CN109205860B

CN109205860B - Method for advanced treatment of coking wastewater through combined action of ozone and polymer microspheres loaded with ferrite compounds

Info

Publication number: CN109205860B
Application number: CN201811363655.XA
Authority: CN
Inventors: 王琼杰; 张勇; 汪金晓雪; 王育来; 孟冠华
Original assignee: Anhui University of Technology AHUT
Current assignee: Anhui University of Technology AHUT
Priority date: 2018-11-16
Filing date: 2018-11-16
Publication date: 2021-04-02
Anticipated expiration: 2038-11-16
Also published as: CN109205860A

Abstract

The invention belongs to the field of treatment of industrial refractory wastewater, and particularly relates to a method for deeply treating coking wastewater by joint action of ozone and polymer microspheres loaded with a ferrite compound.

Description

Method for advanced treatment of coking wastewater through combined action of ozone and polymer microspheres loaded with ferrite compounds

Technical Field

The invention belongs to the field of treatment of industrial refractory wastewater, and particularly relates to a method for deeply treating coking wastewater by combined action of ozone and polymer microspheres loaded with ferrite compounds.

Background

With the rapid development of economy in China, the energy demand is continuously increased, and as a big country taking coal as a main energy source, coking wastewater with large amount and high concentration is easily generated in the processes of coal coking, coal gas purification, chemical product refining, coking product recovery and the like, and the coking wastewater becomes one of the important pollution sources of the industry in China. The coking wastewater has complex components and various pollutant types, contains a large amount of phenol, biphenyl, heterocyclic ring, polycyclic aromatic hydrocarbon and other refractory organic pollutants, has high pollutant concentration and poor biodegradability, and is difficult to discharge after conventional treatment.

Even after the coking wastewater is subjected to secondary biochemical treatment, the effluent still contains natural organic matters, metabolites of a microbial growth process in the biological treatment, artificially synthesized refractory organic compounds and the like, and the following hazards are easily generated after the coking wastewater is discharged into a water body: (1) the COD and BOD values in the effluent are increased, and sensory indexes such as color, smell and taste of the effluent are influenced; (2) a large amount of bacteria are easy to breed in the water distribution system, so that the pipeline is corroded; (3) increasing the dosage of the medicament of the advanced treatment process; (4) increasing the use of disinfectants and producing a large amount of by-products.

Disclosure of Invention

The invention provides a method for deeply treating coking wastewater by joint action of ozone and polymer microspheres loaded with ferrite compounds, wherein the diameter of the polymer microspheres loaded with the ferrite compounds is 100-500 mu m, the preparation method comprises the steps of fully mixing a polymerization monomer, a cross-linking agent and an iron oxide compound for initiating polymerization,

the polymerized monomer consists of methacrylic acid, ethyl acrylate and butyl methacrylate, and the mass ratio of the methacrylic acid to the ethyl acrylate to the butyl methacrylate is 100: 65-85: 190-230 of the total weight of the alloy,

the crosslinking agent is triallyl isocyanurate, and the mass ratio of the crosslinking agent to methacrylic acid is 65-85: 100,

when the polymer microsphere loaded with the ferrite compound is prepared, the specific operation is as follows:

(1) adding sodium chloride into water, fully stirring to obtain sodium chloride solution,

wherein the solute mass fraction of the sodium chloride is 5-15%,

(2) adding a polymerized monomer, a cross-linking agent and an initiator into an organic solvent, fully mixing to obtain a polymerized monomer solution,

the organic solvent is toluene, xylene, ethyl acetate and the like, and the mass ratio of the used amount to the total amount of the comonomer is 100-300: 100,

the initiator is azobisisobutyronitrile or benzoyl peroxide, and the mass ratio of the initiator to the total amount of the comonomer is 0.2-2: 100,

(3) adding a surfactant and an iron oxide compound into the polymerized monomer solution obtained in the step (2), fully dispersing to obtain an oil phase dispersion liquid,

the ferrite compound is added in a granular form, and the mass ratio of the ferrite compound to the total amount of the comonomer is 8-60: 100,

the mass ratio of the surfactant to the ferrite compound is 0.05-0.12: 1,

(4) and (3) adding the oil phase dispersion liquid obtained in the step (3) into the sodium chloride solution obtained in the step (1), mixing fully, then carrying out heating reaction, filtering after full reaction, drying the obtained filter cake, then carrying out alkali liquor treatment, filtering again after full alkali liquor treatment, and cleaning and drying the filter cake.

When the polymer microspheres loaded with the ferrite compound are used for treating coking wastewater, ozone is introduced into the coking wastewater in the process that the coking wastewater flows through the polymer microspheres loaded with the ferrite compound,

the flow speed of the coking wastewater flowing through the polymer microspheres loaded with the ferrite compound is 0.5-5 BV/h,

the mass ratio of the polymer microspheres loaded with the ferrite compound to the coking wastewater to be treated is 1: 3-1: 6,

the rate of ozone introduction is 0.2-1 BV/h,

the treatment temperature is normal temperature.

Drawings

FIG. 1 is a schematic structural diagram of an apparatus and a related process flow for treating wastewater in each of examples and comparative examples of the present invention, wherein 1-an oxygen source (nitrogen source), 2-an ozone generator (nitrogen generator), 3-a flow meter, 4-a mixing reaction tower, 5-an iron oxide-loaded polymer microsphere material, 6-a porous sieve plate, 7-a water inlet, 8-a water outlet, and 9-a tail gas absorption apparatus.

Detailed Description

Example 1

(1) Preparing a sodium chloride solution with the mass fraction of sodium chloride of 14 percent at normal temperature (25 ℃, the same below);

(2) to 850 parts by weight of ethyl acetate, 100 parts by weight of methacrylic acid, 75 parts by weight of ethyl acrylate, 205 parts by weight of butyl methacrylate, 70 parts by weight of triallyl isocyanurate and 2.5 parts by weight of azobisisobutyronitrile were added at normal temperature (25 ℃ C., the same applies hereinafter), and a polymerization monomer solution was obtained after thorough mixing,

(3) adding 4 parts by weight of sodium dodecyl benzene sulfonate and 50 parts by weight of ferroferric oxide particles with the particle size of 0.5 mu m into the polymerization monomer solution obtained in the step (2), and fully dispersing to obtain an oil phase dispersion liquid;

(4) adding the oil-phase dispersion liquid obtained in the step (3) into 2000 parts by weight of the sodium chloride solution obtained in the step (1), heating to 55 ℃ for reaction for 6 hours after fully mixing, heating to 85 ℃ for reaction for 10 hours, filtering after fully reacting, drying the obtained filter cake, adding the filter cake into a mixed solution of ethanol with the mass 2 times of that of the filter cake and sodium hydroxide solution with the mass 4 times of that of the filter cake (the mass fraction of solute is 30%), heating to 75 ℃ for reaction for 8 hours, filtering again, fully washing the filter cake with deionized water, and fully drying at 55 ℃ to obtain the ferroferric oxide-loaded polymer microspheres.

Adding the ferroferric oxide-loaded polymer microspheres obtained in the embodiment into a mixed reaction tower, continuously introducing simulated coking wastewater (the composition of the simulated coking wastewater is 45mg/L of o-methylphenol, 30mg/L of quinoline, 20mg/L of 4-methyl-3-hexanone and the balance of water) into the mixed reaction tower, allowing the simulated coking wastewater to flow through the polymer microspheres in the tower from top to bottom, and introducing nitrogen into a polymer microsphere region in the tower in a bottom-up ventilation mode, wherein the water temperature of the simulated coking wastewater is 25 ℃, the flow rate of the simulated coking wastewater during introduction is 4BV/h, and the mass ratio of the polymer microspheres to the simulated coking wastewater in the mixed reaction tower is 1: 5, the speed of nitrogen gas introduced into the mixed reaction tower is 1 BV/h. The specific reaction device is shown in attached figure 1.

The method comprises the following steps of starting timing when simulated coking wastewater enters a mixed reaction tower at the beginning, sampling the treated simulated coking wastewater flowing out of the mixed reaction tower every 30 minutes, and detecting the concentration of pollutants in the wastewater, wherein the specific steps are shown in the following table:

TABLE 1

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	22mg/L	16mg/L	8mg/L
60 minutes	31mg/L	22mg/L	15mg/L
				90 minutes	38mg/L	27mg/L	19mg/L

In the above test, no ozone is introduced, so the adsorption performance of the microspheres is used to reduce the content of the relevant pollutants in the wastewater, but as the time is prolonged, the adsorption of the microspheres to the pollutants gradually reaches saturation, and the adsorption decontamination capacity is reduced. From the data in the table above, it can be simply calculated that:

at the node of 30 minutes, the adsorption contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are 23mg/L, 14mg/L and 12mg/L respectively,

at the node of 60 minutes, the adsorption contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 14mg/L, 8mg/L and 5mg/L,

when the node is reached within 90 minutes, the adsorption contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 7mg/L, 3mg/L and 1 mg/L;

in this example, based on the above detection test, the "nitrogen" is replaced by "ozone" (i.e. the scheme of claim 6), and the rest of the test is performed as above.

TABLE 2

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	3mg/L	1mg/L	1mg/L
60 minutes	10mg/L	8mg/L	6mg/L
				90 minutes	19mg/L	13mg/L	11mg/L

In the above table of detection tests, the adsorption performance of the microspheres and the catalytic performance of the iron oxide supported on the microspheres are simultaneously utilized to reduce the content of the relevant pollutants in the wastewater, and the content can be simply calculated according to the relevant data in table 2:

when the node is 30 minutes, the comprehensive removal contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 42mg/L, 29mg/L and 19mg/L,

at the node of 60 minutes, the comprehensive removal contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 35mg/L, 22mg/L and 14mg/L,

when the node is reached within 90 minutes, the comprehensive removal contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 26mg/L, 17mg/L and 9 mg/L;

the adsorption contribution at the relevant time node detected from table 1 is subtracted to give:

at the node of 30 minutes, the catalytic contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 19mg/L (42 mg/L-23 mg/L), 15mg/L (29 mg/L-14 mg/L) and 7mg/L (19 mg/L-12 mg/L),

at the node of 60 minutes, the catalytic contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 21mg/L (35 mg/L-14 mg/L), 14mg/L (22 mg/L-8 mg/L) and 9mg/L (14 mg/L-5 mg/L),

at the 90-minute node, the catalytic contributions of the microspheres to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 19mg/L (26 mg/L-7 mg/L), 14mg/L (17 mg/L-3 mg/L) and 8mg/L (9 mg/L-1 mg/L).

It can be seen that when the ferroferric oxide supported polymer microspheres prepared by the method are used for continuously treating coking wastewater, the catalytic performance of the iron oxide serving as an active ingredient is not reduced due to the increase of the amount of pollutants adsorbed on the microspheres, which is not easily foreseen by a person skilled in the art.

Comparative example 1

The crosslinking agent "triallyl isocyanurate" used in the preparation of the polymeric microspheres in example 1 was replaced with equimolar amounts of "trimethylolpropane trimethacrylate", and the remaining preparation operations, as well as the subsequent simulated coking wastewater types and associated wastewater treatment operations, were the same as in example 1.

In the coking wastewater treatment experiment of introducing nitrogen, the treated simulated coking wastewater flowing out of the mixed reaction tower is sampled every 30 minutes from the beginning of the timing when the simulated coking wastewater enters the mixed reaction tower, and the concentration of pollutants in the treated simulated coking wastewater is detected, which is shown in the following table:

TABLE 3

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	20mg/L	16mg/L	7mg/L
60 minutes	31mg/L	21mg/L	16mg/L
				90 minutes	37mg/L	27mg/L	19mg/L

Ozone is not introduced, so that the adsorption performance of the microspheres is utilized to reduce the content of related pollution in the wastewater, and the content can be simply calculated according to the data in the table:

at the node of 30 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 25mg/L, 14mg/L and 13mg/L,

at the node of 60 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are 14mg/L, 9mg/L and 4mg/L respectively,

at the node of 90 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 8mg/L, 3mg/L and 1 mg/L;

in the coking wastewater treatment experiment of ozone introduction, the treated simulated coking wastewater flowing out of the mixed reaction tower is sampled every 30 minutes from the beginning of the timing when the simulated coking wastewater enters the mixed reaction tower, and the concentration of pollutants in the treated simulated coking wastewater is detected, which is shown in the following table:

TABLE 4

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	4mg/L	5mg/L	0mg/L
60 minutes	21mg/L	14mg/L	13mg/L
				90 minutes	34mg/L	24mg/L	19mg/L

In the ozone-introducing detection test, the adsorption performance of the microspheres and the catalytic performance of the iron oxide loaded on the microspheres are simultaneously utilized to reduce the content of related pollution in the wastewater, and the content can be simply calculated according to related data in a table 4:

at the node of 30 minutes, the microspheres prepared in the comparative example respectively contribute 41mg/L, 25mg/L and 20mg/L to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater,

at the node of 60 minutes, the microspheres prepared in the comparative example respectively contribute to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater by 24mg/L, 16mg/L and 7mg/L,

when the node is 90 minutes, the comprehensive removal contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 11mg/L, 6mg/L and 1 mg/L;

the adsorption contribution at the relevant time node detected from table 3 is subtracted to give:

at the node of 30 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in wastewater are respectively 16mg/L (41 mg/L-25 mg/L), 11mg/L (25 mg/L-14 mg/L) and 7mg/L (20 mg/L-13 mg/L),

at the node of 60 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 10mg/L (24 mg/L-14 mg/L), 7mg/L (16 mg/L-9 mg/L) and 3mg/L (7 mg/L-4 mg/L),

at the 90-minute node, the catalytic contributions of the microspheres prepared in this comparative example to o-methylphenol, quinoline, and 4-methyl-3-hexanone in the wastewater were 3mg/L (11 mg/L-8 mg/L), 3mg/L (6 mg/L-3 mg/L), and 0mg/L (1 mg/L-1 mg/L), respectively.

It can be seen that when the polymer microspheres prepared in this comparative example are used for continuously treating coking wastewater, as the amount of pollutants adsorbed on the microspheres increases, the catalytic performance of the active ingredient iron oxide decreases, which can be interpreted as follows: when the microspheres adsorb pollutants to a certain degree, the microspheres can have the similar shielding and covering effects on the active ingredients loaded on the microspheres, so that the catalytic capability is reduced. This is also a routine knowledge in the art.

Comparative example 2

The procedure of example 1 was followed except that "butyl methacrylate" in the polymerized monomers used in the preparation of the polymer microspheres in example 1 was replaced with equimolar "ethyl acrylate", and the type of the remaining preparation operations, and the subsequent simulated coking wastewater and the associated wastewater treatment operations were the same.

TABLE 5

at the node of 30 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 17mg/L, 9mg/L and 10mg/L,

at the node of 60 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 8mg/L, 4mg/L and 4mg/L,

at the node of 90 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 2mg/L, 0mg/L and 1 mg/L;

TABLE 6

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	10mg/L	6mg/L	0mg/L
60 minutes	26mg/L	19mg/L	10mg/L
				90 minutes	38mg/L	28mg/L	16mg/L

In the ozone-introducing detection test, the adsorption performance of the microspheres and the catalytic performance of the iron oxide loaded on the microspheres are simultaneously utilized to reduce the content of related pollution in the wastewater, and the content can be simply calculated according to related data in a table 6:

at the node of 30 minutes, the microspheres prepared in the comparative example respectively contribute 35mg/L, 24mg/L and 20mg/L to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater,

at the node of 60 minutes, the microspheres prepared in the comparative example respectively contribute to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater by 19mg/L, 11mg/L and 10mg/L,

when the node is 90 minutes, the comprehensive removal contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 7mg/L, 2mg/L and 4 mg/L;

the adsorption contribution at the relevant time node detected from table 5 is subtracted to give:

at the node of 30 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 18mg/L (35 mg/L-17 mg/L), 15mg/L (24 mg/L-9 mg/L) and 10mg/L (20 mg/L-10 mg/L),

at the node of 60 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 11mg/L (19 mg/L-8 mg/L), 7mg/L (11 mg/L-4 mg/L) and 6mg/L (10 mg/L-4 mg/L),

at the 90-minute node, the catalytic contributions of the microspheres prepared in this comparative example to o-methylphenol, quinoline, and 4-methyl-3-hexanone in the wastewater were 5mg/L (7 mg/L-2 mg/L), 2mg/L (2 mg/L-0 mg/L), and 3mg/L (4 mg/L-1 mg/L), respectively.

It can be seen that when the polymer microspheres prepared in the comparative example are used for continuously treating coking wastewater, the catalytic performance of the iron oxide serving as an active ingredient is reduced along with the increase of the amount of pollutants adsorbed on the microspheres.

Comparative example 3

The preparation procedure of example 1 was the same as that of example 1 except that "methacrylic acid" in the polymerized monomers used in the preparation of the polymer microspheres was replaced with equimolar "ethyl acrylate", and the type of the subsequent simulated coking wastewater and the relevant wastewater treatment procedure were the same.

TABLE 7

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	23mg/L	15mg/L	9mg/L
60 minutes	33mg/L	24mg/L	15mg/L
				90 minutes	38mg/L	28mg/L	20mg/L

at the node of 30 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are 22mg/L, 15mg/L and 11mg/L respectively,

at the node of 60 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 12mg/L, 6mg/L and 5mg/L,

at the node of 90 minutes, the adsorption contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 7mg/L, 2mg/L and 0 mg/L;

TABLE 8

	O-methyl phenol	Quinolines	4-methyl-3-hexanones
				30 minutes	4mg/L	0mg/L	1mg/L
60 minutes	24mg/L	16mg/L	12mg/L
				90 minutes	34mg/L	24mg/L	19mg/L

In the ozone-introducing detection test, the adsorption performance of the microspheres and the catalytic performance of the iron oxide loaded on the microspheres are simultaneously utilized to reduce the content of related pollution in the wastewater, and the content can be simply calculated according to related data in a table 8:

at the node of 30 minutes, the microspheres prepared in the comparative example respectively contribute 41mg/L, 30mg/L and 19mg/L to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater,

at the node of 60 minutes, the microspheres prepared in the comparative example respectively contribute 21mg/L, 14mg/L and 8mg/L to the comprehensive removal of o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater,

the adsorption contribution at the relevant time node detected from table 7 is subtracted to give:

at the node of 30 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 19mg/L (41 mg/L-22 mg/L), 15mg/L (30 mg/L-15 mg/L) and 8mg/L (19 mg/L-11 mg/L),

at the node of 60 minutes, the catalytic contributions of the microspheres prepared in the comparative example to o-methylphenol, quinoline and 4-methyl-3-hexanone in the wastewater are respectively 9mg/L (21 mg/L-12 mg/L), 8mg/L (14 mg/L-6 mg/L) and 3mg/L (8 mg/L-5 mg/L),

at the 90-minute node, the catalytic contributions of the microspheres prepared in this comparative example to o-methylphenol, quinoline, and 4-methyl-3-hexanone in the wastewater were 4mg/L (11 mg/L-7 mg/L), 4mg/L (6 mg/L-2 mg/L), and 1mg/L (1 mg/L-0 mg/L), respectively.

Claims

1. A method for deeply treating coking wastewater by combining ozone and polymer microspheres loaded with ferrite compounds is characterized by comprising the following steps: the preparation method of the polymer microsphere loaded with the ferrite compound comprises the steps of fully mixing a polymerization monomer, a cross-linking agent and the ferrite compound, then carrying out initiated polymerization,

the polymerization monomer is composed of methacrylic acid, ethyl acrylate and butyl methacrylate, and the mass ratio of the methacrylic acid to the ethyl acrylate to the butyl methacrylate is 100: 65-85: 190-230 of the total weight of the alloy,

the crosslinking agent is triallyl isocyanurate, and the mass ratio of the crosslinking agent to the methacrylic acid is 65-85: 100,

the concrete operation for preparing the polymer microsphere loaded with the ferrite compound is that,

(1) adding sodium chloride into water, and fully stirring to obtain a sodium chloride solution;

(2) adding the polymerized monomer, the cross-linking agent and the initiator into an organic solvent, and fully mixing to obtain a polymerized monomer solution;

(3) adding a surfactant and the iron oxide compound into the polymerized monomer solution obtained in the step (2), and fully dispersing to obtain an oil phase dispersion liquid;

2. The method for deeply treating coking wastewater according to claim 1, characterized in that: the organic solvent in the step (2) is toluene, xylene or ethyl acetate, and the mass ratio of the used amount of the organic solvent to the total amount of the comonomer is 100-300: 100.

3. the method for deeply treating coking wastewater according to claim 1, characterized in that: the mass ratio of the iron oxide compound to the total amount of the comonomer in the step (3) is 8-60: 100.

4. the method for deeply treating coking wastewater according to claim 1, characterized in that: the method for deeply treating the coking wastewater comprises the step of introducing ozone into the coking wastewater in the process that the coking wastewater flows through the polymer microspheres loaded with the ferrite compounds.

5. The method for deeply treating coking wastewater according to claim 4, characterized in that: the flow speed of the coking wastewater flowing through the polymer microspheres loaded with the ferrite compound is 0.5-5 BV/h.

6. The method for deeply treating coking wastewater according to claim 4, characterized in that: the mass ratio of the polymer microspheres loaded with the ferrite compounds to the coking wastewater is 1: 3-1: 6.