CN108529735A

CN108529735A - Method for treating water and water treatment facilities

Info

Publication number: CN108529735A
Application number: CN201810175249.4A
Authority: CN
Inventors: 安保贵永; 皆川正和
Original assignee: Mitsubishi Chemical Water Solutions Inc
Current assignee: Wilsey Co
Priority date: 2017-03-03
Filing date: 2018-03-02
Publication date: 2018-09-14
Anticipated expiration: 2038-03-02
Also published as: CN108529735B

Abstract

The method for treating water of water process can be effectively performed by providing.It is containing can be by the method for treating water of the waste water of oxidative pollutant matter comprising following processes：(i) reaction process, adding ferrous ion and hydrogen peroxide into the waste water for meeting following condition A in a manner of meeting following condition B makes the oxidation processes that can be aoxidized by oxidative pollutant matter in waste water, so that the ferric ion generated by oxidation processes is reduced to the reduction treatment of ferrous ion in the presence of iron reducing catalyst to obtain reaction solution；(ii) chemical industry sequence is not dissolved, reaction solution pH is adjusted to 6 or more 10 hereinafter, make the ferrous ion in reaction solution and ferric ion insolubleization, obtains the suspended suspension for having ferrous compound and ferric iron compound；(iii) enrichment process isolates processing water from suspension, obtains the concentrated concentration suspension of the sludge containing ferric iron compound；A pH value of waste water is 1 or more 4 hereinafter, B ratios R₁It is 1.9 or more 100 or less.

Description

Method for treating water and water treatment facilities

Technical field

The present invention relates to method for treating water and water treatment facilities.

Background technology

Fenton (Fenton) reaction is that hydrogen peroxide reacts the reaction for generating hydroxyl radical free radical with ferrous ion.Hydroxyl free Base has very strong oxidability, using its very strong oxidability, is expected to be applied to sterilization, harmful substance and hard-decomposed dirt Contaminate the every field such as the decomposition of substance.

The ferrous ion used in Fenton's reaction is aoxidized with the progress of reaction, becomes ferric ion.For example, Using Fenton's reaction handle containing can be by the waste water of oxidisability dirty substance when, the sludge containing ferric iron compound becomes discarded Object, the processing cost is high and becomes problem.

A part for the known ferric ion generated in Fenton's reaction in the presence of hydrogen peroxide, gone back by a part Originally it was ferrous ion.However, it is known that this reduction reaction is very slow compared with Fenton's reaction.In this regard, it has been known that there is addition promotion is above-mentioned The iron reducing catalyst of reduction reaction, the method for being carried out at the same time Fenton's reaction and above-mentioned reduction reaction.Such example can be enumerated Add example (patent document 1 and patent document 2) of the activated carbon as iron reducing catalyst.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Application 56-48290 bulletins

Patent document 2：No. 5215578 bulletins of Japanese Patent No.

Invention content

Problem to be solved by the invention

Treatment effeciency is sometimes low in the method described in patent document 1 and patent document 2.

Therefore, an embodiment of the invention, it is intended that using with ferric ion reduction reaction In the water process of Fenton's reaction, the water treatment facilities that can effectively carry out water process and the water process side using the device are provided Method.

The technical solution solved the problems, such as

To solve the above-mentioned problems, present inventor has performed further investigations, as a result, it has been found that hydrogen peroxide is that iron reduction is made to urge One of the principal element of agent inactivation.Further, it was found that comparing R by calculated according to the following formula₁It is 1.9 or more and 100 or less Under conditions of carry out Fenton's reaction, the inactivation of iron reducing catalyst can be inhibited, so as to complete the present invention.

R₁=A₁/B₁

A₁Indicate mass concentration (unit of the iron reducing catalyst relative to reaction solution total amount：mg/L).

B₁Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time Gross mass (the unit of hydrogen peroxide：Mg amount (the unit of the waste water) divided by process (i) handled in setting time：L it) counts It obtains.

That is, the present invention has following manner.

[1] a kind of containing can include following processes by the method for treating water of the waste water of oxidative pollutant matter, the method for treating water (i)~(iii)：

(i) reaction process carries out oxidation processes and reduction treatment in the process to obtain reaction solution, wherein the oxidation processes Ferrous ion is added into the waste water for meeting following conditions (A) and hydrogen peroxide comes in a manner of meeting following conditions (B) Make in the waste water it is described can be aoxidized by oxidative pollutant matter, the reduction treatment makes in the presence of iron reducing catalyst The ferric ion generated by the oxidation processes is reduced to ferrous ion；

(ii) it does not dissolve chemical industry sequence, the reacting liquid pH value is adjusted to 6 or more and 10 hereinafter, making the reaction solution in the process In ferrous ion and ferric ion insolubleization, obtain the suspended suspension for having ferrous compound and ferric iron compound；

(iii) enrichment process isolates processing water from the suspension in the process, obtains the sludge containing ferric iron compound Concentrated concentration suspension；

(A) pH value of waste water is 1 or more and 4 or less

(B) calculated according to the following formula to compare R₁For 1.9 or more and 100 hereinafter,

R₁=A₁/B₁

Wherein, A₁Indicate mass concentration (unit of the iron reducing catalyst relative to reaction solution total amount：Mg/L),

B₁Indicate the mass concentration (unit of the hydrogen peroxide：Mg/L), it is to be added to by being used in the setting time Gross mass (the unit of the hydrogen peroxide in the waste water：Mg described in handling in setting time) divided by process (i) Amount (the unit of waste water：L it) is calculated.

[2] according to the method for treating water described in [1] comprising suspension reflow process makes the suspension extremely in the process Any of a few part and at least part of the concentration suspension or the two flow back into the process (i).

[3] according to the method for treating water described in [1] or [2] comprising Magneto separate process, using magnetic to described outstanding in the process Paramagnetism object is detached contained in any of turbid and the concentration suspension or the two.

[4] method for treating water according to any one of [1]~[3], wherein the iron reducing catalyst is selected from by living At least one of the group that property charcoal and zeolite are formed.

[5] method for treating water according to any one of [1]~[4], wherein, will be described using acid in the process (i) PH value of waste water is adjusted to 1 or more and 4 or less.

[6] according to the method for treating water described in any one of [1]~[5], wherein in the process (i), add ferrous salt or Ferrocyanide.

[7] method for treating water according to any one of [1]~[6], wherein in the process (iii), use filter membrane Obtain the concentration suspension.

[8] method for treating water according to any one of [1]~[7], has separation process, and NF membrane is used in the process Or reverse osmosis membrane, by the processing water be separated into contained in the processing water it is described can be by oxidative pollutant matter and filtration Water.

[9] a kind of water treatment facilities has following (1)~(3)：

(1) reactive tank compares R in the slot calculated according to the following formula₂For 1.9 or more and 100 it is below under the conditions of, utilize sweet smell Reaction pause to can be aoxidized by oxidative pollutant matter contained in waste water, while being made using described by iron reducing catalyst The ferric ion that Fenton's reaction generates is reduced to ferrous ion, obtains reaction solution,

R₂=A₂/B₂

Wherein, A₂Indicate mass concentration (unit of the iron reducing catalyst relative to the reaction solution total amount in the reactive tank： Mg/L),

B₂Indicate the mass concentration (unit of the hydrogen peroxide：Mg/L), it is to be added to by being used in the setting time Gross mass (the unit of hydrogen peroxide in the waste water：Mg described in) divided by setting time being flowed into the reactive tank Amount (the unit of waste water：L it) is calculated；

(2) insolubleization slot makes ferrous ion and ferric ion insolubleization contained in the reaction solution in the slot, generates Ferrous compound and ferric iron compound obtain the suspended suspension for having ferrous compound and ferric iron compound；

(3) enrichment facility, the device isolate processing water from the suspension, obtain the sludge containing ferric iron compound through dense The concentration suspension of contracting.

[10] according to the water treatment facilities described in [9], has suspension reflux mechanism, which makes the suspension at least Any of at least part of a part of and described concentration suspension or the two flow back into the reactive tank.

[11] according to the water treatment facilities described in [9] or [10], has magnetic separating device, the device is using magnetic to described outstanding Paramagnetism object is detached contained in any of turbid and the concentration suspension or the two.

[12] according to the water treatment facilities described in [10] or [11], have：

Catalyst concn determination part, mass concentration of the determination part to the iron reducing catalyst relative to the suspension total amount At least one of mass concentration with the iron reducing catalyst relative to the concentration suspension total amount is measured；

Control unit, control unit control is described to compare R₂It is 1.9 or more and 100 or less；

Wherein, the control unit is according to the measurement result of the catalyst concn determination part, extremely to the suspension of reflux Flow and the iron reduction catalysts of any of a few part and at least part of the concentration suspension or the two The additive amount of agent is determined, and determines the additive amount of the hydrogen peroxide simultaneously.

[13] according to the water treatment facilities described in any one of [9]~[12], has a catalyst addition mechanism, the mechanism is to institute It states and adds the iron reducing catalyst in reactive tank.

[14] water treatment facilities according to any one of [9]~[13], has：

First pH regulating devices, the device supply acid or alkali into the reactive tank to adjust the pH of the waste water；

2nd pH regulating devices, the device supply alkali into the insolubleization slot to adjust the pH of the reaction solution.

[15] according to the water treatment facilities described in [14], wherein the acid is sulfuric acid or hydrochloric acid.

[16] water treatment facilities according to any one of [9]~[15], wherein the enrichment facility has filter membrane, uses The filter membrane obtains the suspension.

[17] water treatment facilities according to any one of [9]~[16], wherein the enrichment facility is arranged described insoluble In solutionization slot.

[18] water treatment facilities according to any one of [9]~[17], has separator, which has NF membrane Or the processing water is separated into contained in the processing water by reverse osmosis membrane using the NF membrane or the reverse osmosis membrane It is described can be by oxidative pollutant matter and filtered water.

[1] a kind of method for treating water comprising following process (i)~(v)：

(i) oxidation operation, will be containing can be adjusted to 1.0 or more and 4.0 in the process by the pH value of waste water of oxidative pollutant matter Hereinafter, comparing R calculated according to the following formula simultaneously₁For 2.0 or more and 100 it is below under the conditions of, carry out Fenton's reaction, oxidation It is described can by oxidative pollutant matter,

R₁=A₁/B₁

Wherein, A₁Indicate that the iron reducing catalyst obtained in the oxidation operation is (single relative to the mass concentration of reaction solution total amount Position：Mg/L),

B₁Indicate mass concentration (unit of the hydrogen peroxide relative to the waste water total amount being sent into the oxidation operation：mg/ L)；

(ii) do not dissolve chemical industry sequence, in the process by the reacting liquid pH value be adjusted to 6.0 or more and 10.0 hereinafter, make it is ferrous from Son and ferric ion insolubleization generated using the Fenton's reaction, generate ferrous compound and ferric iron compound；

(iii) enrichment process makes suspended have the suspension of the ferrous compound and the ferric iron compound point in the process From for the sludge containing the ferric iron compound and processing water, obtain the concentrated suspension of the sludge；

(iv) suspension reflow process makes at least part of the suspension flow back into the oxidation operation in the process；

(v) process is restored, so that the ferric ion is reduced to the ferrous ion by iron reducing catalyst in the process.

[2] according to the method for treating water described in [1], wherein the iron reducing catalyst is in activated carbon and zeolite It is at least one.

[3] according to the method for treating water described in [1] or [2], wherein in the oxidation operation, using acid by the wastewater pH Value is adjusted to 1.0 or more and 4.0 or less.

[4] method for treating water according to any one of [1]~[3], wherein in the oxidation operation, add ferrous salt Or ferrocyanide.

[5] method for treating water according to any one of [1]~[4], wherein in the enrichment process, use filter membrane Obtain the suspension.

[6] method for treating water according to any one of [1]~[5], has separation process, and NF membrane is used in the process Or reverse osmosis membrane, by the processing water be separated into contained in the processing water it is described can be by oxidative pollutant matter and filtration Water.

[7] a kind of water treatment facilities has following (1)~(4)：

(1) reactive tank compares R in the slot calculated according to the following formula₂For 2.0 or more and 100 it is below under the conditions of, utilize sweet smell Reaction pause to can be aoxidized by oxidative pollutant matter contained in waste water, while being made using described by iron reducing catalyst The ferric ion that Fenton's reaction generates is reduced to ferrous ion, obtains reaction solution,

R₂=A₂/B₂

Wherein, A₂Indicate mass concentration (unit of the iron reducing catalyst in the reactive tank relative to reaction solution total amount：mg/ L),

B₂Indicate mass concentration (unit of the hydrogen peroxide relative to the waste water total amount for being flowed into the reactive tank：mg/L)；

(2) insolubleization slot, make in the slot ferrous ion contained in the reaction solution supplied from the reactive tank and Ferric ion insolubleization generates ferrous compound and ferric iron compound.

(3) enrichment facility, the device make suspended have the ferrous compound and the suspension of the ferric iron compound to be separated into Sludge containing the ferric iron compound and processing water, obtain the concentrated suspension of the sludge.

(4) suspension reflux mechanism, the mechanism make at least part of the suspension flow back into the reactive tank.

[8] according to the water treatment facilities described in [7], have：

Catalyst concn determination part, it is dense relative to the quality of the suspension total amount which measures the iron reducing catalyst Degree；

Control unit, control unit control is described to compare R₂For 2.0 or more and 100 hereinafter,

Wherein, the control unit determines the suspension of reflux according to the measurement result of the catalyst concn determination part Flow and the additive amount for confirming iron reducing catalyst, and the additive amount of the hydrogen peroxide is determined simultaneously.

[9] according to the water treatment facilities described in [7] or [8], has catalyst addition mechanism, the mechanism is into the reactive tank Add the iron reducing catalyst.

[10] water treatment facilities according to any one of [7]~[9], has：

[11] according to the water treatment facilities described in [10], wherein the acid is sulfuric acid or hydrochloric acid.

[12] water treatment facilities according to any one of [7]~[11], wherein the enrichment facility has filter membrane, uses The filter membrane obtains the suspension.

[13] water treatment facilities according to any one of [7]~[12], wherein the enrichment facility is arranged described insoluble In solutionization slot.

[14] water treatment facilities according to any one of [7]~[13], has separator, which has NF membrane Or the processing water is separated into contained in the processing water by reverse osmosis membrane using the NF membrane or the reverse osmosis membrane It is described can be by oxidative pollutant matter and filtered water.

[1] a kind of method for treating water comprising following processes (i)~(vi)：

(i) oxidation operation makes in the process that Fenton can be utilized by oxidative pollutant matter contained in waste water in acid condition Reaction is aoxidized；

(ii) do not dissolve chemical industry sequence, in the process by the reacting liquid pH value obtained in the oxidation operation be adjusted to 6.0 or more and 10.0 hereinafter, make include ferrous ion and using the Fenton's reaction generate ferric ion iron insolubleization, generation Asia Iron compound and ferric iron compound；

(iii) enrichment process makes suspended have the suspension of the ferrous compound and the ferric iron compound point in the process From for the sludge containing the ferric iron compound and processing water, obtain the concentrated concentration suspension of the sludge；

(iv) suspension reflow process makes in the process at least part of the concentration suspension flow back into the oxidation work Sequence；

(v) process is restored, so that the ferric ion is reduced to the ferrous ion by iron reducing catalyst in the process；

(vi) Magneto separate process, using magnetism to any of the suspension and the concentration suspension or two in the process Paramagnetism object contained in person detaches.

[3] according to the method for treating water described in [1] or [2], wherein in the oxidation operation, acid item is set as using acid Under part.

[4] method for treating water according to any one of [1]~[3], wherein in the oxidation operation, addition is selected from At least one of ferrous salt and ferrocyanide.

[5] method for treating water according to any one of [1]~[4], wherein in the enrichment process, use filter membrane Obtain the concentration suspension.

[7] a kind of water treatment facilities has following (1)~(4)：

(1) reactive tank, using Fenton's reaction to can be aoxidized by oxidative pollutant matter contained in waste water in the slot, simultaneously Make to be reduced to ferrous ion to the ferric ion of generation using the Fenton's reaction by the iron reducing catalyst；

(2) insolubleization slot makes the ferrous ion and trivalent contained in the reaction solution supplied from the reactive tank in the slot Iron ion insolubleization generates ferrous compound and ferric iron compound；

(3) enrichment facility makes suspended have the ferrous compound and the suspension of the ferric iron compound to be separated into the slot Sludge containing the ferric iron compound and processing water, obtain the concentrated concentration suspension of the sludge；

(4) suspension reflux mechanism, the mechanism make at least part of the concentration suspension flow back into the reactive tank；

(5) magnetic separating device, the device is using magnetism to any of described suspension and the concentration suspension or both Contained in paramagnetism object detached.

[8] according to the water treatment facilities described in [7], wherein have addition mechanism in the reactive tank, mechanism addition is selected from At least one of ferrous salt, ferrocyanide, trivalent iron salt and ferric oxide.

[9] according to the water treatment facilities described in [8], has catalyst concn determination part, which measures the iron reduction Mass concentration of the catalyst relative to reaction solution total amount, according to the measurement result of the catalyst concn determination part, described in addition Iron reducing catalyst, while adding and being selected from least one of above-mentioned group.

[10] according to the water treatment facilities described in any one of [7]~[9], has a catalyst addition mechanism, the mechanism is to institute It states and adds the iron reducing catalyst in reactive tank.

[11] water treatment facilities according to any one of [7]~[10], has：

[12] according to the water treatment facilities described in [11], wherein the acid is sulfuric acid or hydrochloric acid.

[13] water treatment facilities according to any one of [7]~[12], wherein the enrichment facility has filter membrane, uses The filter membrane obtains the concentration suspension.

[14] water treatment facilities according to any one of [7]~[13], wherein the enrichment facility is arranged described insoluble In solutionization slot.

[15] according to the water treatment facilities described in any one of [7]~[14], wherein the magnetic separating device setting selected from In at least one of the reactive tank, the insolubleization slot and suspension reflux mechanism.

[16] water treatment facilities according to any one of [7]~[15], has separator, which has NF membrane Or the processing water is separated into contained in the processing water by reverse osmosis membrane using the NF membrane or the reverse osmosis membrane It is described can be by oxidative pollutant matter and filtered water.

Invention effect

According to embodiment of the present invention, in the water using the Fenton's reaction with ferric ion reduction reaction In processing, the water treatment facilities that can effectively carry out water process and the method for treating water using the device are improved.

Description of the drawings

Fig. 1 is the schematic configuration diagram for indicating water treatment facilities 1.

Fig. 2 is the schematic configuration diagram for indicating water treatment facilities 2.

Reference sign

1 ... water treatment facilities, 11 ... reactive tanks, 14,24 ... pH regulating devices, 15 ... ferrons addition mechanism, 17 ... are urged Agent add mechanism, 19A ... concentration of hydrogen peroxide determination part, 18,19B ... catalyst concn determination parts, 19C ... control units, 21 ... insolubleization slots, 22 ... enrichment facilities, 32 ... suspensions reflux mechanism, 34 ... magnetic separating devices, 42 ... separators

Specific implementation mode

In the following, referring to attached drawing, embodiments of the present invention will be described.It is explained, in following whole attached drawing, For ease of understanding attached drawing, size and ratio of each integral part etc. are suitably changed.

[water treatment facilities]

The structure of water treatment facilities 1 to being used in the method for treating water of present embodiment illustrates.Fig. 1 is to indicate this implementation The schematic configuration diagram of the water treatment facilities 1 of mode.As shown in Figure 1, water treatment facilities 1 have reactive tank 11, insolubleization slot 21, Regulating tank 41 and retention basin 61.

Water treatment facilities 1 has at reactive tank 11：PH regulating devices 14, ferron addition mechanism 15, hydrogen peroxide add Add mechanism 16, catalyst addition mechanism 17 and concentration of hydrogen peroxide determination part 19A.

Water treatment facilities 1 has at insolubleization slot 21：Catalyst concn determination part 19B, pH regulating device 24.This Outside, enrichment facility 22 is provided in insolubleization slot 21.

In this specification, pH regulating devices 14 are equivalent to the first pH regulating devices in claims.In addition, pH is adjusted Device 24 is equivalent to the 2nd pH regulating devices in claim.

Water treatment facilities 1 has control unit 19C.

In addition, water treatment facilities 1 has suspension reflux mechanism 32 between insolubleization slot 21 and reactive tank 11.

Water treatment facilities 1 has separator 42 between regulating tank 41 and retention basin 61.

(waste water)

Using water treatment facilities 1 water process in, using Fenton's reaction to containing can by the waste water of oxidative pollutant matter into Row oxidation processes.It can be enumerated by oxidative pollutant matter：Using biological treatment be difficult to the organic matter decomposed or phosphorous acid and The inorganic matters such as hypophosphorous acid.

Above-mentioned organic matter can illustrate such as：The organic solvents such as 1,4- dioxanes, humus etc..Humus refers to that will use hydroxide The alkali carries such as sodium fetch earth component obtained by earth or with natural water extract soil obtained by extracting solution be adsorbed onto XAD resin (styrene Or the copolymer of acrylic acid and divinylbenzene), the component further eluted from the adsorbate with dilute alkaline aqueous solution.

Contain phosphorous acid and hypophosphorous acid in plant chimney stalk of electroplating facility etc..

(reactive tank)

Using Fenton's reaction to can be aoxidized by oxidative pollutant matter contained in waste water in reactive tank 11, while passing through iron Reducing catalyst makes the ferric ion generated using Fenton's reaction be reduced to ferrous ion.Production is at least filled in reactive tank 11 Raw ferrous ion (Fe²⁺) ferron, hydrogen peroxide and iron reducing catalyst.

First flow path 12 and second flow path 13 are connected to reactive tank 11.First flow path 12 makes containing can be by oxidative pollutant The waste water of matter flows into (supply) and arrives reactive tank 11.It is explained, in the water treatment facilities 1 of present embodiment, waste water can connect It is flowed into reactive tank 11 continuously, reactive tank 11 can also be flowed intermittently into.It can in addition, can also be arranged in first flow path 12 Measure the measuring instrument of wastewater flow and flow velocity.Second flow path 13 makes the reaction solution being discharged from reactive tank 11 flow into (supply) to not Dissolvingization slot 21.

In water treatment facilities 1 as shown in Figure 1, make the method that reaction solution is supplied to insolubleization slot 21 from reactive tank 11 It is not particularly limited, can be with pump come supply response liquid, it can also be using overflow come supply response liquid.

It is explained, in water treatment facilities 1 as shown in Figure 1, shows the example of one reactive tank 11 of setting, also may be used With the multiple reactive tanks of arranged in series 11.In this case, the time needed for Fenton's reaction can be extended, therefore can be anti-in Fenton Hydrogen peroxide is fully consumed in answering.

In addition, when configuring multiple reactive tanks 11, the method that the second reactive tank is transported to from the first reactive tank is not special It does not limit, can be conveyed with pump, can also be conveyed using overflow.

It is explained, in this specification, the reactive tank in claims is made of the first reactive tank and the second reactive tank.

(ferron addition mechanism)

Ferron addition mechanism 15 is that the mechanism of ferron is added into reactive tank 11.

Ferron as long as be dissolved in the water can generate ferrous ion as long as be not particularly limited, preferably ferrous salt or ferrous iron Oxide.Wherein, due to being not necessarily to be managed according to waste water standard and dissolubility is excellent, preferably sulfuric acid iron or iron chloride. Further, since high universalizable and low-corrosiveness, therefore more preferable ferric sulfate.

In addition, in present embodiment, ferric ion reduction, ferrous ion is set to regenerate by iron reducing catalyst, therefore Ferric iron compound can be used as ferron.

The ferron of solid state can be added into reactive tank 11, and it is water-soluble ferron can also to be added into reactive tank 11 The ferron of liquid condition as liquid.

(hydrogen peroxide addition mechanism)

Hydrogen peroxide addition mechanism 16 is that the mechanism of hydrogen peroxide is added into reactive tank 11.

In reactive tank 11, ferrous ion and hydroperoxidation generate hydroxyl radical free radical.It can quilt contained in waste water When oxidative pollutant matter is organic matter, hydroxyl radical free radical oxygenolysis that organic matter is generated.In addition, being phosphorous acid and secondary When the inorganic matters such as phosphoric acid, aoxidized respectively by hydroxyl radical free radical, phosphorous acid is oxidized to orthophosphoric acid, hypophosphorous acid be oxidized to phosphorous acid or Orthophosphoric acid.

On the other hand, it in reactive tank 11, is acted on by hydrogen peroxide, ferrous ion is oxidized to ferric ion.

In present embodiment, hydrogen peroxide can be also used for generating using Fenton's reaction other than being used for Fenton's reaction Ferric ion reduction reaction in.It is therefore preferable that the amount of hydrogen peroxide added by hydrogen peroxide addition mechanism 16 is more than Fenton The theoretical value used in reaction.

When configuring multiple reactive tanks 11, the reactive tank 11 of hydrogen peroxide is added from hydrogen peroxide addition mechanism 16, preferably It is set as the slot other than most downstream reactive tank 11.The reactive tank 11 of hydrogen peroxide is added closer to upstream, can more more be extended Time needed for Fenton's reaction, therefore hydrogen peroxide can be fully consumed in Fenton's reaction.Thereby, it is possible to inhibit reactive tank 11 The leakage of unreacted hydrogen peroxide in the insolubleization slot 21 and regulating tank 41 in downstream.Furthermore it is possible to inhibit by unreacted peroxide Change the increase of COD in processing water caused by hydrogen.

(the first pH regulating devices)

PH regulating devices 14 are that acid or alkali are added into reactive tank 11 to adjust the dress of pH in reactive tank 11 according to pH value in slot It sets.

Being adjusted in reactive tank 11, which can make ferron be dissolved in the water, generates ferrous ion and can generate hydroxyl radical free radical PH within the scope of.In present embodiment, the pH in reactive tank 11 is adjustable in 1.0 or more and 4.0 or less range.If anti- It is 1.0 or more and 4.0 hereinafter, can then keep the dissolubility of ferron in water well to answer pH in slot 11, while can Improve the contacting efficiency of ferric ion and iron reducing catalyst.PH in reactive tank 11 be preferably 2.0 or more and 3.0 hereinafter, More preferably 2.5 or more and 3.0 or less.

Additionally, it is preferred that setting measures the determining instrument of pH value in slot in reactive tank 11 (diagram is omited).

The type of acid can illustrate such as：The inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid；Oxalic acid, citric acid, formic acid, acetic acid etc. Organic acid.Wherein, preferably sulfuric acid or hydrochloric acid, it is more excellent due to the hydroxyl radical free radical generated in Fenton's reaction that defies capture Select sulfuric acid.These acid can be used alone, and can also be used in combination of two or more.

The type of alkali can illustrate such as：Sodium hydroxide, sodium carbonate, calcium hydroxide, magnesium hydroxide etc..Wherein, since high pass is used It property and is not reacted with the substance generated in Fenton's reaction, therefore preferred sodium hydroxide.

These alkali can be used alone, and can also be used in combination of two or more.

(catalyst addition mechanism)

Catalyst addition mechanism 17 is that the mechanism of iron reducing catalyst is added into reactive tank 11.

As long as iron reducing catalyst does not substantially hinder Fenton's reaction, at the same promote by hydrogen peroxide make ferric iron from Son is reduced and ferrous ion regenerated reaction.Iron reducing catalyst is preferably chosen from activated carbon and zeolite extremely Angle that is one few, being handled from catalyst efficiency and dead catalyst, more preferable activated carbon.

In the past, in the water process using the Fenton's reaction with ferric ion reduction reaction, with Fenton's reaction Progress and iron reducing catalyst inactivate, Fenton's reaction efficiency may be low.To solve the above-mentioned problems, the present inventor carries out Further investigation, as a result, it has been found that hydrogen peroxide is one of the principal element for making iron reducing catalyst inactivate.Further, it was found that by pressing Compare R according to following formula is calculated₂For 1.9 or more and 100 it is below under the conditions of carry out Fenton's reaction, iron reduction catalysts can be inhibited The inactivation of agent.

R₂=A₂/B₂

A₂Indicate mass concentration (unit of the iron reducing catalyst relative to the reaction solution total amount in reactive tank 11：mg/L).

B₂Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time Gross mass (the unit of hydrogen peroxide：Mg) divided by setting time it is flowed into the amount (unit of the waste water of reactive tank 11：L) and It is calculated.It is explained, above-mentioned two setting time length is identical.

That is, finding to be adjusted to by the mass concentration by iron reducing catalyst relative to the reaction solution total amount in reactive tank 11 Compare R according to above formula is calculated₂For 1.9 or more and 100 hereinafter, the inactivation of iron reducing catalyst can be inhibited.

As an embodiment, above-mentioned A₂The iron reducing catalyst of reactive tank 11 is added to relative to being reserving at reaction The mass concentration of reaction solution total amount in slot 11.Estimation above-mentioned A in Fenton's reaction₂It does not change.

When waste water duration is flowed into reactive tank 11, as long as hydrogen peroxide is not made to be flowed into reactive tank 11, peroxidating The mass concentration of hydrogen will decline.If the mass concentration of hydrogen peroxide declines, target Fenton's reaction or ferric ion are also Original reaction is possible to be difficult to carry out.Therefore, in the water treatment facilities 1 of present embodiment, confirm the peroxidating in each setting time The mass concentration of hydrogen, so that the mass concentration of hydrogen peroxide will not become too low.

In the water treatment facilities 1 of present embodiment, setting time is set according to 11 capacity of reactive tank and waste water flow velocity It is fixed.In the water treatment facilities 1 of present embodiment, setting time is, for example, 10 minutes.

It is explained, when waste water intermittence is flowed into reactive tank 11, above-mentioned B₂Can also be to be added to reactive tank 11 Mass concentration of the hydrogen peroxide relative to the waste water total amount being flowed into reactive tank 11.

If comparing R according to above formula is calculated₂It is 1.9 or more, then can fully inhibits the inactivation of iron reducing catalyst. Therefore, if this compares R₂It is 1.9 or more, then can fully obtains the effect for promoting ferric ion reduction reaction.This compares R₂It is higher, The inactivation that iron reducing catalyst can more more be inhibited, if it is greater than 100, then relatively the mass concentration of hydrogen peroxide can be lower, because This target Fenton's reaction or ferric ion reduction reaction are possible to be difficult to carry out.In this regard, if comparing R₂For 100 hereinafter, then may be used Inhibit the usage amount of iron reducing catalyst, inhibits the cost needed for iron reducing catalyst.

It treatment effeciency higher and is reduced using iron reducing catalyst cost from the method for treating water for make present embodiment Angle is set out, above-mentioned to compare R₂Preferably 1.9 or more and 80 hereinafter, more preferably 2.5 or more and 40 hereinafter, further preferably 2.7 or more and 30 hereinafter, particularly preferably 3.0 or more and 15 or less.

Iron reducing catalyst is preferably 50000mg/L or less relative to the mass concentration of reaction solution total amount.Iron reduction is set to urge The mass concentration of agent reaches the decomposition reaction for the hydrogen peroxide that 50000mg/L or less can inhibit using iron reducing catalyst.This Outside, the sludge condensation containing iron compound of iron ion insolubleization is made to become easy using aftermentioned enrichment facility.Further, When the concentration suspension made by suspension reflux mechanism 32 flows back into reactive tank 11, can inhibit to be used for reactive tank 11 The usage amount for the acid that interior pH is adjusted.

From the angle of catalyst efficiency, iron reducing catalyst is preferably shaped to powder shaped.Further, since being easy back Catalyst is received, therefore the grain size of iron reducing catalyst is preferably 0.05 μm~100 μm.

(concentration of hydrogen peroxide determination part)

Concentration of hydrogen peroxide determination part 19A is the determination part for measuring hydrogen peroxide relative to the mass concentration of reaction solution total amount.

Assay method of the hydrogen peroxide relative to the mass concentration of reaction solution total amount, can enumerate following methods：Sampling reaction Reaction solution in slot 11 develops the color the hydrogen peroxide sampled in reaction solution with potassium iodide, and utilization extinction photometer (such as strain formula Chemical and Chemical Research Institute system, name of product " Digital Pack Test " found altogether in commercial firm) it is measured.In addition, other methods can be lifted Go out the mass concentration for measuring the relative index of refraction of sampling reaction solution using index meter and calculating hydrogen peroxide by relative index of refraction Method.In addition, can enumerate using densitometer measure sampling reaction solution density and by density calculate hydrogen peroxide quality it is dense The method of degree.Further, the method that can also enumerate the mass concentration that hydrogen peroxide is measured using oxygen electrode method.

It is explained, in present embodiment, concentration of hydrogen peroxide determination part 19A can not also be set.

(insolubleization slot)

Insolubleization slot 21 is to remove ferrous ion from reaction solution and made using the ferric ion that Fenton's reaction generates Insoluble metaplasia at ferrous compound and ferric iron compound slot.

In present embodiment, " suspension " refers to the liquid generated by processing by insolubleization in insolubleization slot 21 Body." suspension " in present embodiment includes (a) removing or reducing from the waste water of object to be processed can be by oxidation contact scar Processing water, (b) ferrous compound, (c) ferric iron compound, (d) sludge of substance.In present embodiment, due to insoluble Change in slot 21 and have enrichment facility 22, therefore " suspension " is " concentration suspension ".The insolubleization slot of present embodiment as a result, Exist in 21 " concentration suspension ".

In present embodiment, " concentration suspension " refer to insolubleization slot 21 enrichment facility 22 in given birth to by concentration At liquid." concentration suspension " in present embodiment is as being obtained from removing (a) processing water from above-mentioned " suspension " (b) concentrate of ferrous compound, (c) ferric iron compound, (d) sludge.

In present embodiment, ferrous ion and ferric ion become the iron chemical combination such as iron oxide, water iron oxide or iron chloride Object and insolubleization.

(the 2nd pH regulating devices)

PH regulating devices 24 are to be add aed base to adjust pH in insolubleization slot 21 into insolubleization slot 21 according to pH value in slot Device.PH ranges can be adjusted in insolubleization slot 21 to making ferrous ion and ferric ion insolubleization.Insolubleization slot PH in 21 is adjusted in 6.0 or more and 10.0 or less range.PH in insolubleization slot 21 be preferably 7.0 or more and 9.0 hereinafter, more preferably 7.5 or more and 8.5 hereinafter, further preferably 7.8 or more and 8.3 or less.

Additionally, it is preferred that setting measures the determining instrument of pH value in slot in insolubleization slot 21 (diagram is omited).

The type of the alkali of addition can enumerate alkali identical with the alkali that pH regulating devices 14 can be used to add.

When can be the inorganic matters such as phosphorous acid and hypophosphorous acid by oxidative pollutant matter contained in waste water, if addition hydrogen Calcium oxide forms sediment as alkali, the then phosphorous acid in reaction solution with calcium hydroxide reaction.Therefore, aftermentioned enrichment facility 22 In can precipitate be separated into acid deposit containing phosphorous and processing water.In addition, the orthophosphoric acid in reaction solution is reacted with ferric ion Form sediment.Therefore, precipitation can be made to be separated into sediment containing orthophosphoric acid and processing water in aftermentioned enrichment facility 22.

《Enrichment facility》

Enrichment facility 22 is to make suspended have the suspension of ferrous compound and ferric iron compound to be separated by solid-liquid separation as containing iron chemical combination The sludge of object and iron reducing catalyst handles water and obtains the device of the concentrated concentration suspension of sludge.Enrichment facility 22 is adopted With the full dose filter type for having used the first membrane module 23.By using the first membrane module 23, even if containing highly concentrated in suspension When the sludge of degree, it can also be detached with high separation capacity.

Have the filter membranes such as microfiltration membranes or ultrafiltration membrane in first membrane module 23.Microfiltration membranes can enumerate integral type film.Ultrafiltration membrane can It enumerates：Hollow-fibre membrane, flat membrane, tubular film.Wherein, since volume filling rate is high, it is preferable to use hollow-fibre membranes.

When using hollow-fibre membrane in the first membrane module 23, material can be enumerated：Cellulose, polysulfones, gathers partially polyolefin Difluoroethylene (PVDF), polytetrafluoroethylene (PTFE) (PTFE) etc..Wherein, the material of hollow-fibre membrane becomes from chemical reagent resistance and to pH Change strong angle to set out, preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE).

, it is preferable to use film made of ceramics when using integral type film in the first membrane module 23.

The average pore size of the micropore formed in microfiltration membranes or ultrafiltration membrane is preferably 0.01 μm~1.0 μm, more preferably 0.05 μ M~0.45 μm.If the average pore size of the micropore is lower limiting value or more, the pressure restraining needed for separation of solid and liquid can be made to enough It is enough small.On the other hand, if the average pore size of the micropore be upper limit value hereinafter, if can inhibit containing iron compound and iron also The sludge of raw catalyst leaks into processing water.

In present embodiment, using iron reducing catalyst relative to reaction solution total amount mass concentration as iron when standard also Raw catalyst is (below sometimes referred to as " concentration rate ") preferably dense relative to the multiplying power of the mass concentration of concentration suspension total amount It is reduced to 4~20 times of degree.If concentration rate is 4 times or more, keep concentration outstanding by aftermentioned suspension reflux mechanism 32 When turbid flows back into reactive tank 11, the usage amount for the acid adjusted of the pH in reactive tank 11 can be inhibited.In addition, if concentration Multiplying power is 20 times hereinafter, then having used the concentration of the sludge of enrichment facility 22 and having used the concentration of suspension reflux mechanism 32 outstanding The reflux of turbid becomes easy.

Third flow path 31 is connected to the first membrane module 23.Third flow path 31 is the microfiltration membranes by the first membrane module 23 or surpasses The concentrated device 22 of processing water of filter membrane filtration is discharged and is flowed into the flow path of regulating tank 41.Pump is provided on third flow path 31 31a.Above-mentioned processing water can be discharged from insolubleization slot 21 as a result,.

Additionally, it is preferred that setting measures the measurement device of total concentration of iron in processing water on third flow path 31.It is filled by the measurement It sets, if it is determined that when total concentration of iron is higher than 0.04ppm in processing water, then take appropriate measures the pH value made in insolubleization slot 21 Or the first separation of solid and liquid or the two in membrane module 23 reaches suitable.

In addition, can have the aerator for the film surface cleaning being configured at below the first membrane module 23 in enrichment facility 22 Structure.Well known mechanism may be used in the aeration mechanism.

Further, other separating mechanisms other than the first membrane module 23 can also be applied in combination in enrichment facility 22.Its He can illustrate such as at separating mechanism：Sand filtration, pressure floatation separation, centrifugation, belt filter press, sedimentation basin precipitation etc..

(suspension reflux mechanism)

Suspension reflux mechanism 32 is that at least part for the concentration suspension for keeping sludge concentrated flows back from insolubleization slot 21 To the mechanism of reactive tank 11.Suspension reflux mechanism 32 has the 5th flow path 33.5th flow path 33 is to make concentration suspension extremely A few part from the discharge of insolubleization slot 21 and flow into (supply) to reactive tank 11 flow path.

Pump 33a is provided on the 5th flow path 33.Thereby, it is possible to make at least one of the concentration suspension in insolubleization slot 21 Divide from insolubleization slot 21 and flows back into reactive tank 11.

When configuring multiple reactive tanks 11, at least part of reaction of the concentration suspension to flow back from insolubleization slot 21 Slot 11 is preferably set to the slot other than most downstream reactive tank 11.The reactive tank 11 for making at least part of concentration suspension flow back It more leans on into upstream, so that the ferric iron compound in concentration suspension is dissolved as ferric ion, further can more prolong Length is from ferrous ion is reduced to the time for Fenton's reaction.Ferric iron compound in the concentration suspension to flow back as a result, It can effectively be recycled in Fenton's reaction.

In present embodiment, discarded ferric iron compound can recycle in the water process using Fenton's reaction.Cause This can also reduce in addition to that can reduce the expense needed for ferric iron compound processing and add what mechanism 15 added by ferron The amount of ferron.

(catalyst concn determination part)

Catalyst concn determination part 19B is the measurement for measuring iron reducing catalyst relative to the mass concentration of concentration suspension total amount Portion.In present embodiment, mass concentration and catalyst concn that can be according to iron reducing catalyst relative to reaction solution total amount be surveyed The measurement result of portion 19B is determined to find out concentration rate.

Iron reducing catalyst can enumerate following methods relative to the assay method of the mass concentration of concentration suspension total amount：It takes Concentration suspension in sample insolubleization slot 21, according to by concentration suspension sampling amount and dry concentration suspension obtain it is residual Slag amount is calculated.In addition, other methods can enumerate the amount of scattered light measured when using up irradiation to the concentration suspension of sampling And the method for measuring the mass concentration of iron reducing catalyst.Catalyst concn determination part 19B is can to implement this assay method Device.

In present embodiment, the example that catalyst concn determination part 19B is arranged in insolubleization slot 21 is shown, It can be arranged among suspension flows back mechanism 32.

(control unit)

Control unit 19C is control hydrogen peroxide addition mechanism 16 and catalyst addition mechanism 17 so that calculated according to the following formula Compare R₂For 1.9 or more and 100 control units below.

R₂=A₂/B₂

B₂Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time Gross mass (the unit of hydrogen peroxide：Mg it) divided by setting time is flowed into the amount of the waste water of reactive tank 11 and calculates It arrives.

Control unit 19C at least adds mechanism 16 with hydrogen peroxide and catalyst addition mechanism 17 is connect.Control unit 19C according to The measurement result of catalyst concn determination part 19B determines the addition of the flow and iron reducing catalyst of the concentration suspension of reflux Amount, and the flow (additive amount of hydrogen peroxide) of the concentration and hydrogen peroxide of the hydrogen peroxide of addition is determined simultaneously.Moreover, passing through Catalyst, which adds mechanism 17, will determine that the iron reducing catalyst of additive amount is added in reactive tank 11.In addition, passing through hydrogen peroxide Addition mechanism 16 will determine that the hydrogen peroxide of additive amount is added in reactive tank 11.

When configuring multiple reactive tanks 11, control unit 19C is in the reactive tank 11 of most upstream, control hydrogen peroxide addition mechanism 16 and catalyst addition mechanism 17 so that according to above formula is calculated comparing R₂It is 1.9 or more and 100 or less.

(regulating tank)

Regulating tank 41 is the slot stored to the processing water supplied from insolubleization slot 21 via third flow path 31.

7th flow path 55 is connected to regulating tank 41.7th flow path 55 is that the processing water for making to be reserving in regulating tank 41 is discharged simultaneously It is flowed into the flow path of separator 42.Pump 55a and regulating valve 55b is provided on the 7th flow path 55.Above-mentioned processing water energy as a result, It is enough to be discharged from regulating tank 41.It is explained, regulating valve 55b can should not.

Separator 42 is to make the processing moisture film isolated in enrichment process be separated into contained in processing water to be aoxidized The device of contact scar substance, filtered water.Separator 42 is using the cross-flow filtration mode for having used the second membrane module 43.By adopting With cross-flow filtration mode, accumulation that can be by oxidative pollutant matter on the surface of the film can be inhibited, and filtration flux can be kept.

Have NF membrane or reverse osmosis membrane in second membrane module 43.When using NF membrane in the second membrane module 43, material Matter can be enumerated：It is polyethylene kind, class containing aromatic polyamide or the polyamide-based of crosslinked polyamide class, aliphatic amine condensation polymer, miscellaneous Cyclopolymerization species, polyvinyl alcohol, cellulose acetate Type of Collective object etc..

When using reverse osmosis membrane in the second membrane module 43, material can be enumerated：Polyamide, polysulfones, cellulose acetate etc., It is preferred that the polyamide containing aromatic polyamide or crosslinked aromatic polyamide.

4th flow path 51 is connected to the second membrane module 43.4th flow path 51 be make the second membrane module of filtration 43 NF membrane or The filtered water of reverse osmosis membrane is discharged by separator 42 and is flowed into the flow path of retention basin 61.Using above-mentioned pump 55a to second The filtering surface side (upstream side) of membrane module 43 applies pressure, thus enables that above-mentioned filtered water is discharged from regulating tank 41, Neng Gouli UF membrane is carried out with separator 42.Adjusting for flow can be carried out by pumping the output adjusting of 55a.

(retention basin)

Retention basin 61 is the slot to being stored from separator 42 via the filtered water that the 4th flow path 51 supplies.It is reserving at and stores Filtered water in slot 61 can use the dilutions such as industrial water, be discharged into river etc..

According to the water treatment facilities 1 with above structure, anti-using the Fenton with ferric ion reduction reaction In the water process answered, inhibit the inactivation of the iron reducing catalyst for reduction reaction, Fenton's reaction efficiency excellent.That is, according to water Water process can be effectively performed in processing unit 1.

[method for treating water]

Have in the method for treating water of present embodiment：Oxidation operation (oxidation processes), enrichment process, divides at insoluble chemical industry sequence From process, suspension reflow process and reduction process (reduction treatment).

In this specification, oxidation operation and reduction process are equivalent to " reaction process " in claims.

The method for treating water for using water treatment facilities 1 as shown in Figure 1 is illustrated.The water process side of present embodiment In method, in reactive tank 11, adjusting, which contains, first to be 1.0 or more and 4.0 or less by the pH value of waste water of oxidative pollutant matter. Compare R calculated according to the following formula simultaneously₁For 1.9 or more and 100 it is below under the conditions of, carry out Fenton's reaction, pair can be by oxygen Change contact scar substance to be aoxidized (oxidation operation).

R₁=A₁/B₁

B₁Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time Gross mass (the unit of hydrogen peroxide：Mg amount (the unit of the waste water) divided by oxidation operation handled in setting time： L it) is calculated.

Then, in insolubleization slot 21, the reacting liquid pH value obtained in oxidation operation is adjusted to 6.0 or more and 10.0 Hereinafter, ferric ion insolubleization for making ferrous ion and being generated using Fenton's reaction, generates ferrous compound and ferric iron Compound (insoluble chemical industry sequence).

Further, by enrichment facility 22 make it is suspended have the suspension of ferrous compound and ferric iron compound be separated by solid-liquid separation for containing There are the sludge of iron compound and iron reducing catalyst and processing water, obtains the concentrated concentration suspension (enrichment process) of sludge.

Then, the processing water isolated in enrichment process is held in regulating tank 41.Moreover, making processing water from adjusting Slot 41 flows out to separator 42, and UF membrane (separation process) is carried out by separator 42.In separation process, moisture will be handled From for processing water contained in can be by oxidative pollutant matter and filtered water.Further, it is held in separation process in retention basin 61 In the filtered water isolated.

Suspension flows back in mechanism 32, and the concentration suspension concentrated in enrichment process is made to be flowed back into from insolubleization slot 21 Reactive tank 11 (suspension reflow process).In addition, by control unit 19C, according to the measurement knot of catalyst concn determination part 19B Fruit determines the additive amount of the flow and iron reducing catalyst of the suspension of reflux, and determines the additive amount of hydrogen peroxide simultaneously.And And adding mechanism 17 by catalyst makes the iron reducing catalyst of determining additive amount be added in reactive tank 11.In addition, passing through Hydrogen oxide addition mechanism 16 makes to determine that the hydrogen peroxide of additive amount is added in reactive tank 11.

The ferric iron compound flowed back into the suspension of reactive tank 11 is dissolved as ferric ion in reactive tank 11, and It is reduced to ferrous ion (reduction process) by hydrogen peroxide and iron reducing catalyst.

According to the method for treating water with the above method, the Fenton's reaction with ferric ion reduction reaction is being utilized Water process in, inhibit the inactivation of the iron reducing catalyst for reduction reaction, Fenton's reaction efficiency is excellent.That is, according to this reality The method for treating water of mode is applied, water process can be effectively performed.

[water treatment facilities]

The structure of water treatment facilities 2 to being used in the method for treating water of present embodiment illustrates.Fig. 2 is present embodiment Water treatment facilities 2 schematic configuration diagram.As shown in Fig. 2, water treatment facilities 2 and the water treatment facilities 1 of first embodiment have A part of structure is identical.As a result, in present embodiment, identical attached drawing is marked to inscape same as the first embodiment Label, and its detailed description is omitted.

Water treatment facilities 2 has in reactive tank 11：PH regulating devices 14, ferron addition mechanism 15, hydrogen peroxide addition Mechanism 16, catalyst addition mechanism 17 and catalyst concn determination part 18.

Water treatment facilities 2 has suspension reflux mechanism 32 between insolubleization slot 21 and reactive tank 11.In addition, suspended Has magnetic separating device 34 in liquid reflux mechanism 32.

(catalyst concn determination part)

Catalyst concn determination part 18 is that measurement iron reducing catalyst is dense relative to the quality of the reaction solution total amount in reactive tank 11 The determination part of degree.In present embodiment, according to the measurement result of catalyst concn determination part 18, addition iron reducing catalyst so that Iron reducing catalyst reaches predetermined concentration relative to the mass concentration of reaction solution total amount.Meanwhile ferron is added so that iron restores The mass concentration ratio of catalyst and ferron reaches predetermined value.The predetermined concentration of iron reducing catalyst refers to use and purpose processing The hydrogen peroxide of the corresponding additive amount of water quality, the concentration of iron reducing catalyst needed for ferric ion reduction reaction.In addition, iron The predetermined value of the mass concentration ratio of reducing catalyst and the ferron is the iron for referring to carry out ferric ion reduction reaction The mass concentration ratio of reducing catalyst and the ferron.

The assay method of iron reducing catalyst in reactive tank 11 relative to the mass concentration of reaction solution total amount, can enumerate with Lower method：Sample reactive tank 11 in reaction solution, to by reaction solution sampling amount and dry reaction liquid obtained from mass of residue It is calculated.In addition, other methods can enumerate the method that the scattering light to the reaction solution transmitted light of sampling is measured.Catalyst Concentration mensuration portion 18 is the device that can implement this assay method.

When configuring multiple reactive tanks 11, catalyst concn determination part 18 measures the iron reduction catalysts of most upstream reactive tank 11 The mass concentration of agent.

(suspension reflux mechanism)

Suspension reflux mechanism 32 be keep sludge concentrated concentration suspension at least part from insolubleization slot 21 via Magnetic separating device 34 flows back into the mechanism of reactive tank 11.

《Magnetic separating device》

Magnetic separating device 34 makes paramagnetism object contained in concentration suspension be detached using magnetism from concentration suspension Device.

In the past, in the water process using the Fenton's reaction with ferric ion reduction reaction, with Fenton's reaction Progress and iron reducing catalyst inactivate, Fenton's reaction efficiency may be low.For this problem, in order to be added into reactive tank New iron reducing catalyst, using the method for recycling iron reducing catalyst.But in traditional water process, only recycling has Active iron reducing catalyst, there are no the methods of the iron reducing catalyst of effective recycling inactivation.

On the other hand, to solve the above-mentioned problems, present inventor has performed further investigations, as a result, it has been found that with Fenton's reaction Progress, on iron reducing catalyst surface formed slightly solubility iron oxide crystal.The present inventor speculates due to forming slightly solubility Iron oxide crystal, the reaction site on iron reducing catalyst surface is lost, therefore iron reducing catalyst inactivates.

Additionally, it was found that iron oxide crystal, main component contain ferroso-ferric oxide or γ-di-iron trioxide or this two Person.Also, it has been found that since ferroso-ferric oxide and γ-di-iron trioxide show paramagnetism, it, can by using magnetism The iron reducing catalyst of inactivation is effectively set to be fetched into outside reaction system.

Known magnetic separating device may be used in magnetic separating device 34.Generating magnetic mechanism can enumerate：Permanent magnet, electromagnetism Iron or superconducting magnet, especially because high-intensity magnetic field can be generated, therefore preferred superconducting magnet.It is isolated with magnetic separating device 34 suitable Magnetic material can be fetched into outside by reducing the magnetic field intensity of magnetic separating device 34 from magnetic separating device 34.Utilizing electromagnetism When the magnetic separation device of iron or superconducting magnet, magnetic field intensity can be reduced by reducing power supply.Magnetic separation device 34 Can have known recovery device, the paramagnetism object isolated with magnetic separation device 34 can be recycled.

Magnetic separation device 34 has the 6th flow path 39.6th flow path 39 is the concentration suspension made after separation paramagnetism object Flow into the flow path that (supply) arrives reactive tank 11.

Magnetic separation device 34 can be arranged upper in either one or two of reactive tank 11 and the cycle of insolubleization slot 21 cycle. In present embodiment, the example for making magnetic separation device 34 that the mechanism 32 that flows back in suspension is set is shown, but be not limited to This.Magnetic separating device 34 can be set in reactive tank 11, insolubleization slot 21 and suspension reflux mechanism 32 extremely It is one few.

Due to seldom worrying to corrode and be easy mass concentration of the management iron reducing catalyst relative to reaction solution total amount, It is preferably provided in insolubleization slot 21 or suspension reflux mechanism 32.

In addition, such as present embodiment, can medial launder be set in the cycle that reactive tank 11 and insolubleization slot 21 recycle Magnetic separation device 34 can also be arranged in (being unillustrated) in medial launder.

According to the water treatment facilities 2 with above structure, anti-using the Fenton with ferric ion reduction reaction In the water process answered, the iron reducing catalyst of inactivation can effectively be made to be fetched into outside reaction system.That is, according to water treatment facilities 2, water process can be effectively performed.

[method for treating water]

The method for treating water of present embodiment is identical as a part of process of the method for treating water of first embodiment.Present embodiment Method for treating water and first embodiment method for treating water the difference is that comprising Magneto separate process.

In the Magneto separate process of present embodiment, in suspension reflow process, using setting in suspension reflux mechanism Magnetic separation device 34 in 32 concentrates paramagnetism object contained in suspension using magnetism from concentration suspension separation.

According to the method for treating water with the above method, the Fenton's reaction with ferric ion reduction reaction is being utilized Water process in, so that the iron reducing catalyst of inactivation is fetched into outside reaction system.That is, according to the present embodiment Water process can be effectively performed in method for treating water.

It is explained, the water treatment facilities and method for treating water of present embodiment are not limited to above-mentioned embodiment. For example, in water treatment facilities 1 or water treatment facilities 2, regulating tank 41 can also be saved and separator 42 is not isolated process. In this case, it will can also be directly reserving in retention basin 61 by the processing water of enrichment facility 22.

In addition, for example in the above-described embodiment, the sludge concentration method of enrichment facility 22 has been used to be not necessarily utilization The method of first membrane module 23.For example, it is also possible to using above-mentioned sand filtration, pressure floatation separation, centrifuge, belt press filtration Machine, sedimentation basin precipitation etc..

Further, it shows the example that enrichment facility 22 is arranged in insolubleization slot 21, concentration can not also be filled 22 settings are set in insolubleization slot 21.At this point, other slots can also be configured between insolubleization slot 21 and regulating tank 41, Enrichment facility 22 is set in this slot.At this moment, there is " suspension " in insolubleization slot 21, in the slot for being provided with enrichment facility 22 In the presence of " concentration suspension ".The magnetic separating device 34 of present embodiment is using in the Magnetic Isolation suspension and concentration suspension Either one or two of or both contained in paramagnetism object.

When enrichment facility 22 not being arranged in insolubleization slot 21, the structure of the first membrane module 23 can be following institute The structure shown.For example, fixing filter membrane in a manner of separating the upstream side and downstream side of filter membrane (secondary filter or ultrafiltration) in putamina. Moreover, the upstream side of the filter membrane in putamina is by circulation stream and is reserving with comprising containing iron compound and iron reducing catalyst Sludge is connected with the tank that stores of the suspension of processing water, and the downstream side of filter membrane can connect suction pump.

Water treatment facilities 1 or water treatment facilities 2 can also save suspension reflux mechanism 32 without suspension reflux work Sequence.

In the reactive tank 11 of first embodiment, the catalyst concn determination part 18 of second embodiment can also be set. At this moment, control unit 19C can be determined according to the measurement result of catalyst concn determination part 18 and catalyst concn determination part 19B Reflux concentration suspension flow and iron reducing catalyst additive amount, and simultaneously determine addition hydrogen peroxide concentration and The flow (additive amount of hydrogen peroxide) of hydrogen peroxide.Control unit 19C is easy to control hydrogen peroxide addition mechanism 16 and urges as a result, Agent adds mechanism 17 so that calculated according to the following formula to compare R₂It is 1.9 or more and 100 or less.

R₂=A₂/B₂

A₂Indicate mass concentration (unit of the iron reducing catalyst in reactive tank 11 relative to reaction solution total amount：mg/L).

B₂Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time Gross mass (the unit of hydrogen peroxide：Mg) divided by setting time it is flowed into the amount (unit of the waste water of reactive tank 11：L) And it is calculated.

Compare R in such management₂In water treatment facilities within the above range, the inactivation of iron reducing catalyst can be inhibited. Water process can be effectively performed in this water treatment facilities as a result,.

In the suspension reflux mechanism 32 of first embodiment, can also have the magnetic separating device of second embodiment 34.It is considered as Fenton's reaction efficiency thereby, it is possible to which the iron reducing catalyst of inactivation is efficiently separated and reduced from reactive tank 11 One of low reason.Water process can be effectively performed in this water treatment facilities as a result,.

The water treatment facilities 2 of second embodiment can also have the control unit 19C of first embodiment.At this moment, it controls Portion 19C can confirm the additive amount of iron reducing catalyst according to the measurement result of catalyst concn determination part 18, and confirm simultaneously The concentration of the hydrogen peroxide of addition and the flow (additive amount of hydrogen peroxide) of hydrogen peroxide.Moreover, adding machine by catalyst Structure 17 makes to determine that the iron reducing catalyst of additive amount is added in reactive tank 11.In addition, adding mechanism 16 by hydrogen peroxide makes Determine that the hydrogen peroxide of additive amount is added in reactive tank 11.

The concentration of hydrogen peroxide determination part of first embodiment can also be set in the reactive tank 11 of second embodiment 19A.In addition, the catalyst concn determination part of first embodiment can also be arranged in the insolubleization slot 21 of second embodiment 19B.Thereby, it is possible to so that hydrogen peroxide is reacted with iron reducing catalyst with more suitably ratio.

Embodiment

In the following, by embodiment, the present invention is described in detail, but the present invention is not limited in described in hereafter Hold.It is explained, for structure identical with water treatment facilities 1 as shown in Figure 1, is illustrated using identical title.

[calculating of the removal rate of total organic carbon]

The removal rate (sometimes referred to as " total organic carbon " is " TOC " below) of total organic carbon is to indicate the active index of iron reducing catalyst One of, the TOC removal rates the high then it is believed that the activity of iron reducing catalyst is also higher.The TOC removal rates of embodiment and comparative example It is calculated by the TOC concentration in the TOC concentration and processing water in raw water (waste water model) according to formula (S1).

[number 1]

It is explained, the measurement for handling the TOC concentration in water is according to JIS K0102 " 22. organic body carbons (TOC) ", profit It is measured with combustion method total organic carbon analyzer (Mitsubishi of Co., Ltd. chemistry ANALYTECH systems, model " TOC-300V ").

Repeat the water process of raw water daily using the water treatment facilities of embodiment and comparative example, the water of sampling processing daily.And And it calculates to what is obtained and handles time (below sometimes referred to as " deactivation time ") of the TOC removal rates in water less than 50%.This The the time the long, thinks that the inactivation of iron reducing catalyst is more suppressed, the service life of iron reducing catalyst is longer.

Each reagent uses following material.

Ferron：Ferric sulfate (II) heptahydrate (FeSO₄·7H₂O)

Iron reducing catalyst：Activated carbon (DiaFellow CT, Mitsubishi Chemical's water solution Co. Ltd. system)

[embodiment 1]

Make the water treatment facilities having following structure：First reactive tank, the second reactive tank being connected in series with the first reactive tank, Has the insolubleization slot of enrichment facility.In the present embodiment, the reactive tank in claims is anti-by the first reactive tank and second Slot is answered to constitute.In addition, dimethyl sulfoxide (DMSO) (DMSO) is added in pure water become 200mg/L (total organic carbon amount be 65mg/ L), dissolving forms solution as waste water model.It is explained, prior confirmation DMSO cannot be tightly held by activated carbon removal substantially. Water process is carried out to this waste water model by the water treatment facilities of making.

Be explained, in embodiment below, waste water model, for waste water model pH value adjust acid or alkali, ferron, It is mixed with the amount of hydrogen peroxide and the mixed liquor of iron reducing catalyst, keeps the amount of the reaction solution after mixed liquor reaction identical.As a result, Using the amount of mixed liquor as the amount of reaction solution in the calculating of each mass concentration.

The film for having the first membrane module uses ultrafiltration membrane (the beautiful yang edema solution Co. Ltd. system of Mitsubishi, nominal pore size 0.05μm)。

First, raw water flows into (supply) to the first reactive tank, by making its overflow be supplied to the second reactive tank and not successively Dissolvingization slot.The delay of consideration is not given the flow by the suspension reflux mechanism concentration suspension that never dissolvingization slot flows back Time, set in the first reactive tank for 4 hours, in the second reactive tank be 1 hour, in insolubleization slot be 1 hour.Further, With pH value in sulfuric acid the first reactive tank of adjusting to 2.9.On the other hand, with pH value in sodium hydroxide adjusting insolubleization slot to 8.0.

Hydrogen peroxide is added into the first reactive tank so that hydrogen peroxide reaches relative to the mass concentration of raw water total amount 600mg/L。

In addition, adding ferron into the first reactive tank and the second reactive tank so that the quality of ferron is relative to first The concentration of reactive tank and the reaction solution total amount in the second reactive tank slot reaches 1200mg/L, and (it is 240mg/ to be converted into ferrous ion L)。

In addition, adding iron reducing catalyst into any of first reactive tank and the second reactive tank or both so that Iron reducing catalyst reaches 2000mg/ relative to the mass concentration of the reaction solution total amount in the first reactive tank and the second reactive tank slot L。

It is calculated according to the following formula to compare R in embodiment 1₂For 3.3 (A₂=2000mg/L, B₂=600mg/L).

R₂=A₂/B₂

A₂Indicate mass concentration (unit of the iron reducing catalyst in reactive tank relative to reaction solution total amount：mg/L).

B₂Indicate the mass concentration (unit of hydrogen peroxide：Mg/L), it is by being added in waste water in setting time with this Hydrogen peroxide gross mass (unit：Mg) divided by setting time (10 minutes) it is flowed into the amount of the waste water of reactive tank (unit：L it) is calculated.

In addition, adding ferron into insolubleization slot so that ferron is suspended relative to the concentration in insolubleization slot The mass concentration of liquid total amount reaches 12000mg/L (it is 2400mg/L to be converted into ferrous ion).In addition, adding into insolubleization slot Add iron reducing catalyst so that iron reducing catalyst is reached relative to the mass concentration of the concentration suspension total amount in insolubleization slot To 20000mg/L.Moreover, the sludge containing ferric iron compound and iron reducing catalyst is made to flow back into first from insolubleization slot In reactive tank so that iron reducing catalyst is dense relative to the quality of the reaction solution total amount in the first reactive tank and the second reactive tank slot Degree remains 2000mg/L.

Water process is carried out to waste water model using the water treatment facilities with above structure, the result is that handling in water Time of the TOC removal rates less than 50% is 15 days.

[embodiment 2]

Ferron is added into the first reactive tank and the second reactive tank so that ferron is reacted relative to the first reactive tank and second The mass concentration of reaction solution total amount in slot slot reaches 600mg/L (it is 120mg/L to be converted into ferrous ion).

In embodiment 2, compare R according to above formula is calculated₂For 3.3 (A₂=2000mg/L, B₂=600mg/L).

In addition, adding ferron into insolubleization slot so that ferron is suspended relative to the concentration in insolubleization slot The mass concentration of liquid total amount reaches 6000mg/L (it is 1200mg/L to be converted into ferrous ion).In addition to the above operation, with reality Example 1 is applied similarly to be operated.

Water process is carried out to waste water model using the water treatment facilities with above structure, the result is that handling in water Time of the TOC removal rates less than 50% is 8 days.

[embodiment 3]

Ferron is added into the first reactive tank and the second reactive tank so that ferron is reacted relative to the first reactive tank and second The mass concentration of reaction solution total amount in slot slot reaches 4500mg/L (it is 900mg/L to be converted into ferrous ion).In addition, to first Iron reducing catalyst is added in any of reactive tank and the second reactive tank or both so that iron reducing catalyst is relative to the The mass concentration of one reactive tank and the reaction solution total amount in the second reactive tank slot reaches 1500mg/L.

In embodiment 3, compare R according to above formula is calculated₂For 2.5 (A₂=1500mg/L, B₂=600mg/L).

In addition, adding ferron into insolubleization slot so that ferron is suspended relative to the concentration in insolubleization slot The mass concentration of liquid total amount reaches 45000mg/L (it is 9000mg/L to be converted into ferrous ion).In addition, adding into insolubleization slot Add iron reducing catalyst so that iron reducing catalyst is reached relative to the mass concentration of the concentration suspension total amount in insolubleization slot To 15000mg/L.In addition to the above operation, it is similarly operated with embodiment 1.

Water process is carried out to waste water model using the water treatment facilities with above structure, the result is that handling in water Time of the TOC removal rates less than 50% is 13 days.

[embodiment 4]

Ferron is added into the first reactive tank and the second reactive tank so that ferron is reacted relative to the first reactive tank and second The mass concentration of reaction solution total amount in slot slot reaches 720mg/L (it is 144mg/L to be converted into ferrous ion).

In embodiment 4, compare R according to above formula is calculated₂For 2.0 (A₂=1200mg/L, B₂=600mg/L).

In addition, adding ferron into insolubleization slot so that ferron is suspended relative to the concentration in insolubleization slot The mass concentration of liquid total amount reaches 7200mg/L (it is 1440mg/L to be converted into ferrous ion).In addition to the above operation, with reality Example 1 is applied similarly to be operated.

[comparative example 1]

Ferron is added into the first reactive tank and the second reactive tank so that ferron is reacted relative to the first reactive tank and second The mass concentration of reaction solution total amount in slot slot reaches 600mg/L (it is 120mg/L to be converted into ferrous ion).In addition, to first Iron reducing catalyst is added in any of reactive tank and the second reactive tank or both so that iron reducing catalyst is relative to the The mass concentration of one reactive tank and the reaction solution total amount in the second reactive tank slot reaches 1000mg/L.

In comparative example 1, compare R according to above formula is calculated₂For 1.7 (A₂=1000mg/L, B₂=600mg/L).

In addition, adding ferron into insolubleization slot so that ferron is total relative to the suspension in insolubleization slot The mass concentration of amount reaches 6000mg/L (it is 1200mg/L to be converted into ferrous ion).In addition, adding iron into insolubleization slot Reducing catalyst so that iron reducing catalyst reaches relative to the mass concentration of the suspension total amount in insolubleization slot 10000mg/L.In addition to the above operation, it is similarly operated with embodiment 1.

Water process is carried out to waste water model using the water treatment facilities with above structure, the result is that handling in water Time of the TOC removal rates less than 50% is 2 days.

[comparative example 2]

Iron reducing catalyst is added into any of first reactive tank and the second reactive tank or both so that iron reduction catalysts Agent reaches 1000mg/L relative to the mass concentration of the reaction solution total amount in the first reactive tank and the second reactive tank slot.

In comparative example 2, compare R according to above formula is calculated₂For 1.7 (A₂=1000mg/L, B₂=600mg/L).

Iron reducing catalyst is added into insolubleization slot so that iron reducing catalyst is relative to outstanding in insolubleization slot The mass concentration of turbid total amount reaches 10000mg/L.In addition to the above operation, it is similarly operated with embodiment 1.

Embodiment and the result of comparative example are shown in table 1.

[table 1]

As shown in table 1, R will compared according to above formula is calculated₂For in 1.9 or more and 100 Examples 1 to 4 below, Compare R with above-mentioned₂Comparative example 1 less than 1.9 is compared with comparative example 2, and deactivation time extends.That is, the application present invention's In the Examples 1 to 4 of one mode, the inactivation of iron reducing catalyst is suppressed, and Fenton's reaction efficiency is excellent.

In addition, by embodiment 1 and embodiment 2 as a result, and above-mentioned comparing R₂It is 1.9 or more and 100 or less, it is believed that pass through Increase ferron makes deactivation time extend relative to the mass concentration of reaction solution total amount.That is, embodiment 1 and embodiment 2 compare, and the inactivation of iron reducing catalyst is more suppressed, and Fenton's reaction efficiency is better.

It may indicate that the present invention has practicability by above-mentioned.

Claims

1. a kind of containing can include following processes by the method for treating water of the waste water of oxidative pollutant matter, the method for treating water (i)~(iii)：

(A) pH value of waste water is 1 or more and 4 or less

R₁=A₁/B₁

Wherein, A₁Mass concentration of the expression iron reducing catalyst relative to reaction solution total amount, unit mg/L,

B₁The mass concentration for indicating the hydrogen peroxide is by being added in the waste water in the setting time The amount of the waste water handled in setting time in the gross mass divided by process (i) of the hydrogen peroxide and be calculated, The unit of the mass concentration of the hydrogen peroxide is mg/L, and the unit of the amount of the waste water is L, the gross mass of the hydrogen peroxide Unit be mg.

2. method for treating water according to claim 1 comprising suspension reflow process makes the suspension in the process At least part and any of at least part or the two of the concentration suspension flow back into the process (i).

3. method for treating water according to claim 1 or 2 comprising Magneto separate process, using magnetism to institute in the process Paramagnetism object contained in any of suspension and the concentration suspension or the two is stated to be detached.

4. method for treating water described in any one of claim 1 to 3, wherein the iron reducing catalyst be selected from At least one of the group being made of activated carbon and zeolite.

5. method for treating water according to any one of claims 1 to 4, wherein, will using acid in the process (i) The pH value of waste water is adjusted to 1 or more and 4 or less.

6. method for treating water according to any one of claims 1 to 5, wherein in the process (i), addition is ferrous Salt or ferrocyanide.

7. according to method for treating water according to any one of claims 1 to 6, wherein in the process (iii), use filter Film obtains the concentration suspension.

8. method for treating water according to any one of claims 1 to 7, has separation process, using receiving in the process Filter membrane or reverse osmosis membrane, by the processing water be separated into contained in the processing water it is described can be by oxidative pollutant matter and filter Cross water.

9. a kind of water treatment facilities has following (1)~(3)：

R₂=A₂/B₂

Wherein, A₂Indicate mass concentration of the iron reducing catalyst relative to the reaction solution total amount in the reactive tank, unit For mg/L,

B₂The mass concentration for indicating the hydrogen peroxide is by being added in the waste water in the setting time The gross mass of hydrogen peroxide divided by the amount for the waste water being flowed into setting time in the reactive tank and be calculated, The unit of the mass concentration of the hydrogen peroxide is mg/L, and the unit of the amount of the waste water is L, the gross mass of the hydrogen peroxide Unit be mg；

10. water treatment facilities according to claim 9, has suspension reflux mechanism, which makes the suspension At least part and any of at least part or the two of the concentration suspension flow back into the reactive tank.

11. water treatment facilities according to claim 9 or 10, has magnetic separating device, the device is using magnetism to institute Paramagnetism object contained in any of suspension and the concentration suspension or the two is stated to be detached.

12. the water treatment facilities according to claim 10 or 11, has：

13. the water treatment facilities according to any one of claim 9~12 has catalyst addition mechanism, the mechanism The iron reducing catalyst is added into the reactive tank.

14. the water treatment facilities according to any one of claim 9~13, has：

15. water treatment facilities according to claim 14, wherein the acid is sulfuric acid or hydrochloric acid.

16. the water treatment facilities according to any one of claim 9~15, wherein the enrichment facility has filter membrane, makes The suspension is obtained with the filter membrane.

17. the water treatment facilities according to any one of claim 9~16, wherein the enrichment facility is arranged described In insolubleization slot.

18. the water treatment facilities according to any one of claim 9~17, has separator, which, which has, receives The processing water is separated into institute in the processing water by filter membrane or reverse osmosis membrane using the NF membrane or the reverse osmosis membrane Contain it is described can be by oxidative pollutant matter and filtered water.