm, the resin adsorption tower is filled with unlimited shape of mesoporous activated carbon, the resin type is macroporous resin such as strong base type styrene resin, the empty tower filtering speed is 4-8 m/h, and the contact time is 20-60 min.
Advantageous effects
The invention adopts the synergistic effect of various reduction, catalysis and adsorption processes of the electro-catalysis tank and the electro-flocculation tank, and removes fluoride in perfluorinated compound wastewater through each stage of filtering device.
The foregoing is only an overview of the technical solutions of the present invention, and in order to more clearly understand the technical solutions of the present invention, the present invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is a diagram of an electrochemical cell apparatus of the present invention;
FIG. 2 is a diagram of an overall apparatus of the present invention;
FIG. 3 is a graph showing the effect of removing fluorine compounds in examples 2 to 5.
1-PLC; 2-acid-base pool; 3-an aeration pump; 4-a check valve; 5-water inlet pipe; 6-titanium based coated electrodes; 7-stainless steel or carbon-based composite gas diffusion cathodes; 8-a pH meter; 9-an electrocatalysis cell; 10-a magnetic stirrer; 11-a metal sacrificial anode; 12-stainless steel plate electrodes; 13-water outlet pipe; 14-an electric flocculation tank; 15-external power supply I; 16-external power supply II; 17-an inclined tube sedimentation tank; 18-a multi-media filter; 19-a cartridge filter; 20-resin adsorption tower.
Detailed Description
The invention discloses an electric flocculation concerted catalysis method and a device for treating perfluorinated compound wastewater.
In order to understand the present invention, the following examples are given to further illustrate the present invention.
Example 1:
as shown in figures 1 and 2, an electrochemical advanced treatment device for perfluorinated compound wastewater comprises an electrochemical unit and a filtering unit, wherein the electrochemical unit comprises an electro-catalysis tank 9 and an electro-flocculation tank 14 which are connected in sequence, a check valve 4 is arranged between the electro-catalysis tank 9 and the electro-flocculation tank 14, the electro-catalysis tank 9 and the electro-flocculation tank 14 are respectively and electrically connected with a first external power supply 15 and a second external power supply 16 through leads, the first external power supply 15 is respectively connected with an anode electrode and a cathode electrode in the electro-catalysis tank 9 through leads, the second external power supply 16 is respectively connected with the anode electrode and the cathode electrode in the electro-flocculation tank 14 through leads, the outer end of the electro-catalysis tank 9 is provided with a water inlet pipe 5, the outer end of the electro-flocculation tank 14 is provided with a water outlet pipe 13, the interiors of the electro-flocculation tank 14 and the electro-catalysis tank 9 are both provided with a pH meter 8, the acid-base pool 2 is connected with the aeration pump 3 respectively, and the aeration pump 3 is electrically connected with a PLC 1;
the filtering unit comprises an inclined tube sedimentation tank 17, a multi-media filter 18, a cartridge filter 19 and a resin adsorption tower 20 which are connected in sequence.
The anode electrode in the electric flocculation tank 14 is a metal sacrificial electrode 11, the metal sacrificial electrode 11 is an aluminum metal, iron metal, zinc metal or aluminum-iron-zinc composite metal sacrificial electrode, and the cathode electrode in the electric flocculation tank 14 is a stainless steel plate electrode 12; an anode electrode in the electro-catalysis cell 9 is a titanium-based coating electrode 6, a cathode electrode in the electro-catalysis cell 9 is a stainless steel electrode or a carbon-based composite gas diffusion cathode 7, the titanium-based coating electrode 6 is tubular or plate-shaped, and the metal sacrificial electrode 11 is annular or plate-shaped.
The magnetic stirrers 10 are arranged at the bottoms of the electric flocculation tank 14 and the electric catalysis tank 9.
The capacity of the acid-base pool 2 is 5-20L, and the pH value range is 3-8.
The aeration rate of the aeration pump 3 is 10-200L/min.
The sizes of the cathode electrode and the anode electrode of the electro-catalysis tank 9 and the electro-flocculation tank 14 are 0.4-2.0 m2/m3。
Example 2:
electrochemical advanced treatment process for perfluorinated compound wastewater
500mL of perfluorinated compound wastewater with the concentration of 40mg/L is prepared, the perfluorinated compound wastewater enters an electro-catalysis tank 9 through a water inlet pipe 5, the aeration amount of an aeration pump 3 is adjusted to 20L/min, the voltage between electrodes in the electro-catalysis tank 9 is adjusted to 10V through an external power supply I15, the current is 500A, the perfluorinated compound wastewater enters the electro-catalysis tank 9 for treatment for 4h, then the perfluorinated compound wastewater enters an electro-flocculation tank 14 through a check valve 4, the pH value in the electro-flocculation tank 14 is adjusted to 5.0, the voltage between the electrodes in the electro-flocculation tank 14 is adjusted to 8V through an external power supply II 16, the current is 400A, after reaction for 2h, the perfluorinated compound wastewater sequentially enters an inclined tube sedimentation tank 17, a multi-media filter 18, a security filter 19 and a resin adsorption tower 20 through pipelines, and the clear solution is filtered to obtain the degradation rate of the perfluorinated compound.
Example 3:
the method is the same as the example 2, and is characterized in that: the current in the electro-catalysis cell 9 is adjusted to be 600A through the external power supply I15, the current in the electro-flocculation cell is adjusted to be 500A through the external power supply I16, and the degradation rate of the perfluorinated compounds is calculated.
Example 4:
the method is the same as the example 2, and is characterized in that: the current in the electro-catalysis cell 9 is adjusted to 700A through the external power supply I15, the current in the electro-flocculation cell is adjusted to 600A through the external power supply I16, and the degradation rate of the perfluorinated compounds is calculated.
Example 5:
the method is the same as the example 2, and is characterized in that: the current in the electro-catalysis cell 9 is adjusted to be 800A through the external power supply I15, the current in the electro-flocculation cell is adjusted to be 700A through the external power supply I16, and the degradation rate of the perfluorinated compounds is calculated.
The results of examples 2 to 5 are shown in fig. 3, in which the degradation rate of the perfluoro compound obtained in example 2 was 79.6%, the degradation rate of the perfluoro compound obtained in example 3 was 84.9%, the degradation rate of the perfluoro compound obtained in example 4 was 91.3%, and the degradation rate of the perfluoro compound obtained in example 5 was 97.2%.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. An electrochemical advanced treatment device for perfluorinated compound wastewater comprises an electrochemical unit and a filtering unit, and is characterized in that:
the electrochemical unit comprises an electro-catalysis tank and an electro-flocculation tank which are sequentially connected, a check valve is arranged between the electro-catalysis tank and the electro-flocculation tank, the electro-catalysis tank and the electro-flocculation tank are respectively and electrically connected with a first external power supply and a second external power supply through leads, the first external power supply is respectively connected with an anode electrode and a cathode electrode in the electro-catalysis tank through leads, the second external power supply is respectively connected with the anode electrode and the cathode electrode in the electro-flocculation tank through leads, a water inlet pipe is arranged at the outer end of the electro-catalysis tank, a water outlet pipe is arranged at the outer end of the electro-flocculation tank, pH meters are respectively arranged in the electro-flocculation tank and the electro-catalysis tank, an acid-base tank is respectively connected with the electro-flocculation tank through an aeration pump, and the aeration pump is electrically connected with a PLC;
the filtering unit comprises an inclined tube sedimentation tank, a multi-media filter, a security filter and a resin adsorption tower which are connected in sequence.
2. The electrochemical advanced treatment device for the perfluorinated compound wastewater as claimed in claim 1, wherein: the anode electrode in the electrocoagulation cell is a metal sacrificial electrode, the metal sacrificial electrode is an aluminum metal, iron metal, zinc metal or aluminum-iron-zinc composite metal sacrificial electrode, and the cathode electrode in the electrocoagulation cell is a stainless steel plate electrode; the anode electrode in the electro-catalysis cell is a titanium-based coating electrode, the cathode electrode in the electro-catalysis cell is a stainless steel electrode or a carbon-based composite gas diffusion cathode, the titanium-based coating electrode is tubular or plate-shaped, and the metal sacrificial electrode is annular or plate-shaped.
3. The electrochemical advanced treatment device for the perfluorinated compound wastewater as claimed in claim 1, wherein: and magnetic stirrers are arranged at the bottoms of the electric flocculation tank and the electric catalysis tank.
4. The electrochemical advanced treatment device for the perfluorinated compound wastewater as claimed in claim 1, wherein: the capacity of the acid-base pool is 5-20L, and the pH value range of the acid-base pool is 3-8.
5. The electrochemical advanced treatment device for the perfluorinated compound wastewater as claimed in claim 1, wherein: the aeration rate of the aeration pump is 10-200L/min.
6. The electrochemical advanced treatment device for the perfluorinated compound wastewater as claimed in claim 1, wherein: the sizes of the cathode electrode and the anode electrode of the electro-catalysis tank and the electro-flocculation tank are 0.4-2.0 m2/m3。
7. An electrochemical advanced treatment process for perfluorinated compound wastewater, which is characterized in that: an electrochemical advanced treatment apparatus for perfluoro-compound wastewater as defined in any one of claims 1 to 6, and comprising the steps of: the method comprises the steps of enabling perfluorinated compound wastewater to enter an electro-catalysis tank through a water inlet pipe, measuring a result according to a pH meter, adjusting the pH value of the perfluorinated compound wastewater by using a PLC (programmable logic controller) and a peristaltic pump, enabling the perfluorinated compound wastewater to enter an electro-flocculation tank through a one-way valve after the electro-catalysis tank is electrified and continuously stirring, and enabling the perfluorinated compound wastewater to sequentially pass through an inclined tube sedimentation tank, a multi-media filter, a security filter and a resin adsorption tower after the electro-catalysis tank is electrified and reacted to obtain treated waste liquid.
8. The electrochemical advanced treatment process for perfluorinated compound wastewater as claimed in claim 7, wherein the electrochemical advanced treatment process comprises the following steps: the voltage of an external power supply I of the electro-catalysis cell is 10V, the current is 500-800A, and the processing time is 4 h; the voltage of the second external power supply of the electric flocculation cell is 8V, the current is 400-700A, and the treatment time is 2 h.
9. The electrochemical advanced treatment process for perfluorinated compound wastewater as claimed in claim 7, wherein the electrochemical advanced treatment process comprises the following steps: the filtering flow rate in the multi-media filter is 6-12 m/h, the filtering precision of the security filter is less than or equal to 10 microns, the resin adsorption tower is filled with unlimited shape mesoporous activated carbon, the resin type is macroporous resin such as strong base styrene resin, the empty tower filtering speed is 4-8 m/h, and the contact time is 20-60 min.
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