Waste fluid or waste water treatment method and its apparatus

Abstract

A method for electrochemical oxidation decomposition of difficult to decompose compounds like aromatic compounds, organic chlorine compounds, agricultural chemicals, dioxin, PCB and water soluble polymers that are contained in waste fluid, such as print developing waste fluid, factory waste water and industrial waste water of things such as landfill soil seeping waste water by carrying out electrolysis at a high current density to eliminate and purify difficult to decompose substances in the waste fluid. Waste fluid containing difficult to decompose substances is introduced into an electrolytic chamber with an anode that is a ferrite electrode, electrolysis is performed at a high current density of 10 A/dm2 or higher, hypohalogenous acid and active oxygen are generated in the waste fluid along with a strong anode oxidation action being brought about, and the oxidation decomposition is repeated by re-circulating the waste fluid through a filter, electrolyzer and intermediate collecting chamber.

Description

BACKGROUND OF THE INVENTION

[0001] This invention pertains to electrochemical oxidation decomposition of difficult to decompose substances such as aromatic compounds (benzene, chlorobenzene types, chlorophenol) that are contained in things such as waste fluid of things such as developing waste fluid, incinerator exhaust gas treatment water, waste water of things such as industrial waste, landfill soil seeped waste water and washing waste water of landfill soil, organic compounds (such as trichloroethylene, tetrachloroethylene, tetrachloroethane), agricultural chemicals (such as DDT, PCP, parathion, TPN.tetrachloroisophthalonitril, triforin, MEP.sumithion, diazinon), dioxin, PCB, water soluble polymers such as poly(vinyl alcohol), polyacrylonitrile, polyether) and nitrate ions.

BRIEF DESCRIPTION OF THE PRIOR ART

[0002] Treatment of waste fluid or waste water that contains difficult to decompose substances such as the aforementioned aromatic compounds (benzene, chlorobenzene types, chlorophenol), organic chlorine compounds (such as trichloroethylene, tetrachloroethylene, tetrachloroethane), agricultural chemicals (such as DDT, PCP, parathion, TPN tetrachloroisophthalonitril, triforin, MEP sumithion, diazinon), dioxin types, PCB.biphenyl chloride types, water soluble polymers (such as poly(vinyl alcohol), polyacrylonitrile, polyether) and nitrate ions is difficult. Adequate treatment by bio-treatment methods or absorption methods that have been previously widely used was difficult for the above-mentioned difficult to decompose compounds in waste fluid or waste water with seeped waste water from landfill soil after waste treatment, developing waste fluid and waste water of chemical factories.

[0003] The present inventors filed patents as follows pertaining to waste fluid or waste water purification and sterilization methods and their apparatus.

[0004] (1) Japanese Patent Application H7-004319

[0005] “Waste Fluid Treatment Equipment”

[0006] According to this prior patent application, a circulating current path is established between an intermediate collection chamber that collects waste fluid and an electrolytic chamber, electrolysis is carried out within an electrolytic chamber wherein active oxygen is generated within the circulating waste fluid, and the oxidation decomposition action of the active oxygen that is generated is brought in contact with the waste fluid. A sodium halide or a potassium halide is utilized for generating active oxygen.

[0007] A decrease of COD 10520 of waste printing plate developing solution to COD 300 is achieved with an electrode surface area of 40 dm2, a voltage of 7 V, a current of 100 A and a current density of 2.5 dm2. However, problems remain such as the suppression of the generation of chlorine gas and the need for further improving the treatment efficiency. In particular, a high current density is necessary for a high oxidation electrolysis efficiency of difficult to decompose compounds by anode oxidation. However, increasing current density to greater than 2.5 dm2 results in corrosion of the titanium platinum plated (1.5 μ) anode. Further, repeated electrolysis must be carried out under conditions of high residual chlorine concentrations for 3 to 6 hours in an acidic range for decreasing COD. But, there were the problems that chlorine gas was frequently generated and trihalomethanes were easily generated byproducts.

[0008] (2) Japanese Patent Application H9-299084

[0009] “Water Purification Method and Its Equipment”

[0010] This prior patent application describes purifying and sterilizing things such as bath water and pool water through electrolysis by an electrolyzer that is established in a circulating current path while holding to a fixed conductivity by supplying electrolytes for water with a low electrical conductivity such as bath water or pool water. According to this application purification and sterilization is possible by electrolysis of water with a low electrical conductivity due to having ferrite electrodes as the anodes. However, there is still the problem of ferrite electrode damage due to the terminal section being heated when the electrical current value increases.

[0011] Filtering with things like filters is also often carried out for the purification of used water and waste water. There is the problem of refreshing filters because of filter clogging.

[0012] (3) Japanese Patent Application H8-203814

[0013] “Filter Washing and Refreshing Equipment”

[0014] This prior patent application describes a method for washing and refreshing filters using an electrolyzer.

[0015] Effective electrolysis is possible when a filter is not established on the side toward the electrolyzer due to the elimination of suspended matter in the water to be treated when using an electrolyzer for the purification and sterilization of used water or waste water. A decrease of the treated amount when the filter becomes covered is a problem.

[0016] (4) Japanese Patent Application 2000-168578

[0017] “Electrolyzer”

[0018] This prior patent application describes an electrolysis method that is characterized by using a low melting point metal or mercury with good conductivity for forming the junction of the terminal main body with a nickel ferrite electrode as the anode. An electrolyzer that can purify and sterilize even water with a low conductivity such as low conductivity bio-use, waste water, bath water and pool water can be developed by this prior patent application, but oxidation decomposition treatment of difficult to decompose substances that are contained in waste fluid or waste water is not possible.

SUMMARY OF THE INVENTION

[0019] The carrying out of electrolysis with high current density is desirable for electrochemical oxidation decomposition of difficult to decompose substances in waste fluid and waste water. The electrodes that are generally used in the past have the problem of the anodes corroding in a short period under highly acidic conditions due to being exposed to strong acids.

[0020] This invention has the object of providing an electrochemical oxidation decomposition method and apparatus for difficult to decomposable compounds such as aromatic compounds (benzene, chlorobenzene types, chlorophenol), organic chlorine compounds (such as trichloroethylene, tetrachloroethylene, tetrachloroethane), agricultural chemicals (such as DDT, PCP, parathion, TPN tetrachloroisophthalonitril, triforin, MEP sumithion, diazinon), dioxin types, PCB.biphenyl chloride types, water soluble polymers (such as poly(vinyl alcohol), polyacrylonitrile, polyether) and nitrate ions that are contained in things such as waste fluid of developing waste fluid, factory waste water and industrial waste water of things such as landfill soil seeped waste water with electrolysis performed at high current density using a simple process at low cost with a ferrite electrode as the anode.

[0021] The means as follows are devised as an electrolysis method of this invention for solving the aforementioned problems.

[0022] Waste fluid or waste water that contains difficult to decompose substances is introduced in an electrolyzer 1 with an anode 11 that is a ferrite electrode and a powerful oxidation decomposition action is imparted by generating hypohalogenous acid and active oxygen for waste fluid or waste water through electrolysis with a current density of 10 A/dm2 or higher.

[0023] Electrode oxidation by electrolysis which is carried out at a high current density has oxidation decomposition action due to the hypohalogenous acid and active oxygen that are generated by that with this powerful oxidation decomposition.

[0024] This is powerful as active oxygen such as a hydroxide radical (OH.) is generated at the anode, but the life of active oxygen such as this hydroxide radical (OH.) is short. The life is much longer than that of active oxygen such as a hydroxide radical (OH.) when hypohalogenous acid that is generated in the electrolytic treatment solution is in contact with things such as organic substances. The hypohalogenous acid in the electrolytic treatment solution temporarily decomposes from contact with things such as organic substances and oxidation decomposition of difficult to decompose compounds is possible by the generation of active oxygen of things such as a hydroxy radical (OH.).

[0025] When there is electrolysis at a high current density, a nickel ferrite electrode may be damaged by heat generated in the metal terminal section. The present invention solves the problem of terminal heat generation by using a low temperature melting point metal with a melting point of 150° C. or less, preferably of 100° C. or less, or mercury which has good electrical conductivity, for a low melting point metal junction or mercury filled section 14 of nickel ferrite electrode 11 and anode terminal main body 15. The terminal main body of the solid rod terminal is inserted to make internal contact to a long cylindrical electrode length-wise, and a broad electrical contact surface is maintained due to being filled with a melted low melting point metal or mercury.

[0026] Electrolysis at a high current density of 10˜1000 dm2 becomes possible by the means discussed in the proceeding paragraph. The present invention can be applied to waste fluid or waste water that includes a wide range of difficult to decompose substances, but being carried out at a current density of 20˜300 A/dm2 is desirable as economical for current demands.

[0027] The electrode surface area easily can be increased by easily increasing the number of individual units by connecting a number of cylindrical nickel ferrite electrodes 11 in a number of units length-wise separated by means of a separator 14 that is water resistant and corrosion resistant.

[0028] When the electrical conductivity of the waste fluid or waste water is low, strong anode oxidation action can be carried out by the flow of the current at a high current density of 10 A/dm2 or higher by adding sodium halide or potassium halide (bromine or chlorine as the halogen).

[0029] Waste fluid or waste water is introduced into an electrolytic path (reaction section) 13, electrolytic treatment is repeatedly carried out, and elimination is by successive oxidation decomposition from substances that are comparatively easily decomposed, then the substances that are easily oxidized by electrode oxidation or active oxygen of the generated hypohalogenous acid are reacted and the difficult to decompose substances remain unreacted, but oxidation decomposition can be carried out with good efficiency on difficult to decompose substances by repeating electrolytic treatment through circulation.

[0030] Carrying out electrolysis of waste fluid or waste water in an electrolytic path 13 of an electrolyzer 1 only one time is inadequate for carrying out effective electrolysis for waste fluid or waste water that contains difficult to decompose compounds. The construction is such that a circulating current path 51 is established between an intermediate collection chamber 4 that collects waste fluid or waste water and the electrolyzer 1, electrolysis is carried out in the electrolytic path 13 of the electrolyzer 1 such as generating hypohalogenous acid and active oxygen in the circulating waste fluid or waste water, and bringing about oxidation decomposition action of the generated hypohalogenous acid and active oxygen for the waste fluid or waste water that is collected in the intermediate collection chamber 4. The aforementioned waste fluid or waste water collection chamber successively sends the waste fluid and waste water that has arrived from the electrolyzer 1 back to the electrolyzer. The purified part is discharged from the treated water outlet 33 through the treated water strainer 32, this is repeated for waste fluid or waste water since the construction is such that the same amount as that is introduced through the strainer 31 from the waste fluid or waste water tank 6 and continues along with receiving the anode oxidation action in this electrolytic path 13 and oxidation decomposition treatment is possible for waste fluid or waste water.

[0031] Along with removing filtered substances in waste fluid or waste water by the placement of a filter 3 in the circulating current path 51 on the side toward the electrolyzer 1, the oxidation decomposition action of hypohalogenous acid and active oxygen that are generated in the circulating water is imparted to the difficult to decompose substances in the filtered substances that are accumulated in the filter 3, and the oxidation decomposition action is imparted to the difficult to decompose substances along with the organic substances in the accumulated filtered substances.

[0032] Effective decomposition treatment is possible by selective combinations of things such as current density, electrical conductivity, electrode surface area, treatment flow rate, and independent or mixed (mixing molar ratio range from 6:4 to 1:9) halogen ions, bromine ions and chlorine ions corresponding to any difficult to decompose compounds that are contained in waste fluid or waste water such as developing waste fluid types (such as color developing.fixing solution, printing making developing.stabilizing solution), aromatic compounds, organic chlorine compounds, agricultural chemicals, dioxin types, PCB-biphenyl chloride types, and water soluble polymers.

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] FIG. 1 is a system flow diagram that shows the conditions when there are circulation and repeated oxidation decomposition action of waste fluid or waste water that contains difficult to decompose substances by establishing a circulating current path 51 between intermediate collection chamber 4, filter 3 and electrolyzer 1;

[0034] FIG. 2 is a system flow diagram of an electrolytic treatment experimental apparatus;

[0035] FIG. 3A is a lateral cross-sectional diagram and FIG. 3B a cut-away planar diagram that show the conditions with a low melting point metal junction or a mercury filled section 6 inserted with a terminal main body 15 inside an anode of an electrolyzer that is constructed by a cylindrical anode 11 and cathode 12; and

[0036] FIG. 4 is an exploded-view diagram detailing the elements of the electrolyzer of FIGS. 3A and 3B.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0037] Actual embodiments of this invention are explained by referring to the figures that originate in the actual examples, but this invention is not limited to these.

[0038] In the system flow diagram of FIG. 1, electrolytic treatment is performed by an electrolyzer for waste fluid or waste water through a circulating pump 5 causing waste fluid or waste water that contains difficult to decompose compounds to flow through a crude water strainer 31 from waste fluid or waste water tank 6. The oxidation decomposition action of hypohalogenous acid and active oxygen is executed during collection of electrolytic treated water in intermediate collection chamber 4. Then, this flows through circulating current path 51 and circulating pump 5 and circulates to the electrolyzer 1, and the process is repeated until adequate oxidation decomposition is performed and there is purification. When necessary, a filter 3 that removes the filtered substances in the waste fluid or wastewater is established in the circulating current path 51.

[0039] An experimental apparatus that is shown by the system flow diagram of FIG. 2 is used in this actual example and the power source substrate is 12 A, 60 V for the control.power source apparatus 2.

[0040] Dilute solution with color photograph developing waste fluid diluted to 5-fold was electrolytically treated. Developing solution waste fluid and fixing solution waste fluid were combined in a ratio of 5:9 for this developing waste fluid. Electrolytically treated water, which was electrolytically treated by being sent to electrolyzer 1 by a circulating pump 5 after the treated liquid was put in intermediate collecting chamber 4, flowed through circulating current path 51 and reached intermediate collecting chamber 4. Oxidation decomposition with good effects for difficult to decomposable substances was the experimental objective; with continued circulating, purification was carried out by repeating the electrolytic treatment in the electrolytic path (reaction section) 13 of electrolyzer 1 and elimination by successive oxidation decomposition from comparatively easily decomposed substances.

EXAMPLE I

[0041] This example uses an electrolyzer 1 that is shown by a lateral cross-sectional view (FIG. 3A) and a cut-away cross-sectional view (FIG. 3B).

[0042] A long solid rod terminal main unit 15 was inserted into an open section of the cylindrical nickel ferrite anode 11, and heated and melted low melting point metal or mercury was used for filling when there was electrode production for the interval of the anode 11 and terminal main body 15. A spacing of 1.6 mm was provided at the outside of the cylindrical anode 11, a cylindrical titanium cathode 12 was set such as to create an electrolytic path (reaction zone) 13. The effects which were obtained by performance tests were considered, and NaCl:NaBr was added in a mixture of a mixing molar ratio of 80:20 for 5-fold dilute solution and the conductivity was adjusted such as becoming 25,000 μS/cm.

[0043] Having an electrode surface area of 2 dm2 (dm2=square decimeter=100 cm2) for the electrolyzer 1, 5,000 cc of treatment liquid was put into intermediate collection chamber 4 and electrolysis was carried out while being circulated by circulating pump 5. The circulated amount was 500 cc per minute. The 5000 cc of treatment liquid was re-circulated once every 10 minutes and electrolytically treated, thus electrolytic treatment was done six times in 60 minutes. The effects of carrying out the test at current densities of 12, 18, and 24 A/dm2 are shown in Table 1. The COD when the current density was raised to 24 A/dm2 decreased to less than 100 mg/L, and can be discharged “as is” into the sewer. The maximum residual chlorine concentration even when less than one circulation per 5 minutes, in comparison with prior methods, was to the extent of 1,500 mg/L for the electrolysis time, and the generation of chlorine gas was also undesirable. The electrolytically treated water was extracted with hexane as per established methods and analyzed by ECD gas chromatography, but lower aliphatic halides such as chloroform and tetrachloroethylene were not tested.

[0044] TABLE 1 Electrolytic Treatment of Developing Waste Fluid

[0045] (Developing Waste Fluid Solution: Fixative Waste Fluid Solution 5:9)

TABLE 1
Current	A	12	24	36	48
Electrical	μS/cm	25,500	25,200	25,000	25,300
Conductivity
COD before	mg/L	12,400	12,400	12,400	12,400
Electrolytic
Treatment
COD	mg/L
Current Density	A/dm2	6	12	18	24
Electrolysis time	0	12,400	12,400	12,400	12,400
(min.)	10	11,100	8,820	6,990	3,120
	20	10,200	6,750	4,350	1,135
	30	9,830	5,620	3,420	535
	40	9,560	4,855	2,890	260
	50	9,440	4,560	2,615	125
	60	9,370	4,430	2,460	95
decomposition		24	64	80	99
rate %

EXAMPLE II

[0046] This example provides an oxidation decomposition example of industrial waste water by performing electrolysis while circulating washing waste water of things such as a synthesis reaction apparatus of a factory that manufactures polyether.

[0047] This example was based on the system flow chart of FIG. 1, using a filter with a ceramic type filter medium that was added to a cylinder which was used in Example 3 of Japanese Patent Application H8-203814 “Filter Washing Refreshing Equipment” of these inventors for filter 3, and electrolysis was carried out while 3,000 cc of treated liquid was put into the intermediate collection chamber 4 and was circulated by a circulating pump 3. The re-circulated amount was 300 cc every minute. The 3,000 cc treated liquid was re-circulated once every 10 minutes, thus electrolytic treatment was done such as being repeated six times in 60 minutes. Sodium chloride was added to the test wastewater and the electrical conductivity was adjusted such as becoming 25,060 μS/cm.

[0048] FIG. 4 is an exploded drawing of an electrolyzer 1 that is used in this example. The spacing of the cylindrical nickel ferrite anode 11 and the cylindrical titanium cathode 12 is 1.6 mm. The cylindrical nickel ferrite anode 11 uses one unit independently; two units are used by being connected when the electrode surface area is 0.44 dm2, and are proportionate when the electrode surface area is 0.88 dm2. The currents are respectively 12, 24 and 36 A. The current densities are 13.5, 27 and 41 A/dm2 for 0.88 dm2 with two units connected, and the current densities of one independent unit are 27, 54 and 82 A/dm2. The effects when the test was carried out are shown in Table 2.

[0049] The decrease in the COD by only using and circulating through a filter 3 under conditions that prevented electrolytic treatment was undesirable. Further, the circulating current amount decreased because the filter resistance decreased when the circulation continued. Even for conditions like that, electrolysis treatment began, the filter pressure increased when continued and the circulating current amount returned to the initial conditions. The filtered substance that accumulated in the filter for this repeatedly received the oxidation action of the hypohalogenous acid and active oxygen that are generated in the circulating water, and the wide contact surface of the filter showed effective oxidation decomposition for electrolytically treated water. The residual chlorine concentration was not related to the electrode surface area, and was generated in a completely proportion ratio to the current value, but a large COD decrease effect was determined even though the residual chlorine concentration was not very high when the current density was high.

[0050] The COD resistance effect for the electrolytic treatment of industrial waste water (polyether manufacturing) with the manufacture of polyether is shown in Table 2 through the relationship of current density and COD.

[0051] The electrode surface is compared for when there are cases with 0.88 dm2 and 0.44 dm2.

TABLE 2
Electrode Surface	dm2	0.88 dm2	0.44 dm2
Area
Current	A	12	24	32	12	24	32
Electrical	μS/cm	25,800	25,500	25,600	25,200	25,000	25,300
Conductivity
COD before	mg/L	1,600	1,600	1,600	1,600	1,600	1,600
Electrolytic
Treatment
COD mg/1
Current Density	A/dm2	13.5	27	41	27	54	82
Electrolysis Time	0	1,600	1,600	1,600	1,600	1,600	1,600
Minutes	10	1,580	1,490	1,390	1,560	1,470	1,380
	20	1,510	1,350	1,190	1,480	1,310	1,140
	30	1,290	1,020	790	1,210	960	680
	40	1,080	760	510	980	630	295
	50	990	660	450	820	440	95
	60	980	650	440	750	380	34
Electrolytic		39	59	72	53	76	98
Efficiency

EXAMPLE III

[0052] The COD could be effectively reduced by oxidation treatment by the electrolysis of the present application for things like pond water and wastewater of golf courses and washing waste water of used agricultural chemical containers. However, since things like organic substances of the soil are mixed in with things like pond water and waste water, in the present actual example, tests were carried out by dissolving only agricultural chemicals that are commercially available in the water for confirming whether or not the COD decrease showed an elimination of agricultural chemicals.

[0053] The agricultural chemicals that were used in the present actual example were increased to the following.

[0054] (1) TPN Powder “Daconil Powder”

[0055] Component: TPN (Inorganic Chlorine Type, C Class) . . . 4%

[0056] When diluted 30-fold with pure water, the COD was 2,800 mg/L and dilute aqueous solutions of this concentration were used for the test.

[0057] [Compound 1] Component:TPN Chemical Structure 1

[0058] Tetrachloroisophthalonitril

[0059] (2) Triforin Emulsion “Saprol Emulsion”

[0060] Component: Triforin (Ergosterol Biosynthysized Composite, A Class) . . . 15%

[0061] When diluted 50-fold with pure water, the COD was 2,680 mg/L, and dilute aqueous solutions of this concentration were used for the test.

[0062] [Compound 2] Component: Triforin Chemical Structure 2

[0063] 1,4-bis-(2,2,2-trichloro-1-formamide ether)-biperidine

[0064] (3) MEP Emulsion “Sumithion Emulsion”

[0065] Component: MEP (Organic Phosphorous Type, B Class) . . . 50%

[0066] When diluted 100-fold with pure water, the COD was 3,280 mg/L and dilute aqueous solutions of this concentration were used for the test.

[0067] [Compound 3] Component: MEP Chemical Structure 3

[0068] O, O-dimethyl-O-(3-methyl-4-nitrophenyl) thiophosphate

[0069] In the system flow diagram of FIG. 2, 3,000 cc of dilute aqueous agricultural chemical was put into an intermediate collection chamber 4 and electrolytically treated by an electrolyzer with a circulating pump 5. The oxidation decomposition action of hypohalogenous acid and active oxygen was executed during the re-circulation in the intermediate collection chamber 4 for the electrolytically treated water. Again circulated to the electrolyzer 1 through the re-circulating current path 51 and circulating pump 5, this was repeated until the water was purified by carrying out adequate oxidation decomposition. The filter, which had little filtered substance, was not used in the present example.

[0070] The electrode surface area of the electrolyzer 1 in the present example was 0.44 dm2, 5,000 cc of treatment liquid was put into the intermediate collection chamber 4, and electrolysis was carried out while being re-circulated by pump 5. The aqueous solution had an electrical conductivity of 200˜300 μS/cm and a mixture of NaCl:NaBr of a mixed molar ratio of 60:40 was added and the electrical conductivity was adjusted as becoming 30,000 μS/cm. The re-circulating amount was 500 cc every minute, thus the 5,000 cc of treated liquid was repeatedly electrolytically treated 6 times in 60 minutes.

[0071] The effects with the test carried out at a current density of 82 and 136 A/dm2 are shown in Table 3.

[0072] Since the component content amount was different for the agricultural chemicals that were utilized in the present example, and this was done so that the COD became the same level by changing the dilution ratio. The decomposition rate obtained an effect of 90% or more during the electrolysis time of 60 minutes at electrolytic currents of 36 and 60 A. The relationship of current density and COD relative to the electrolysis time for the electrolytic treatment of three types of agricultural chemical aqueous solutions is shown in Table 3.

	TABLE 3
		Daconil Powder		Sumithion Emulsion
		TPN (organic	Saprol Emulsion	MEP (organic
		chlorine type)	Triforin	phosphorous type)
	Component	4%	15%	50%
Number-Folds	-fold	30	50	100
Dilution
COD	mg/L	2800	2680	3280
Current	A	36	60	36	60	36	60
Electrical	μS/cm	30,100	30,100	31,000	31,000	30,900	30,900
Conductivity
COD before	mg/L	2,800	2,800	2,680	2,680	3,280	3,280
electrolytic
treatment
current	A/dm2	82	136	82	136	82	136
density
COD	mg/L	TPN 36	TPN 60	TFN 36	TFN 60	MEP 60	MEP 60
Electrolysis	0	2,900	2,900	2,680	2,680	3,280	3,280
Time in	10	1,650	1,230	1,530	1,070	2,150	1,410
Minutes	20	1,230	720	1,030	680	1,350	495
	30	1,080	480	755	430	865	225
	40	990	350	560	260	715	135
	50	975	255	524	155	694	95
	60	970	230	520	85	685	54
decomposition rate %	66	92	80	96	79	98

EXAMPLE IV

[0073] The ability to effectively decrease the COD by oxidation treatment by electrolysis of the present application for things like the washing waste water of used agricultural chemical containers was determined in Example 3. The chemical structure of dioxin is close to these agricultural chemicals and the applications of the present application can be considered possible.

[0074] A subject of the present actual example is seeped wastewater that collects from seeping wastewater treatment containers of landfill soil of things like industrial waste, and are often harmful substances. The clear top layer with the filtered substances sedimented and removed was converted to 2,3,7,8-dibenzodioxin tetrachloride and contains 32 nanograms/L of dioxin. Further, after drying the filtered substances which were sedimented out, the dioxin was tested when Soxhlet extraction with toluene and analysis were performed.

[0075] A test apparatus that is shown in the system flow diagram of FIG. 1 was used in the present actual example and the control-power source apparatus 2 was made with the power source substrate of 12 A, 60 V within 5 units. A 5 μm Cuno filter was used for the filter 3 (maximum 60 A, 60 V). The clear top layer part with the filtered substances sedimented and removed was used for the test. The SS of this clear top layer was 18, the pH was 7.6, electrical conductivity was 980, COD was 285 and the total nitrogen was T-N 18.

[0076] The electrical conductivity was adjusted such as becoming respectively 30,000 μS/cm by adding only sodium chloride for the control and a mixture of NaCl:NaBr of a mixed molar ratio of 60:40 with the best effects obtained by the previously established test.

[0077] Dioxin was detected when there was Soxhlet extraction with toluene and analysis after collection with the Cuno filter adhering substances by the COD decomposition rate being 87% with the current density being 136 A/d since the electrical conductivity was adjusted such as becoming respectively 30,000 μS/cm by adding only sodium chloride for electrolysis.

[0078] The dioxin could not be detected as the COD decomposition rate reached 94% at the current density being 136 A/dm2 with the mixture being a NaCl:NaBr weight ratio of 60:40.

[0079] Moreover, the dioxin could not be detected in Soxhlet extraction with toluene and analysis after the Cuno filter adhering substances were collected.

[0080] The seeping waste water of landfill soil contained 18 mg/L as the total nitrogen T-N of things like ammonious type nitrogen NH4-N and nitric nitrogen NO3—N, but could be decreased to 3 mg/L (decomposition rate of 83%) for %-N with electrolytic treatment of a current density of 136 A. As shown in FIG. 4, the COD and total nitrogen could be effectively decreased by carrying out electrolysis at a high current density.

	TABLE 4
	NaCl (100)	NaCl:NaBr (60:40)
Current	A	36	60	36	60
Electrical	μS/cm	30,100	30,600	30,180	30,900
Conductivity
Current Density	A/dm2	82	136	82	136
	mg/L	COD	T-N	COD	T-N	COD	T-N	COD	T-N
electrolysis time	0	285	18	285	18	285	18	285	18
in minutes	10	295	23	320	25	315	27	330	32
	20	310	17	187	14	255	15	168	18
	30	290	12	124	9	156	10	98	10
	40	185	8	83	6	112	8	54	6
	50	152	8	47	4	65	5	39	4
	60	95	7	36	4	42	4	18	3
decomposition rate %	66	61	87	77	85	77	94	83

[0081] Features and advantages of the present invention are reported as described in the following be being constructed as explained above.

[0082] With the present invention, a powerful anode oxidation reaction can be brought about for waste fluid or waste water that is introduced into the electrolysis chamber by being done such that electrolysis can be performed at a high current density of 10 A/dm2 or higher by the anode 11 being a nickel ferrite electrode. Further, the decomposition rate can become even higher when there is circulating treatment since powerful oxidation action can be imparted by generating a high concentration of hypohalogenous acid and active oxygen.

[0083] With the present invention, a conductive bond can often be used for the junction of the nickel ferrite electrode 11 and terminal main body 15. The electrode is damaged by further raising the temperature by the load being undesirable by doing things like the bond contracting due to the thermal influence by the load when continued over a long time period. The full contact state without any spacing for the junction section of the nickel ferrite anode 11 and terminal unit 15 can be maintained by using a low melting point metal or mercury. Mercury absorbs the stretching and contracting due to the thermal expansion of the nickel ferrite electrode and terminal main body differing since mercury is a liquid. Further, a low temperature melting point metal is a solid at room temperature but becomes fluid in response to the increase in the current and voltage and flowability appears, and thus can absorb the contraction and expansion due to the heat of the anode 11 and the terminal unit 15. Further, a long solid rod terminal unit is inserted length-wise such as making contact within the cylindrical electrode and a melted low melting point metal or mercury fills in that spacing, thus a broad electrical contact surface can be maintained. Therefore, the decomposition and purification of things like difficult to decompose substances becomes possible by being done such that electrolysis is possible at a high current density.

[0084] With the present invention, oxidation decomposition with good effects is possible for difficult to decompose substances which are difficult to oxidation decompose by prior art electrolytic treatments by carrying out electrolysis at a current density of 10˜1000 A/dm2, preferably at 20˜300 A/dm2.

[0085] With the present invention, the cylindrical nickel ferrite anode 11 is good even without respective establishment of a nickel ferrite anode for every electrode surface area since the anode surface area can simply be wide by the length-wise connection of a number of units by means of water resistant and corrosion resistant separators 22. Generally, the long press time when a ferrite electrode formed is difficult, and there is the problem of easily deforming those that are baked for a long time in a sintering furnace, but this became solvable.

[0086] With the present invention, a wide range of difficult to decompose substances can be oxidation decomposed with good effects by adding sodium halide or potassium halide or a mixture of both when the electrical conductivity of the waste fluid or waste water is low. In particular, difficult to decompose substances can be decomposed even when neutral or weakly alkaline since hypohalogenous acid and active oxygen can be synthesized with good effects at a wide pH range when independent or by combining and using bromine ions as the halogen ions.

[0087] With the present invention, the waste fluid or waste water is introduced into the electrolytic path (reaction section) 13 of the electrolyzer 1, electrolytic treatment is repeatedly carried out and there can be elimination by successive oxidation decomposition from the comparatively easily decomposed substances to the difficult to decompose substances. In this case, oxidation decomposition is possible by effectively applying a high concentration of hypohalogenous acid and active oxygen that is generated by the electrolytic decomposition since there can be a suitable amount of retention time in the intermediate collection chamber 4 or filter 3.

[0088] The hypohalogenous acid and active oxygen of a high concentration in circulating treated water can be repeatedly reacted with the filtered substances that contain difficult to decompose substances in filter 3. Even ones such as the aforementioned difficult to decompose substances in the accumulated substances in the filters can be eliminated, not just ones such as these difficult to decompose substances in waste water, when done as by this invention since there are many filtered substances that contain difficult to decompose substances such as aromatic type compounds (benzene, chlorobenzene types, chlorophenol), organic chlorine compounds (like trichloroethylene, tetrachloroethylene, tetrachloroethane), agricultural chemicals (such as DDT, PCP, parathion, TPN.tetrachloroisophthalonitril, triforin, MEP.sumithion, diazinon), dioxin, PCB and water soluble polymers (such as poly(vinyl alcohol, polyacrylonitrile, polyether), incinerator waste gas treatment water, landfill soil seeped waste water, and landfill soil washing waste water.

[0089] According to the present invention, repeated oxidation decomposition action can be brought about for waste fluid or wastewater by circulation. Further, the effect is great with the possibility of electrolytic treatment by diluting the concentration of the waste fluid or the waste water corresponding to the magnitude of the intermediate collection chamber 4 on that by being able to continuously treat by introduction of the same amount in waste fluid or waste water tank 6 since a part as in the prior item can be discharged as treated water when the size of the intermediate collecting chamber 4 is suitable.

[0090] According to the present invention, the electrolytic efficiency can be increased since the filtered substances in the waste fluid or waste water are eliminated by establishing a filter 3 in the circulating current path 51 on the side toward the electrolytic chamber. The filtered substances that are collected in the filter repeatedly receive the oxidation decomposition action of the hypohalogenous acid and active oxygen that are generated in the circulating water. Even though things such as difficult to dissolve organic compounds, agricultural chemicals, dioxin and PCB in the water adhere by being dissolved in the organic compounds or as particles due to this, they collect on the filter as filtered substances and can be effectually oxidation decomposed by electrolytic treated water on the wide contact surface of the filter.

[0091] According to the present invention, a wide range of difficult to decompose substances such as aromatic compounds, organic chlorine compounds, agricultural chemicals (like DDT, PCP, parathion, TPN.tetrachloroisophthalonitril, triforin, MEP.sumithion, diazinon), dioxin types, PCB.biphenyl chloride types, water soluble polymers (like poly(vinyl alcohol), polyacrylonitrile, polyether) and nitrate ions that are contained in waste fluid or waste water can be easily oxidation decomposed with a simple apparatus.

Explanation of the Symbols

[0092] 1 electrolyzer

[0093] 2 control.power source apparatus

[0094] 3 filter

[0095] 4 intermediate collection chamber

[0096] 5 circulating pump

[0097] 6 waste fluid or wastewater tank

[0098] 7 electrolyte aqueous solution tank

[0099] 11 anode

[0100] 12 cathode

[0101] 13 electrolytic path (reaction zone)

[0102] 14 low melting point metal junction or mercury filled section

[0103] 15 anode terminal main body

[0104] 16 anode terminal

[0105] 17 cathode terminal

[0106] 18 introduction port for water to be treated

[0107] 19 exit port for electrolytically treated water

[0108] 22 spacer

[0109] 23 casing

[0110] 24 casing bottom

[0111] 25 casing cover

[0112] 26 O-ring

[0113] 27 inner case bottom

[0114] 28 inner case cover

[0115] 31 strainer

[0116] 32 treated water strainer

[0117] 33 treated water exit

[0118] 51 circulating current path

[0119] 71 electrolyte aqueous solution injection pump

Claims

1. A waste fluid treatment method which comprises decomposition and purification of difficult to decompose substances by carrying out electrolysis at a high current density of 10 A/dm2 or higher with an anode electrode, and oxidation decomposition action by active oxygen with strong anode oxidation in an electrolytic path with hypohalogenous acid, for bringing about oxidation decomposition by introducing waste fluid which contains difficult to decompose substances into an electrolyzer.

2. A waste fluid or waste water treatment method, as in claim 1, wherein the anode is formed of a low melting point metal, or a mercury filled slit of the junction of the terminal main body with a nickel ferrite electrode.

3. A waste fluid or waste water treatment method as in claim 1, wherein electrolysis is being carried out at a high current density in electrolytic path.

4. A waste fluid treatment method as in claim 3, wherein the current density is 10˜1000 A/dm2.

5. A waste fluid treatment method as in claim 3, wherein the current density is 20˜300 A/dm2.

6. A waste fluid treatment method as in claim 1, wherein a number of units are connected lengthwise by means of a water resistant and corrosion resistant spacer.

7. A waste fluid treatment method as in claim 1, further comprising adding a sodium halide or potassium halide, or a mixture of both to the waste fluid.

8. A waste fluid treatment method as in claim 1, wherein oxidation decomposition of difficult to decompose substances with good effects due to elimination by successive oxidation decomposition from substances that are comparatively easy to decompose by repeated electrolytic treatment of waste fluid or waste water being carried out in an electrolytic path of an electrolyzer by establishing a re-circulating flow of said fluid between an intermediate collection chamber or filter and an electrolyzer.

9. A waste fluid treatment apparatus for carrying out the method of claim 1, comprising an intermediate collection chamber for collecting waste suspension and an electrolyzer for carrying out electrolysis of said waste suspension including difficult to decompose substances, and bringing about oxidation decomposition action by said hypohalogenous acid and active oxygen, and a circulator for re-circulating said waste fluid between said intermediate collection chamber, a strainer and said electrolyzer.

10. A waste fluid treatment apparatus as in claim 9, sized to accommodate waste fluid as it is introduced through a strainer from a waste fluid tank.