JP2019099423A - Production method of green last and its use - Google Patents

Abstract

To provide a method capable of producing a green last suspension at a low cost by a simple method, and a treatment method of water to be treated using the obtained green last.SOLUTION: A production method of green last includes: a step of stirring water in which a reduction catalyst containing 70 to 40 pts.mass of graphite and 20 to 50 pts.mass of at least one selected from the group consisting of iron and ferrite iron are present to cause a redox reaction after adjusting the pH with an acid in the range of 2 to 4; and a step of confirming that a redox potential value becomes in the range of -400 mv to -950 mv when 15 to 300 pts.mass of ferrous ion and/or a ferrous compound is added to adjust the pH on an alkaline side and a reduction test is performed to end the stirring and the pH adjustment to obtain green last generated in the water, and the production method of the green last of the present invention can produce a green last suspension at a low cost by a simple method and the obtained green last suspension is stable for a long time.SELECTED DRAWING: None

Description

  The present invention relates to a green rust (ferrous hydroxide) suspension, a process for its preparation and its use.

  In Patent Document 1, a solution of ferrous sulfate and ferrous chloride is added to the water to be treated, and neutralization with sodium hydroxide (adjustment to pH = 5) generates Greenlast (ferrous hydroxide). It is described that silicic acid in treated water adheres intensively to green last. However, it is described that the deposition of silicic acid interferes with the oxidation reaction to magnetite, which is a magnetic precipitate in Greenlast, and makes it difficult to form a magnetic precipitate.

In paragraphs [0016] to [0018] in Patent Document 2, paragraph [0016], “The green last has a layered hydroxide of ferrous iron (FeII) and ferric iron (FeIII). A blue-green material having a structure in which anions (A: SO ₄ ²⁻ , Cl ^−, etc.) are taken in between the layers, which is represented by the chemical formula, for example, as follows.
_{[FeII (6 - X) FeIII} X (OH) 1 2] X + [A · nH 2 O] X -, 0.9 <x <4.2
Here, when the anion (A) is SO ₄ ² -and x = 2, it is called green last (II) [GR (II)]. There is a statement with ".
In paragraph [0017] “on the other hand, as a ferrite deposit having magnetism,
Iron ferrite deposits mainly composed of magnetite (Fe ^II OFe ^III ₂ O ₃ ) are preferred.
In addition, as the mixture of Greenlast and ferrite precipitate, the ratio of divalent iron to total iron [Fe ^{2 +} / total Fe] of 0.3 or more is used in order to secure a desired reducing power. Be In the paragraph [0018], “Incidentally, the mixture of the above green last and the iron ferrite precipitate has a ratio of the above divalent iron of 0.3 to 0.85, and the larger this ratio is, the reducing power is In addition, in order to ferritize Greenlast by oxidizing slowly, the ratio of the above-mentioned divalent iron is in the range of 0.4 to 0.65, more preferably 0.5 to 0.5. It may be in the range of 6. "

  In Patent Document 2, a mesh material 200 is provided in the septic tanks 100a and 100b held in an airtight state as shown in FIG. 2 of the present specification (corresponding to FIG. 1 of Patent Document 2). And an apparatus and method for removing the heavy metals by supplying green rust and ferrite precipitates having magnetism from the water purification material supply lines 300a and 300b and flowing the water to be treated from the heavy metal-containing water supply lines 1200a and 1200b There is. It is preferable that the heavy metal-containing water supply line be equipped with a pH adjuster 1500 and that an alkaline substance be supplied to maintain the pH in the septic tank in the range of pH 8 to 11 (see paragraph [0025] of Patent Document 2). Is described.

  However, the device of Patent Document 2 is a device requiring a complicated structure such as a sealed septic tank 100a, 100b, exciting coils 900a, 900b, vibrators 2100a, 2100b, etc., in which the inside holds a non-oxidizing atmosphere. There is a need for continuous processing lines that require complicated controls for heavy metal-containing water, water purification material, treated water discharge, and water purification material discharge, and a large-scale device and its control are required.

Japanese Patent Application Laid-Open No. 2002-102863 Unexamined-Japanese-Patent No. 2006-297365

  The present invention solves the problems of the prior art described above, and provides a method for producing a green last suspension inexpensively by a simple method, not a large-scale device or a continuous processing method using a complicated control method. Try to provide a method of treating and purifying water using

  The present inventors have found that a green last suspension can be obtained by stirring graphite and ferrite iron powder in water placed in the atmosphere and continuing the stirring under appropriate pH conditions, and reached the present invention.

That is, the present invention is as follows.
(1) Stirring water containing a reduction catalyst containing 70 to 40 parts by mass of graphite and 20 to 50 parts by mass of at least one selected from the group consisting of iron and ferrite iron as a pH range of 2 to 4 with an acid Oxidation reduction reaction, and adding 15 to 300 parts by mass of ferrous ion and / or ferrous iron compound to adjust the pH to the alkaline side and performing a reduction test to have an oxidation reduction potential value of -400 mv The manufacturing method of the green last which confirms that it becomes in the range of--950mv, finishes stirring and pH adjustment, and obtains the green last produced in the said water.
(2) 2 to 10 parts by mass of at least one additive metal selected from the group consisting of aluminum, yttrium, zinc, copper, tin, chromium and silicon in the reduction catalyst body as metal and / or metal ferrite The manufacturing method of the green last as described in (1) which has.
(3) The reduction catalyst body has 70 to 40 parts by mass of graphite, 20 to 50 parts by mass of at least one selected from the group consisting of iron and ferrite iron, and 2 to 10 parts by mass of silicon flight (1 Or (2).
(4) The method for producing Greenlast according to any one of (1) to (3), wherein the reduction catalyst body is a powder and / or a lump.
(5) A method for treating treated water, wherein the treated water is brought into contact with the green last suspension obtained by the method according to any one of (1) to (4).
(6) The method of treating treated water according to (5), wherein the treated water contains a metal as a contaminant.
(7) The metal in the water to be treated is at least one contaminant selected from the group consisting of zinc, chromium, iron, copper, tin, nickel, aluminum, silicon, ions thereof and compounds thereof (6 The method of treating treated water according to the above.
(8) 1) Step 1 of adding green last to the water to be treated which is raw water in the treatment tank, adjusting pH and stirring;
2) a step 2 of separating the precipitate and the treated water from the treated water obtained in the step 1,
3) Step 3 of removing sludge from separated sediments
4) adding a part or all of the sludge from which the sludge has been removed to raw water to be treated, adding green last, adjusting the pH and stirring;
5) separating the precipitate and the treated water from the treated water obtained in the step 4;
6) A process for treating the water to be treated using the precipitate cyclically, which comprises the step 6 of obtaining the separated liquid and the sediment after repeating the steps 3 and 4 one or more times after the step 5.
(9) The method for treating water to be treated according to (8), wherein the green last is obtained by the method according to any one of (1) to (4).

(10) The treatment of the water to be treated according to any one of (5) to (9), wherein the water to be treated further contains at least one contaminant selected from the group consisting of an acid, an alkali and ammonia. Method.
(11) The method for treating water to be treated according to any one of (5) to (10), wherein the water to be treated is washing water for chimneys.
(12) The water according to any one of (5) to (11), wherein the water to be treated contains at least one contaminant selected from the group consisting of nitrogen, nitrogen compounds, silicon, silicon compounds and ions thereof. How to treat the water of treatment.
(13) In the method of treating water to be treated according to any one of the above (5) to (12), a chemical treatment agent which is a reaction product of Greenlast and / or a dehydrogenase with a water-soluble organic substance as pretreatment. Water to oxidize and decompose at least one selected from ammonia, nitrogen, nitrogen compounds, silicon, silicon compounds, and ions thereof under acidic conditions, and the water to be treated according to any one of (5) to (12) How to handle
(14) In the method of treating treated water according to any one of the above (5) to (13), at least one selected from the group consisting of aluminum, yttrium, zinc, copper, tin, chromium and silicon obtained The manufacturing method of the green last described in (2) which uses the deposit which contains one as a metal, a metal compound, and / or a metal ferrite as an additive metal and / or a metal ferrite as described in (2).

The method for producing Greenlast according to the invention can produce Greenlast suspension inexpensively by a simple method. The resulting Greenlast suspension is stable for a long time.
The method for treating treated water using Greenlast obtained by the method for producing Greenlast according to the present invention utilizes its aggregation and precipitation even without using a large-scale device or a continuous treatment method requiring complicated control. Thus, contaminants in the water to be treated can be removed.
The present invention can achieve at least one of the above effects.

It is a figure which shows manufacture of the green last suspension of this invention, and the processing flow of the to-be-processed water using the green last suspension following it. It is a figure explaining the prior art described in patent document 2 as FIG. The reference numerals are described by multiplying all the numbers by 100 to distinguish them from the drawings of the present invention.

[1. Reduction catalyst body]
The reduction catalyst used in the present invention can be exemplified by the following three types of mixtures.
(1-1) Mixture of 70 to 40 parts by mass of graphite and 20 to 50 parts by mass of iron (1-2) Mixture of 70 to 40 parts by mass of graphite and 20 to 50 parts by mass of ferrite iron (1-3) Graphite 70 The shape of the mixture of a mixture of a 40 to 40 parts by mass and a total of 20 to 50 parts by mass of ferric iron and iron is not limited, and powder, lumps and the like can be exemplified.
These mixtures may be mixed as pure components in this mass ratio range, and iron-containing deposits may be used which are discarded by contaminated water treatment such as ferrite method or iron hydroxide coprecipitation method.
(1-4) The reduction catalyst used in the present invention may further contain the following additive metals in the above-mentioned three types of mixtures. When these metals are contained, the amount is 2 to 20 parts by mass with respect to 100 parts by mass of iron or ferritic iron.
The metals are aluminum (Al), yttrium (Y), zinc (Zn), copper (Cu), tin (Sn), Cr (chromium) and / or silicon (Si). These can be contained as metals, and may be contained as metal ferrites (magnetic iron precipitates) or metal compounds.
(1-5) Among them, a mixture containing 70 to 40 parts by mass of graphite and 20 to 50 parts by mass of at least one selected from the group consisting of iron and ferrite iron and 2 to 10 parts by mass of silicon ferrite is preferable .

<Constructing a reduction catalyst body with a deposit obtained by treating the water to be treated with the Greenlast suspension>
The reduction catalyst body should be kept in water without being in contact with, flowing or being kept in water in the water to be stirred, put in a cylinder such as punching metal and soak in water, or make a container with a wire mesh and soak in water to react it can. A reagent may be used as a raw material of the reduction catalyst body, but a deposit obtained by treating a water to be treated containing metal ions using the Greenlast suspension produced by the method of the present invention can be used. Aluminum (Al), yttrium (Y), zinc (Zn), copper (Cu), tin (Sn) are contained in the precipitate obtained by treating the water to be treated containing metal ions as described later in the examples. And Cr (chromium) and / or silicon (Si) or metal ferrites containing these. Example 2-1 described later is a production experiment of aluminum ferrite used for the reduction catalyst body of the present invention, and is also a removal treatment of aluminum metal in a liquid to be treated using the green last suspension of the present invention.

[2. Manufacturing method of green last]
(2-1) In the method for producing Greenlast of the present invention, when water containing a reduction catalyst is stirred, a redox reaction (also referred to as a primary battery type galvanic cell reaction or a redox reaction) occurs, and the pH of water is 2 to 4 The mixture is stirred to cause a redox reaction, preferably with ferrous iron if the ORP value [redox potential (based on Ag / AgCl electrode, hereinafter referred to as ORP)] reaches 300 mv to 400 mv. Add 15 to 300 parts by mass to 50 parts by mass of medium iron (ferrite iron or iron of reduction catalyst). After addition, preferably the mixture is again stirred until the ORP reaches 300 mv to 400 mv. The pH is adjusted to the alkaline side, reduction test is conducted, and ORP is adjusted to the range of -400 mv to -950 mv, preferably pH 10.5 ± 0.5 to confirm that it becomes the range of -700 to -950 mv, and stirring and pH adjustment To obtain the green last produced in the water. If pH adjustment is required, add acid or alkali. Examples of the acid include hydrochloric acid, sulfuric acid and nitric acid, and examples of the alkali include sodium hydroxide (sodium hydroxide), sodium hypochlorite (sodium hypochlorite), potassium hydroxide (potassium hydroxide), and ferrous iron Ferrous sulfate, ferrous hydrochloride, ferrous nitrate can be exemplified. The stirring tank does not need to be sealed, and the upper part is open to the atmosphere.

The inventor believes that the redox reaction occurs as follows, but is not limited to these mechanisms.
Electrolysis starts when the reduction catalyst body is submerged and water enters from the pores of the reduction catalyst body. The inside of the reduction catalyst body is an ecological reaction and a potential difference is generated, and an anodic electrode (Fe) and a cathodic electrode (C) are formed by corrosion electrolytic action to carry out electrolysis. In the reduction catalyst in water, the anode (iron) reaction and the cathode (carbon) reaction proceed simultaneously. As the electrolytic reaction proceeds, the iron of the anode migrates into water as iron ions. Hydrogen ions become water by hydrogen gas or dissolved oxygen. It is a microcell electrolysis method using the potential difference (1.2 V) generated at the time of immersion in a solution in which the powder is electrolyzed.
The reaction mechanism is based on the following electrochemical reaction of the primary battery.
The reduction catalyst in water causes the anode (iron) reaction and the cathode (carbon) reaction to occur simultaneously. As the electrolytic reaction proceeds, the iron of the anode migrates into water as iron ions. Hydrogen ions become water by hydrogen gas or dissolved oxygen.
Anode (anode) Fe: Fe- ² E → Fe ^{2 +} E (Fe / Fe 2 +) = 0.44 V
Negative (cathode) C: 2H + + 2E → H ₂ E (H + / H 2) = 0.00 V
The cathode reaction of the reduction catalyst (O ₂ ) is
2H + + 2e-→ H ₂ (acidic solution, hydrogen evolution)
O ₂ + 4H + + 4e-→ 2H ₂ O (acidic solution, oxygen reduction)
O ₂ + 2H ₂ O + 4e − → 4OH − (neutral or alkaline, oxygen reduction).
In the case of alkalinity, when the oxygen reduction is small, the pH shifts to the acid side. When the pH is shifted to the acidic side, it is not necessary to add a pH adjuster.
Electrolysis produces OH ions. Metal ions are precipitated by OH ions. When electrolysis is carried out with an acidic solution, Greenlast Fe ²⁺ (OH) ₆ is formed at iron ions with a small amount of oxygen reduction. A part of the layer of Fe ²⁺ (OH) ₆ is substituted by Fe ³⁺ .

When the solution to be electrolyzed is an acidic solution (pH 3.0 or less) and the reduction catalyst is put in water for electrolysis, iron ions from the anode reaction are excessively supplied. The electrolyte lacks oxygen in the cathode reaction (oxygen reduction), and iron ions form Greenlast (Fe ²⁺ (OH) ₆ ). By adjusting the pH of this electrolytic solution to pH 9 to 11.5 with an alkali agent (caustic soda), Greenlast precipitates and separates, and when the precipitated Greenlast is extracted, a Greenlast suspension is obtained.

The change of ferritic iron in the process by electrolysis causes various reactions. Iron in water changes to Fe ₂ O ₄ → Fe ₂ (OH) ₆ → Fe ₃ OH ₄ or the like by the reaction of a corrosion metal (iron). It changes to brown, red, greenish blue and black when it is expressed by rust. When oxidation is dominant, a small amount of brown and red rust is dissolved in water, but green rust (green and blue rust) is formed in the reduced state, and when treating water to be treated, reducing oxyanion (chromate ion) CrO ₄ -, selenate ions SeO ₄ -, nitrate ions NO ₃ -) oxyanion (arsenate ion AsO ₄ -, phosphate ion PO ₄ -) is a part of Fe ²⁺ during Greenlast generated is replaced with Fe ³⁺ gap Anion ions and water molecules enter into these, and these ions are adsorbed to the green last.

(2-2) The production of Green Last is performed by adjusting the pH as described above, but can be controlled more easily by measuring the ORP of the stirring water during production. Add ferrous ion in the pH 2 to 4 range. The pH value is adjusted to a range of 9 to 11.5 and the formation of green last is seen as the suspension becomes light blue clear, dark green, green or light green clear. Although ORP is not limited, when Greenlast is produced, measurement of ORP under alkaline conditions gives values of -400 mv to -950 mv.

[3. Green last, green last suspension]
(3-1) When the pH is kept at a predetermined value, preferably in the range of 4 to 6, more preferably 4.0 ± 0.5, the produced Greenlast suspension is stable for at least one year.
(3-2) The green last suspension can be filtered by a filtration filter using a transfer pump, stored in any container, sold, and distributed.

  The pH of the separated liquid fluctuates to the neutral side in a state where Greenlast is formed and precipitated and separated at pH 9 to 11.5, and the precipitated Greenlast indicates the alkaline side. The following Table 1 is an example, and the present invention is not limited thereto.

The generated green last may be withdrawn from the settling tank and recycled for the most part. Greenlast is represented by Fe ²⁺ (OH) ₆ , but part of Fe ²⁺ is replaced by Fe ³⁺ and stabilized in the interconversion state of Fe ²⁺ ⇔ Fe ³⁺ . As shown in Example 3 later, in the stabilized state, Fe ²⁺ at 90% by mass to 98% by mass and Fe ³⁺ at 2% by mass to 10% by mass, but in the treatment of the water to be treated, it is in Greenlast. Fe ²⁺ may be 50% by mass to 70% by mass, and Fe ³⁺ may be 30% by mass to 50% by mass. When Green Last is recycled, the amount of Fe ³⁺ increases and the amount of precipitation increases. Treatment speed of treated water is increased. The industrially preferable total iron equivalent concentration of the Greenlast suspension can be, for example, 500 mg / L (500 ppm) to 200000 mg / L (200000 ppm). The [Fe ²⁺ / total iron] mass ratio of the Greenlast suspension is preferably 0.3-0.99, more preferably 0.5-0.7, and the [Fe ²⁺ / total iron] mass ratio is high, 0.98-0.99. Is.
It is easy to handle when using for the treatment method of to-be-processed water as it is this range, and it is preferable.
When the aqueous solution in which Greenlast is generated is adjusted to pH 10.5 to 12.0 or more using caustic soda, it changes to ferritic iron (triiron tetraoxide Fe ₃ O ₄ ) and becomes black rust, and the precipitation mass and sedimentation rate decrease to 1/10. Decrease. The black rust forms a film of iron material to protect the internal corrosion. In order to convert to ferritic iron when the redox potential is around minus (−300 mv) (the reaction is reduced to green last by the reaction of Fe ²⁺ ⇔Fe ³⁺ , it is gently stirred in a weak reduction ability of ORP, or explained later Ferrite iron is formed by adding a small amount of a chemical treatment agent, which is a reaction product of a dehydrogenase and a water-soluble organic substance, to oxidize the ORP to a brass (+) condition.

The inventor thinks that one of the stabilization conditions of Greenlast is pH. The difference of the Greenlast suspension of the present invention compared to the prior art Greenlast is that the Fe ²⁺ ⇔Fe ³⁺ cycle is interconverted at equilibrium, so stabilization is possible in the long term.
Water (or sample) enters inside the pores of the reduction catalyst body, and the potential difference between carbon, ferritic iron and reduction catalyst body makes the anode electrode (Fe) and cathode electrode (C) countless, and the microcell electrode is constructed. Do. In the reduction catalyst body, electron transfer (discharge and charge) is facilitated, and since the electrodes are extremely close, the cell becomes a dipole. Ferrite iron (triiron tetraoxide) contains Fe ²⁺ and Fe ³⁺ ions. In the electrolysis process by potential difference, oxygen (cathode reaction) constitutes an electron dielectric in which electrons move between divalent iron and trivalent iron. In the inside of the powder by electrolysis reaction, when there is ^much Fe ³⁺ , it polarizes to [+] and becomes a plane with many positive charges (thin electron surface), and when there is a lot of Fe ²⁺ , it polarizes to [-], It transforms into a dielectric in which a surface with many negative charges (a surface with a high concentration of electrons) is constructed. The equilibrium reaction of the interconversion of Fe ²⁺ ⇔ Fe ³⁺ continues the electrolytic reaction endlessly.
OH ions are accumulated in the electrolytic solution by the cathode reaction depending on the amount of oxygen supplied from the water to be treated, and the pH value fluctuates to alkali.
Stabilization of the Greenlast suspension of the present invention is considered to be the mechanism as described above, and this mechanism is suitable if pH conditions are maintained even if the reduction catalyst is removed from the Greenlast suspension. The same mechanism can be maintained.

In the formation of Greenlast, the reduction catalyst is electrolyzed in an acidic region, iron ions are dissolved in the electrolytic solution by the above action, an alkali agent is added, and pH is adjusted if necessary to produce Greenlast. Even when the greenlast suspension produced by the production method of the present invention is left unsealed for 4 to 5 days, the water surface is oxidized by air (oxygen) and iron oxide (reddish brown) appears, but it is green by shaking lightly Present. Electron transfer of Fe ²⁺ ⇔Fe ³⁺ is performed to stabilize the green last. Prior art Greenlast does not possess such buffering capacity.

※ Stable means that green rust and oxidized Fe ³⁺ iron oxide do not settle when left standing. As long as the pH is maintained at a predetermined value 4 to 6, the produced Greenlast suspension is stable for one year or more, and can be circulated as a suspension.

[4. Treatment method of treated water]
(4-1) Greenlast suspension produced by the production method of the present invention is metal-containing wastewater, acid, alkali and / or ammonia-containing wastewater, nitrogen, nitrogen compounds, silicon, silicon compounds and / or Contamination and removal of contaminants in these waste water by contact with waste water containing these ions, washing water for chimneys, water washing waste containing silicon dioxide (SiO ₂ ) used for solar power generation, etc. Can. The concentration of the Greenlast suspension used varies depending on the contamination conditions of the water to be treated, and is not limited, but it is 100mg / L (100ppm) to 200000mg / L (200000ppm), [Fe ²⁺ / total iron] mass in total iron equivalent concentration The ratio can preferably be used for waste water treatment in the range of 0.5-0.7.
FIG. 1 shows the preparation of the Greenlast suspension of the present invention and the subsequent treatment flow of treated water using the Greenlast suspension.
In the flow shown in FIG. 1, the reduction catalyst is fixed in the aqueous layer and stirred. The redox reaction proceeds, and ferrous ion is additionally added, for example, with ferrous sulfate on the way and further stirred. Thereafter, the pH is adjusted to obtain a green last suspension. The obtained green last can be extracted and used, or the material to be treated in the drainage may be treated as a green last suspension as it is without extraction and precipitated in a settling tank. A portion of the treated water is circulated and added to the pretreated treated water. The metal ferrite can be taken out of the precipitate generated in the precipitation tank and stored, for example, in a ferrite iron storage tank for use.

(4-2) Treatment Method of Treated Water Repetitively Using Active Precipitate The treatment method of the to-be-treated water of the present invention can repeatedly use the active precipitate using the following steps. Here, as to the order of the respective steps, any of the steps not particularly described may be performed first or simultaneously.
1) Step 1 of adding green last to the water to be treated which is raw water in the treatment tank and adjusting pH and stirring, preferably pH 9.5 to 11, more preferably pH 10.5 ± 0.5 .
2) a step 2 of separating the precipitate and the treated water from the treated water obtained in the step 1,
3) Step 3 of removing sludge from separated sediments
4) adding a part or all of the sludge from which the sludge has been removed to raw water to be treated, adding green last, adjusting the pH and stirring;
5) a step 5 of separating the precipitate and the water to be treated from the treated water obtained in the step 4;
6) Step 5 of obtaining the total amount of treated water and a deposit after repeating steps 3 and 4 one or more times after step 5; .
(4-3) When the water to be treated contains an organic matter, in particular, a silicon ion, a silicon compound, a silicon compound, a silicon oxide, a nitrogen compound, a nitrogen oxide, etc., prior to treatment with Greenlast of the present invention, An acidic oxidation treatment (Fenton treatment) is performed by adding a chemical treatment agent which is a reaction product of a dehydrogenase and a water-soluble organic substance described below to remove an oxyanion, and the green last suspension of the present invention is obtained. It is preferable to carry out the treatment using The chemical treatment agent used is described in patent 5194223. A green last suspension may be added as a catalyst together with the chemical treatment agent, or green last may be added to give a total iron equivalent concentration of 300 mg / L (300 ppm) to 30 000 mg / L (30000 ppm).

[Chemical processing agent which is a reaction product of a dehydrogenase and a water-soluble organic substance]
The chemical treatment agent which is a reaction product of a dehydrogenase and a water-soluble organic substance used in the following examples is described as a chemical treatment agent in Patent Specification No. 5194223, and specifically described as a chemical treatment agent Y It is done. An example of a chemical treatment of the present invention as Marokkusu SE III ^TM agent, sold by Corporation adolescents. The description of claim 1 of the specification is as follows, and the chemical treatment agent Y is described in Table 1 of paragraph [0168] of the specification. Chemical treatment agent Y used as Table 48 in Example 4 of the present specification is shown.
[Claim 1] 4000 parts by weight of water, 800 to 1600 parts by weight of sodium hexametaphosphate, 0.010 to 1.000 parts by weight of reduced glutathione, and 0.001 to 0.050 of 50 U / mg of glycerol dehydrogenase A mixture solution (A) is prepared by mixing a unit number of glycerol dehydrogenase corresponding to parts by mass and further incubating for 5 days or more, and 5200 parts by mass of prepared mixture (A) and 5000 U / g of yeast A mixed solution (B) was prepared by mixing a yeast lytic enzyme having the number of units corresponding to 10 to 300 parts by mass of the lytic enzyme and 500 to 1600 parts by mass of glycerol and further incubating for 3 days or more. B) 800 parts by mass, 1000 to 4000 parts by mass of sodium peroxodisulfate and 10 to 100 parts by mass of ethylenediaminetetraacetic acid Mix the corresponding number of moles of ethylenediaminetetraacetic acid and / or its water-soluble salt, and said sodium peroxodisulfate and said ethylenediaminetetraacetic acid and / or its water-soluble salt in an amount capable of dissolving water, and further incubate for 5 days or more Chemical processing agent obtained by preparing a mixture (C) and diluting the prepared mixture (C) as it is or with water.
EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to these examples.

Hereinafter, the abbreviations used in the present specification are the following abbreviations, and the measurement conditions are as follows.
The total iron equivalent concentration, silicon and Cr content (mg / L) in the Greenlast suspension were measured by ICP quantitative analysis. The ORP is a redox potential value (mv), and is measured by adjusting the pH of the liquid measured with Ag / AgCl electrode, herein, to pH 10.5 with sodium hydroxide. COD (mg / L): Chemical oxygen demand, the amount of oxidizable substance in sample water is oxidized by oxidizing agent under certain conditions, and the amount of oxygen necessary for oxidation is determined from the amount of oxidizing agent used at that time The unit is mg / L. The substances to be oxidized include various organic substances and inorganic substances such as nitrites and sulfides, but the main substances to be oxidized are organic substances. It is measured by the acidic high temperature permanganic acid method (COD _Mn ). TOC (mg / L) oxidizes organic carbon contained in sample water to carbon dioxide in the total organic carbon content. Then, the TOC is determined by measuring the amount of carbon dioxide. Measured by combustion oxidation method. DO represents dissolved oxygen and means the concentration of oxygen dissolved in water, which is expressed by how many mg of oxygen is contained in 1 L of water (mg / L), which is measured by the Winkler method. SV represents an activated sludge sedimentation rate, and unless otherwise stated, SV30 represents a volume ratio of settling from a suspension in 30 minutes. The sedimentation rate of the precipitate is represented by the volume ratio at which the solid content has settled from the suspension.

[1. Production of reduction catalyst body]
In the following Examples (1-1) to (1-3), a reduction catalyst was produced and used for production of a green last suspension. The components of the reduction catalyst body are shown in Tables 3 to 6. Me represents a metal, and% represents mass%.

[Example 1: Production of Green Last Suspension]
Example 1-1
Add 10 L of water to a water tank and mix and stir 1 kg of the components of K-1 shown in Table 3 (hereinafter referred to as a reduction catalyst) into a filter cloth inside a long cylindrical punching stainless and fix it in water Water is stirred, and the pH value is adjusted with dilute sulfuric acid to a range of 3.0 to 4.0 using an oxidation-reduction reaction (primary battery system), and after stirring for 40 hours, ferrous sulfate (FeSO ₄ · 7H ₂ ) Add 1200g of O). The ORP at the time of addition dropped below 400 mv. After further stirring for 40 hours, the pH value is adjusted to 10.5 using caustic soda, reduction test is conducted, and it is confirmed that ORP falls within the range of -700 to -800 mv, and stirring and pH adjustment are finished. The formation of green last was confirmed by light blue transparent color or light green transparent color. The Greenlast suspension in the tank was filtered through a filtration filter using a transfer pump and stored in any container.
The measured values of water while stirring the reduction catalyst body K-1 are shown in Table 7 below.

(Example 1-2)
The reduction catalyst body mixed and stirred was fixed and submerged in water and the water was stirred in the same manner as in Example 1-1 except that the reduction catalyst body used was K-2. The measured values of water while stirring the reduction catalyst body K-2 are shown in Table 8 below.

The pH value in the tank was controlled to pH 3.5 by controlling the addition of dilute sulfuric acid with a metering pump. Stirring was further continued, and the redox reaction was continued until the redox potential value became 400 mv or less in the reduction reaction.
A green last was produced in the same manner as in Example 1-1.
The measurement results of the oxidation-reduction potential of the reduction catalyst body K-2 in the production process are shown in Table 9.

ORP is -706 mv when the obtained green last is adjusted to pH 10.5 mv with NaOH, and the total iron equivalent concentration of the obtained green last suspension (iron amount obtained by converting all iron into metal iron, IPC measurement ) Was 36400 mg / L. The [Fe ²⁺ / total iron] mass ratio was 0.90-0.99.

(Example 1-3)
A reduction catalyst body (graphite 54%, ferrite iron 36%, aluminum ferrite) in which 900 g of reduction catalyst body and 100 g of aluminum ferrite obtained by the treatment of the aluminum-containing treated water of Example 2-1 described later are mixed 10%) was submerged in water to operate the stirrer. The pH value in the tank was controlled to pH 3.5 by controlling with a metering pump added with dilute sulfuric acid. Stirring was further continued, and the redox reaction was continued until the redox potential value became 400 mv or less in the reduction reaction. The sample in which the reaction was completed was collected to measure the total iron content, the sample was adjusted to pH 10.5, and the redox potential value (ORP) was measured.
A green rust suspension was obtained using an aluminum metal (M) ferrite-containing reduction catalyst body. The results are shown in Table 10.

(Example 1-4)
9 L of purified water is put in a water tank (reaction tank), a solution prepared by dissolving 50 g of sodium silicate in 1 L of purified water in advance is added and stirred, and the reduction catalyst K-3 is placed in the inner bag of the separation membrane cylindrical container. 1 kg was compounded and mixed. A green last suspension was obtained in the same manner as in Example 1-1 except that the reduction catalyst body K-3 was submerged in water and the stirring device was operated. The addition of 50 g of sodium silicate reduced the galvanic cell reaction time of the reduction catalyst.

[Example 2: Treatment method of treated water]
In the treatment method of the following to-be-processed water, the metal in a metal containing treatment water was removed using a green rust suspension, and the metal ferrite was obtained from the obtained deposit. Metal ferrite can be used as a raw material of the reduction catalyst of the present invention.
In the following description, Green Lust added is a notation in which Green Lust suspension (only the total iron amount equivalent excluding water in each mg is added to 1 L of treated water. For example, As shown in the following table, when the Greenlast suspension to be added (hereinafter, Greenlast is sometimes referred to as GR and Greenlast suspension may be referred to as GRD) is 36400 mg / L (36400 ppm) in terms of total iron equivalent concentration When adding the total iron equivalent amount in 500 mg of Greenlast suspension to 1 L of the water to be treated, the total iron equivalent concentration in the resulting treated water is 36400 × 0.5 = 18200 (mg / L).

(Example 2-1) Treatment of aluminum-containing treated water
Metallic aluminum (reagent) is added to 1000 mL of purified water at a concentration of 100 mg / L, stirring and mixing is performed for 30 minutes at 350 rpm with a magnetic stirrer, and the green rust suspension has a total iron equivalent concentration relative to 1 L of water to be treated The Greenlast suspension with a mass ratio of [Fe ²⁺ / total iron] of 0.5-0.7 is shown in Table 12 below (total iron equivalent to 750 mg equivalent to GRD or total equivalent to 1000 mg GRD) Add iron, adjust the pH to 11.0 ± 0.5 with caustic soda (NaOH), stir for 1 hour, separate by sedimentation, and measure the sedimentation ratio SV60 of the solid content in the sediment separated sediment every 1 hour thereafter It shows in Table 13. It was confirmed that aluminum was below the detection limit in the sedimentation separated water one hour after the addition of the Greenlast suspension, and it was possible to sufficiently remove aluminum harmful substances in the water to be treated at this Greenlast concentration.
Table 14 shows the pH of the water to be treated after 24 to 72 hours, ORP. It can be seen that precipitates containing aluminum are successfully formed at the pH values shown in Table 14. The sediment sample which left sediment for 24 to 72 hours as it is is adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progress, the result of having measured the existence of re-elution of aluminum is shown in Table 15. No re-elution of aluminum was detected, indicating that the aluminum in the treated water was removed by the green last suspension.

  In addition, the particle size distribution of the aluminum ferrite obtained in the case of the green last density | concentration 27300 (mg / l) in the process liquid after addition is shown in Table 16. The particle diameter range was 0.02 to 200000 μm, the dispersion medium name was water, the dispersion medium refractive index was 1.330, and the particle refractive index was 2860. The obtained aluminum ferrite could be used for the reduction catalyst of the present invention.

(Example 2-2) Treatment of Yttrium-Containing Water to be Treated Metal yttrium (reagent) is added to 1000 mL of purified water at a concentration of 100 mg / L to give water to be treated. The amount of the suspension solution is 36,500 mg / L in terms of total iron concentration, and the amount of Greenlast suspension in which the mass ratio of [Fe ²⁺ / total iron] is 0.5 to 0.7 is shown in Table 17 below. The yttrium-containing treated water is treated in the same manner as in Example 2-1 except that it is added, the pH is adjusted to 11.0 ± 0.5 with caustic soda (NaOH), stirring is performed for 1 hour, and sedimentation is performed, and then every 1 hour Sedimentation ratio SV60 of solid content in the sediment separated precipitate is measured and is shown in Table 18. It was confirmed that yttrium was below the detection limit in the precipitated separated water one hour after the addition of the Greenlast suspension, and that yttrium harmful substances in the water to be treated could be sufficiently removed.
Table 19 shows the pH of the water to be treated after 24 to 72 hours, ORP. The pH of the water to be treated and ORP are as shown in Table 19, and it can be seen that a precipitate is formed successfully. The sediment sample which left sediment for 24 to 72 hours as it is is adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progress, the result of having measured the existence of re-elution of yttrium is shown in Table 20. No re-elution of yttrium was detected, and it was found that yttrium in the treated water was precipitated and removed by the Greenlast suspension.

  In addition, the particle size distribution of the yttrium ferrite obtained in the case of the green last density | concentration of 54750 mg / L in the process liquid after addition is shown in Table 21. It was measured under the conditions of a particle diameter range of 0.02 to 200000 μm, a dispersion medium name of water, a dispersion medium refractive index of 1.330, and a particle refractive index of 2860. The obtained yttrium ferrite can be used for the reduction catalyst of the present invention.

(Example 2-3) Treatment of tin-containing treated water Metallic tin (reagent) is added to 1000 ml of purified water at a concentration of 100 mg / l to form treated water, and 1 L of treated water is treated with green last Suspended liquid is 34,600 mg / L in terms of total iron concentration, green rust suspension with [Fe ²⁺ / total iron] mass ratio 0.5-0.7 in the amount shown in Table 22 below (equivalent to GRD 1000 mg equivalent total iron Treat the tin-containing treated water in the same manner as in Example 2-1 except that 1500 mg of total iron equivalent was added, adjust the pH to 11.0 ± 0.5 with caustic soda (NaOH), and stir for 1 hour The sedimentation rate of the solid in the separated sediment is measured every hour, and the results are shown in Table 23. It was confirmed that tin was less than the detection limit in the sedimentation separated water one hour after the addition of the Greenlast suspension, and that tin harmful substances could be sufficiently removed from the treated water.
Table 24 shows the pH and ORP value of treated water after 24 to 72 hours. The pH of the water to be treated and ORP are as shown in Table 24, and it can be seen that a precipitate is formed successfully. The sediment sample which left sediment for 24 to 72 hours as it is is adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progress, the result of having measured the existence of re-elution of tin is shown in Table 25. Re-elution of tin was not detected, and it was found that tin in the treated water was removed by the green last suspension.

  The particle size distribution of tin ferrite obtained in the case of the concentration of 34,600 mg / L in terms of Green Last total iron in the treatment liquid after addition is shown in Table 26. It was measured under the conditions of a particle diameter range of 0.02 to 200000 μm, a dispersion medium name of water, a dispersion medium refractive index of 1.330, and a particle refractive index of 2860. The obtained tin ferrite can be used for the reduction catalyst of the present invention.

(Example 2-4) Treatment of Chromium-Containing Treated Water Metallic chromium (reagent) is added to 1000 mL of purified water to a concentration of 100 mg / L to form treated water, and 1 L of treated water is treated with Green Last. The amount of the suspension solution is 34,600 mg / L in terms of total iron concentration, and the amount of Greenlast suspension with [Fe ²⁺ / total iron] mass ratio 0.5 to 0.7 is shown in Table 27 below (equivalent to GRD 250 mg equivalent total iron Treat the chromium-containing water in the same manner as in Example 2-1 except that 300 mg of total iron equivalent was added, adjust the pH to 11.0 ± 0.5 with caustic soda (NaOH), and stir for 1 hour The sedimentation rate of the solid in the separated precipitate is measured every hour, and the results are shown in Table 28. It was confirmed that tin was less than the detection limit in the sedimentation separated water one hour after the addition of the Greenlast suspension, and it was possible to sufficiently remove the chromium harmful substance in the treated water.
Table 29 shows pH of the treated water after 24 to 72 hours, ORP. The pH of the water to be treated and ORP are as shown in Table 29, and it can be seen that a precipitate is formed successfully. The sediment sample which left sediment for 24 to 72 hours as it is is adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progress, the result of having measured the existence of re-elution of chromium is shown in Table 30. No re-elution of chromium was detected, indicating that the chromium in the treated water was removed by the green last suspension.

  In addition, the particle size distribution of the chromium ferrite obtained in the case of green rust total iron conversion density | concentration 9100 mg / L in the process liquid after addition is shown in Table 31. It was measured under the conditions of a particle diameter range of 0.02 to 200000 μm, a dispersion medium name of water, a dispersion medium refractive index of 1.330, and a particle refractive index of 2860. The obtained chromium ferrite can be used for the reduction catalyst of the present invention.

(Example 2-5) Treatment of Zinc-Containing Water to be Treated Metal zinc (reagent) is added to 1000 mL of purified water to a concentration of 100 mg / L to form water to be treated. Suspended liquid is 36400 mg / L in terms of total iron concentration, and the amount of [Fe ²⁺ / total iron] mass ratio is 0.5 to 0.7 in the amount shown in Table 32 below (total iron equivalent of GRD 800 mg equivalent Treat the chromium-containing water in the same manner as in Example 2-1 except that 1000 mg equivalent (total iron equivalent) was added, adjust the pH to 11.0 ± 0.5 with caustic soda (NaOH), and stir for 1 hour Conduct sedimentation and separation, and then measure the sedimentation rate SV60 of the solid content in the sediment separated sediment every hour, and the results are shown in Table 33. It was confirmed that zinc was less than the detection limit in the precipitated separated water one hour after the addition of the Greenlast suspension, and zinc harmful substances in the treated water could be sufficiently removed.
Table 34 shows pH of the treated water after 24 to 72 hours, ORP. The pH of the water to be treated and ORP are as shown in Table 34, and it can be seen that a precipitate is formed successfully. The sediment sample which left sediment for 24 to 72 hours as it was was adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progressed, the result of having measured the existence of re-elution of zinc is shown in Table 35. No zinc re-elution was detected, indicating that the zinc in the treated water was removed by the green last suspension.

  In addition, the particle size distribution of the zinc ferrite obtained in the case of the density | concentration 29120 mg / L of green last total iron in the process liquid after addition is shown in Table 36. It was measured under the conditions of a particle diameter range of 0.02 to 200000 μm, a dispersion medium name of water, a dispersion medium refractive index of 1.330, and a particle refractive index of 2860. The obtained zinc ferrite can be used for the reduction catalyst of the present invention.

Example 2-6 Treatment of Copper-Containing Treated Water Metal copper (reagent) is added to 1000 mL of purified water to a concentration of 100 mg / L to form treated water, and 1 liter of treated water: The Greenlast suspension had a total iron equivalent concentration of 36500 mg / L, and a mass ratio of [Fe ²⁺ / total iron] of 0.5 to 0.7 in the amount shown in Table 37 below (equivalent to 1000 mg of GRD The copper-containing treated water is treated in the same manner as in Example 2-1 except that iron equivalent or 1250 mg equivalent total iron equivalent) is added, and the pH is adjusted to 11.0 ± 0.5 with caustic soda (NaOH). The mixture is stirred for 1 hour, sedimentation is performed, and then the sedimentation ratio SV60 of the solid content in the sediment is measured every hour, and the results are shown in Table 38. It was confirmed that copper was below the detection limit in the sedimentation separated water one hour after the addition of the Greenlast suspension, and the concentration of this Greenlast could sufficiently remove copper harmful substances in the water to be treated.
Table 39 shows the pH of the water to be treated after 24 to 72 hours, ORP. The pH and ORP value of the water to be treated are as shown in Table 39, and it can be seen that a precipitate was formed successfully. The sediment sample which left sediment for 24 to 72 hours as it was was adjusted to pH 1.5 with hydrochloric acid, and after 48 to 72 hours progressed, the result of having measured the existence of re-elution of copper is shown in Table 40. It was found that copper re-elution was not detected, and copper in the treated water was removed by the green last suspension.

  In addition, the particle size distribution of the copper ferrite obtained in the case of the density | concentration 36750 mg / L of green last total iron in the process liquid after addition is shown in Table 41. It was measured under the conditions of a particle diameter range of 0.02 to 200000 μm, a dispersion medium name of water, a dispersion medium refractive index of 1.330, and a particle refractive index of 2860. The obtained copper ferrite can be used for the reduction catalyst of the present invention.

[Example 3: Evaluation of stability of green last]
(Example 3-1) Evaluation of stability of green last 10000 ml of a green last suspension produced by the method described in example 1-4 is put in a beaker, tracking of change in iron content (divalent + trivalent), liquid The changes over time at room temperature such as gender and appearance were followed. The results are listed in Table 34. The measurement was carried out at room temperature, and the reduced ORP in the table is a value obtained by measuring the redox potential in the state where the pH value of the sample was adjusted to 10.5 with sodium hydroxide. The white at the bottom disappeared with the action of the pipette. We are tracking how many days white sedimentation can be confirmed.

(Example 3-2) Stability evaluation of Greenlast The greenlast suspension produced in Example 1-3 is adjusted to pH 5.4 with caustic soda, and tracking of the iron content (divalent / trivalent) change, The change in liquid temperature, room temperature, etc. was followed. The results are set forth in Table 35. The measurement was performed at room temperature, and the reduced ORP in the table is the value obtained by measuring the oxidation-reduction potential in the state where the pH value of the sample was adjusted to 10.5 with sodium hydroxide. The settling of Greenlast begins in 90 days, and solid-liquid separation starts, and after 210 days, a stirrer may be necessary to maintain stability. The sediment is Greenlast suspension and the composition is unconfirmed.

[Example 4: Sedimentation separation of silicon dioxide (removal of oxyanion)]
A water washing and drainage sample containing silicon dioxide (SiO ₂ ) used for solar power generation and the like in a 2000 ml beaker was used as the water to be treated. An acidic oxidation treatment (Fenton) was performed using the chemical treatment agent Y prepared in Example 1 of Patent No. 5194223 and a green last suspension as a catalyst.
The water quality of the treated water sample used is shown in Table 44.

(experimental method)
<Fenton (acidic oxidation) treatment>
The mixture is stirred at 350 rpm with a magnetic stirrer, adjusted to pH 4.0 with dilute sulfuric acid (24%), and has a total iron equivalent concentration of 32000 mg / L, and a [Fe ²⁺ / total iron] mass ratio of 0.5 to 0.7 green Last pump was added 5000 mg equivalent total iron equivalent, and the value indicated by the oxidation-reduction potentiometer (ORP) in the solution was controlled ON / OFF to control the metering pump of chemical treatment agent Y so that the ORP + 500 mv was maintained. Was added. The dilute sulfuric acid metering pump was controlled on / off so that the value indicated by the pH meter maintained pH 4.0. About 4200 mg of a 10% concentration product, which is a mixture liquid (C) of Table 48 described below, was diluted to 10% by mass, and was added with the ORP value on / off control. About 67 mg of dilute sulfuric acid (24% concentration product) was added under on / off control by pH value.

<Settling treatment using Greenlast suspension>
After that, a total iron equivalent of 36400 mg / L total iron equivalent concentration manufactured in another place and having a [Fe ²⁺ / total iron] mass ratio 0.5-0.7 equivalent to a total iron equivalent of caustic soda is added. The pH was adjusted with (48%) to set the pH to 10.5 and precipitation separation was performed, and the precipitate was subjected to an experiment for the purpose of obtaining and utilizing silicon ferrite iron (magnetic ferrite iron) by ferritizing it.

(Experimental course)
The experimental course is shown in Table 47.

The compounding quantity of each component at the time of manufacture of the chemical processing agent Y used is shown in the following Table 48.

The water to be treated shown in Table 44 contains organic matter, and the oxygen of silicon dioxide separates from the start of the acidic oxidation treatment, but the amount of dissolved oxygen increases, but when the settling separation starts after 8 hours, the amount of dissolved oxygen decreases and silicon precipitates It can be understood in the experimental course shown in Table 47 that it is removed.
(Ferrite treatment of sediments)
After leaving the treatment solution obtained in the above experiment for 12 hours in a static state, 80% of the bottom of the deposit was black, its surface was reddish brown, and the rest was separated with water. When a neodymium magnet (surface magnetic flux density (T) 0.42, adsorption force (N) 25.48 diameter 10 mm) was put in water of the sample, all precipitates were adsorbed. The precipitate was ferriteified and could be separated magnetically and separated by filtration. The silicon content was measured by ICP quantitative analysis as metallic silicon (Si).

[Example 5: Method for producing silicon ferrite with Greenlast suspension by oxyanion decomposition of silicon dioxide (reagent) under reducing conditions]
(Samples and reagents used)
5 g of silicon dioxide (SiO ₂ ) reagent, green rust suspension (total iron concentration 32000 mg / l, pH 10.5 measured ORP, -720 mv) caustic soda (48%) 2.8 ml (green rust suspension pH preparation 4.0 → Used in 10.5)

(experimental method)
In a 500 ml beaker, 500 ml of the Greenlast suspension was added and stirred, caustic soda was added to adjust the pH value to 10.5, and 5 g of silicon dioxide (powder) was weighed and added slowly and directly to the beaker. The experimental course is shown in Table 50.

According to the results in Table 50, since the treated water contains the reagent silicon and does not contain the organic matter, the Greenlast suspension separates the oxygen of silicon dioxide and the amount of dissolved oxygen rises, but sedimentation starts after 12 hours and contains silicon It has been shown that the amount of dissolved oxygen in the supernatant decreased and the amount of silicon in the supernatant separated water decreased to less than 0.01 mg / L due to the precipitation of the Greenlast precipitate.
By the release of the silicon dioxide oxyanion, it can be seen that the oxidation of Greenlast proceeds and the ferrite formation proceeds.

When a neodymium magnet (surface magnetic flux density (T) 0.42, adsorption force (N) 25.48 diameter 10 mm) was added to the sediment, all the sediment was adsorbed. The silicon content (Si) was measured by ICP quantitative analysis.
Sedimentary precipitate can be ferriteified, separated magnetically, separated by filtration, can be easily manufactured as silicon ferrite iron (magnetic iron powder), can improve the technology of forming an insulating film in micromicron units, and can save energy of reactors, motors, etc. Contributes to the reduction in size and weight.

[Example 6: Use of silicon ferrite in green last production]
An experiment was conducted using silicon ferrite for the purpose of obtaining a positive value, a negative difference, and a redox potential of Greenlast on the cathode (minus) side.

Example 6-1 Production of Greenlast Using Sodium Silicate (Oxidation-Reduction Reaction)
9 L of purified water is put in a water tank (reaction tank), and a solution prepared by dissolving 50 g of sodium silicate (Na ₂ SiO ₃ ) in 1 L of purified water is put into a reaction tank (10 L) and stirred. A stirring device was operated by submerging 500 g of graphite and 400 g of ferritic iron (Fe ₃ O ₄ ), which are reduction catalyst bodies mixed and mixed in the inner bag of the container, in water. The value of the in-tank pH meter was controlled by a dilute sulfuric acid metering pump to maintain the pH at 3.5 or less, and a redox reaction (redox) was performed for 12 hours.
The measured values of water while stirring the reduced catalyst body and sodium silicate are shown in Table 51 below.

The metal corrosion reaction solution obtained above is distributed to three 2000 mL containers, and the reduction catalyst, 100 g of graphite and 80 g of ferritic iron are put into the inner bag of the separation membrane cylindrical container and charged into each of three containers. The water in the vessel was stirred with a magnetic stirrer to continue the reduction reaction. After 12 hours, a predetermined amount (240 g, 480 g and 720 g) of ferrous sulfate (FeSO ₄ · 7 H ₂ O) was added, and the reaction was continued until the ORP showed 400 mv or less to form Greenlast, light blue transparent It confirmed by the color or light green transparent color. The reaction-completed suspension was collected to measure the total iron content, the reaction solution was adjusted to pH 10.5, and the redox potential value (ORP) was measured.

  From the results in Table 52, it can be seen that the ORP becomes less than about 400 mv after 2 hours. The total iron equivalent concentration and ORP of the green last suspension obtained by collecting a sample of the reaction solution of each container are measured and shown in Table 53.

(Example 6-2) Precipitation of silicon ferrite using sodium siliconate For the purpose of ferrite iron formation, caustic soda was added to each sample to adjust the pH value to 10.5, agitation was stopped, and sedimentation was performed. Table 54 shows the results of the sedimentation rate according to the amount of ferrous sulfate added to each reaction vessel. The silicon content in the upper separated liquid was measured by ICP quantitative analysis. It can be seen that silicon is incorporated into the precipitate and removed from the upper separation liquid.

A neodymium magnet (surface magnetic flux density (T) 0.42, adsorption force (N) 25.48 diameter 10 mm) was used to remove the ferrite from the precipitate in the solution. The precipitates were all adsorbed in ferrous sulfate (FeSO ₄ · 7H ₂ O) input (240 g, 480 g and 720 g) containers respectively. The magnetically adsorbed precipitate was dried at room temperature and subjected to ferrite particle distribution analysis.
Particle size distribution of the obtained Greenlast (sodium silicate containing) magnetically adsorbed magnetic iron powder, particle size range 0.02 to 200000 μm, dispersion medium name water, dispersion medium refractive index 1.330, particle refractive index 2860, ultrasonic intensity 50% It measured on condition of. The particle size distribution of the obtained silicon ferrite is shown in Table 55.

Example 6-3 Production of Green Last Using Silicon Ferrite (Redox Reaction)
Add 10 L of purified water to a water tank (reaction tank) and stir, and execute 500 g of graphite and 400 g of ferrite iron (Fe ₃ O ₄ ) mixed and mixed in the inner bag of a separation membrane cylinder container (hereinafter referred to as reduction catalyst). Submersion 50 g of silicon ferrite (Si-Fe ₃ O ₄ ) produced by the method of Example 6-1 in water and using it as a reduction catalyst body to operate a stirring apparatus, the value of pH meter in the tank is diluted sulfuric acid A redox pump (redox) was performed for 12 hours while maintaining the pH at 3.5 or less by controlling with a metering pump. Charge ferrous sulfate (FeSO4 · 7H2O) (240 g 480 g 720 g) respectively and continue until the ORP value shows 400 mv or less. The sample in which the reaction was completed was collected to measure the total iron content, and the sample was adjusted to pH 10.5 to measure the redox potential value (ORP).
The measured values of water while stirring the reduced catalyst body and silicon ferrite are shown in the following table.
The measurement results of Example 6-1 shown in Table 51 are shown side by side for comparison. From the experimental results, when silicon ferrite was used due to the difference in the acidity of the pH value of ferritic iron, the iron content of the obtained Greenlast was high, and the silicon content was significantly low. Also, from the ORP of the reduction test results, the production solution of Greenlast using silicon ferrite has a larger polarity plus / minus difference than the production of Greenlast using sodium silicate, and the redox potential value is negative (minus) side Deep value was obtained. The formation reaction of Greenlast when using silicon ferrite is 1.5 to 7 hours, which is very fast, and in a 1000 kg tank, the reaction is performed for 2 hours for 2 hours and the pH is adjusted to 10.5 with caustic soda (-700 mv) It was obtained. The reaction time varies depending on the scale of the reaction vessel, the amount of silicon ferrite used, and other components of the reduction catalyst.
In Table 56, the result of Example 6-1 using 50 g of sodium silicate and the result of comparing the Greenlast suspension (acidic) produced when 50 g of silicon ferrite is used as a reduction catalyst body are shown.

The description of the amount of acid elution in the figure means that the silicon content and the total iron content were measured in the state where the silicon ferrite sample precipitate (pH 10.5) was adjusted to pH 2.0 with hydrochloric acid. Thereafter, the following re-elution test was performed after standing for 24 hours.

  The silicon ferrite sample precipitate (pH 10.5) obtained in the experiment using the silicon ferrite of Table 56 was left for 24 hours in a state where the pH was adjusted to 2.0 with hydrochloric acid, and the re-elution test was performed by ICP quantitative analysis. As a result, it was 0.01 mg / L or less of silicon. It was confirmed that almost no silicon was eluted from the silicon ferrite.

The obtained metal corrosion reaction solution is distributed to three 2000 mL containers, and predetermined amounts (240 g, 480 g and 720 g) of ferrous sulfate (FeSO ₄ · 7 H ₂ O) are added, respectively, and the ORP is 400 mv or less The reaction was continued until indicated.

  The formation of green last was confirmed by light blue transparent color or light green transparent color. Although Table 12 shows the elapse of 12 hours, the generation of Greenlast is completed after 3 hours. The reaction-completed suspension was collected to measure the total iron content, and the redox potential value (ORP) of the reaction solution at pH 10.5 was measured and is shown in Table 58.

  From the experimental results, the total iron content of the green rust suspension in which silicon ferrite was mixed with the reduction catalyst was obtained in the same manner as the method using sodium silicate. On the other hand, in the reduction test results, the plus / minus difference in polarity was large, and the oxidation reduction potential value showed a deep value on the negative (minus) side. The following repeated treatment experiments (Examples 7-9) were conducted using the Greenlast suspension obtained using silicon ferrite.

(Example 7) Treatment of hexavalent chromium-containing wastewater with a greenlast suspension having a total iron concentration of 35400 mg / L manufactured using silicon ferrite (Example 7-1) (first treatment of subsequent repetitive treatment) Applicable to)
Treatment water collected from the chromium cleaning wastewater line of the plating plant was treated, Raw water → Green Last suspension addition stirring → pH adjustment → sedimentation separation.
The processing conditions were: batch processing volume: 2.0 L; pH adjustment was performed with on / off control using the indicated value of the pH electrode attached to the beaker and the constant volume injection pump of caustic soda. The preparation used is a pH adjustment caustic soda reagent (48%), a total iron concentration of 35400 mg / L, and a green rust suspension with a mass ratio of [Fe ²⁺ / total iron] of 0.5-0.7. As described in Table 59, total iron equivalent in 500 mg of GRD or 750 mg of GRD was added to 1 L of water to be treated. The treated water was treated with a stirring time of 15 minutes and a settling time of 25 minutes (calculated from the residence time in the factory).
The measurement results of water quality after treatment based on the conditions of the raw water and the concentration of the added Greenlast suspension are shown in Table 59.

The relationship between the added concentration of GRD and the total iron equivalent concentration in the resulting treated water is shown in Table 60. The amount of hexavalent chromium was measured by ICP mass spectrometry (JIS K 0102 65.2.5).

The pH of the sediment of the treated water, ORP, was measured under the same measurement conditions. The results are shown in Table 61. It can be seen that the treated water shown in Table 59 and the sediment shown in Table 61 have similar measured values as ORP values. The results in Tables 59 and 61 show that the reducibility (electric shade system) is maintained.

Repeated treatment of hexavalent chromium containing waste water with Greenlast suspension manufactured using silicon ferrite (following from Example 7-1, repeated treatment from Example 7)
(Example 7-2-1) Greenlast suspension (addition amount of total iron equivalent in 500 mg of GRD was added to 1 L of treated water) was used repeatedly for active sediment.
The precipitate obtained in Example 7 (step 1: the first treatment described below) is separated from the sludge (steps 2 and 3 below) using a filtration and suction device (filter paper 5C), and separated The substance was put into raw water to be treated (step 4: the second treatment was completed) and coagulation separation was performed. This repetition was repeated for the third time, the fourth time, the fifth time, and the sixth time. Water quality was measured after sedimentation. The results are shown in Table 62. Raw water and the first (Example 7) treatment results are also described for comparison. There is chromium elution after repeated use 6 times. In the fifth round, about 40% of the black sediment and the sixth round, the brown part occupied 50%. The repeated use of 500 mg of GRD was limited to 5 times.
The repeated process repeats the following steps. 1) Add 500 ppm of GRP, the same as in Example 7-1, to the water to be treated in the treatment tank (the concentration after the addition of Example 7-2-1 is 17700 mg / L), adjust the pH and stir Steps 1, 2) Steps 2 and 3) separating sludge and treated water from the treated water obtained in Step 1 Step 3 and 4) removing sludge from the separated sludge Step (5) adding a part or all of the raw water to be treated (all in this case), adjusting the pH and stirring (4, 5) and separating the precipitate from the treated water obtained in step 4 6) treatment of the water to be treated using the active sediment repeatedly comprising the step 5 of obtaining the total amount of the treated water and the sediment after repeating the steps 3, 4 one or more times after the step 5 It is a method.

(Example 7-2-2) Repeated sewage treatment method of Greenlast suspension (total iron equivalent in 750 mg of GRD is added to 1 L of treated water) The same conditions as in Example 7-1-1. However, the green rust suspension added the amount of total iron equivalent in 750 mg of GRD with respect to 1 L of to-be-processed water, and repeated eight times. The other conditions are the same as in Example 8-2. The results are shown in Table 63. There is chromium elution after repeated use 8 times. In the seventh round, about 30% of the black deposit and the eighth brown part occupied 35%. The repeated use of 750 mg of GRD was limited to 7 times.

(Example 8) Treatment of waste water containing hexavalent chromium with a green rust suspension having a total iron concentration of 64,500 mg / L manufactured using silicon ferrite and subsequent treatment method of water to be treated using the active sediment repeatedly Total iron concentration A suspension of 64,500 mg / L of Greenlast was added under the conditions of (Example 8-2-1) and (Example 8-2-2) to use the active sediment repeatedly.
The waste water treatment was performed in the same manner as in Example 7 except that a green rust suspension (total rust concentration of 64,500 mg / L) was used.
(Example 8-2-1) Repeated sewage treatment of Greenlast suspension (total iron equivalent in 500 mg of GRD added to 1 L of treated water) with total iron concentration of 64,500 mg / L As in Example 7, However, 1 L of water to be treated described in Table 14 using Greenlast suspension (hereinafter referred to as GRD) having a total iron concentration of 64,500 mg / L and a mass ratio of [Fe ²⁺ / total iron] of 0.5 to 0.7. On the other hand, the total iron equivalent in 500 mg of GRD was added, and the treated water was treated in the same manner as in Example 7 without changing the other conditions.
The concentration of the Greenlast suspension and the results of the 9-times repeated treatment are shown in Table 64.
As the results are shown in Table 64, chromium eluted with repeated use 9 times. In the ninth round, about 25% of the black sediment and the eighth brown part occupied 20%. The repeated use of 500 mg of GRD was limited to eight times.

(Example 8-2-2) Repeated sewage treatment method of Greenlast suspension (total iron equivalent in 750 mg of GRD added to 1 L of treated water) with total iron concentration of 64500 mg / L Example 7-1- Under the same conditions as 1 except that a greenlast suspension with a total iron concentration of 64500 mg / L was added to 1 L of water to be treated, the total iron equivalent amount in 750 mg of GRD was added, and the repetition was performed 11 times. The other conditions are the same as in Example 8-1-1. The results are shown in Table 65. As the results are shown in Table 65, chromium eluted with repeated use 11 times. At the 10th time, about 30% of the black deposit and the 10th brown area occupied 20%. Repeated use of 750 mg of GRD was limited to 10 times.

Example 9 Treatment of hexavalent chromium-containing wastewater with a green rust suspension with a total iron concentration of 96900 mg / L produced using silicon ferrite and subsequent cyclic treatment A green last suspension with a total iron concentration of 96,900 mg / L It added on the conditions of (Example 9-2-1) and (Example 9-2-2), and performed the repetition drainage process, respectively.
(Example 9-2-1)
In the same manner as in Example 7, except that a green rust suspension (hereinafter referred to as GRD) having a total iron concentration of 96,900 mg / L and a [Fe ²⁺ / total iron] mass ratio of 0.5 to 0.7 is used. The total iron equivalent in 500 mg of GRD was added to 1 L of the water to be described, and the water to be treated was treated in the same manner as in Example 7 without changing the other conditions.
The concentration of the Greenlast suspension and the results of the 11-times repeated treatment are shown in Table 66. As a result, a total iron concentration of 64500 mg / L green rust suspension (Example 8-2-2) was added, and the total iron equivalent amount in 750 mg of GRD was added to 1 L of water to be treated, and the number of repetitions was 11 The results were almost the same as in the case where it was repeated. The number of times that the GR suspension can be repeatedly used is not dependent on the concentration of the GR suspension to be added, but the higher the total iron equivalent concentration in the treated water after addition, the more it can be used more I understood. There is chromium elution after repeated use 10 times. At the 10th time, about 30% of the black deposit and the 10th brown area occupied 20%. The repeated use of 500 mg of GRD was limited to 10 times.

(Example 9-2-2)
In the same manner as in Example 7, except that a green rust suspension (hereinafter referred to as GRD) having a total iron concentration of 96,900 mg / L and a mass ratio of [Fe ²⁺ / total iron] of 0.5 to 0.7 is used. The total iron equivalent amount in 7500 mg of GRD was added to 1 L of the water to be treated described, and the water to be treated was treated in the same manner as in Example 7 without changing the other conditions.
The concentration of Greenlast suspension and the results of 9 treatments repeated 13 times are shown in Table 67. There is chromium elution after repeated use 13 times. In the 12th round, about 25% of the black deposit and the 11th brown part occupied 25%. The repeated use of 750 mg of GRD was limited to 12 times.

<Summary of Examples 7 to 9>
The results of repeated treatments of Examples 7-9 using a 2 L reactor are shown in Table 68. Further, the relationship between the Cr ⁶⁺ removal treatment amount (removal of 19.4 mg / L in one treatment) and the total iron equivalent concentration after the addition of the used Greenlast suspension is shown in Table 69 below. From the results of the treatment experiments of the chromium-containing waste water of Examples 7 to 9, it was shown that the higher the total iron equivalent concentration, the higher the total iron equivalent concentration, the higher the removal efficiency of contained metals, and the higher the COD removal efficiency. .

The effect of deepening the oxidation reduction potential value of the water to be treated to the negative (minus) side was confirmed by using silicon ferrite at the production of Greenlast.
By making silicon into a ferrite body, outflow was avoided and repeated use became possible. Although the number of times of repeated use depends on the total iron content of the Greenlast suspension, repeated use was possible 5 to 12 times.
If silicon is present in the reduction catalyst body, the processing speed of the obtained greenlast is increased to obtain excellent greenlast, but if silicon is contained as a ferrite body in the reduction catalyst body, further, the precipitate obtained from the water to be treated is It can be processed repeatedly. There is no re-elution of Cr when used repeatedly, and when used repeatedly, Cr in the water to be treated can be repeatedly removed, so the waste water treatment capacity is excellent.
During the production of Greenlast, the oxidation reduction potential value in the solution was improved and the reaction time was shortened to 1/2 or less.
A deep (ORP, -700 to -900 mv) value could be achieved on the negative (minus) side of the redox potential value of the treatment liquid using the Greenlast suspension.

  Water to be treated can be purified using the green last suspension obtained by the production method of the present invention. Even without using a large-scale apparatus or a continuous treatment method requiring complicated control, Greenlast can be stabilized over a long period of time, and its aggregation and precipitation action can be used to remove contaminants in the water to be treated.

2, sodium hypochlorite. 3, sulfuric acid. 5, Ma Rocks hydro balls ^TM (of the sintered body). 6, caustic soda. 7, green last. 8. Settling sludge. 9, precipitate containing ferrite. 10, treated water. 11, mixing tank. 12, alkaline reduction tank. 13, pump pit tank. 14. Coagulation tank. 15. Sedimentation tank. 16, sludge storage tank. 17, final neutralization tank. 18, discharge tank. 19, Effluent water. 20, transfer line. 21, ammonia decomposition tank. 22, oxygen reduction tank. 51, tin and zinc containing wastewater treatment line. 52. Ammonia and zinc containing wastewater treatment line. 53, chromium containing wastewater treatment line.
54, acid and alkali containing wastewater treatment line. 100a, 100b septic tank.
200, mesh material (holding member). 300, 300a, 300b Water purification material supply line. 700 wash water supply line. 900a, 900b Excitation coils (holding member magnetizing means). 1200, 1200a, 1200b Water supply line (water supply line with heavy metals). 1500 pH controller (pH control means). 1600, 1600a, 1600b Treated water discharge line. 1900, 1900a, 1900b Water purification material discharge line.
2100a, 2100b Vibrator (vibration application means).

Claims (14)

  Oxidation is carried out by stirring with water an acid containing 70 to 40 parts by mass of graphite and a reduction catalyst body containing 20 to 50 parts by mass of at least one selected from the group consisting of iron and ferrite iron as a pH 2 to 4 range The reduction reaction is carried out, 15 to 300 parts by mass of ferrous ion and / or ferrous compound is added, and the pH is adjusted to the alkaline side, and the reduction test is conducted to find that the oxidation reduction potential value is -400 mv to -950 mv The manufacturing method of green last which obtains that it becomes in the range of, and complete | finishes stirring and pH adjustment, and obtains green last produced | generated in the said water.   At least one additive metal selected from the group consisting of aluminum, yttrium, zinc, copper, tin, chromium and silicon is further contained in the reduction catalyst body in an amount of 2 to 10 parts by mass as metal and / or metal ferrite. The manufacturing method of the green last as described in 1.   The reduction catalyst body has 70 to 40 parts by mass of graphite, 20 to 50 parts by mass of at least one selected from the group consisting of iron and ferritic iron, and 2 to 10 parts by mass of silicon ferrite. The method of producing Green Last described in.   The method for producing Greenlast according to any one of claims 1 to 3, wherein the reduction catalyst is a powder and / or a lump.   A method for treating treated water, wherein the treated water is brought into contact with the green last suspension obtained by the method according to any one of claims 1 to 4.   The method for treating water to be treated according to claim 5, wherein the water to be treated contains a metal as a contaminant.   The metal in the treated water is at least one contaminant selected from the group consisting of zinc, chromium, iron, copper, tin, nickel, aluminum, silicon, ions thereof and compounds thereof. How to treat the water of treatment. Process 1 of adding green last to the water to be treated which is raw water in the treatment tank, adjusting pH and stirring;
Step 2 of separating the precipitate and the treated water from the treated water obtained in the step 1;
Step 3 of removing sludge from separated sediment
Adding a part or all of the sludge from which the sludge has been removed to raw water, which is raw water, adding Greenlast, adjusting pH and stirring 4;
Step 5 of separating the precipitate and the treated water from the treated water obtained in the step 4 and the steps 3 and 4 next to the step 5 are repeated one or more times, and then the total amount of treated water and the precipitate are separated. 6. A method for treating treated water, wherein the deposit is recycled, having step 6).   The method for treating treated water according to claim 8, wherein the green last is the green last obtained by the method according to any one of claims 1 to 4.   The method for treating water to be treated according to any one of claims 5 to 9, wherein the water to be treated further contains at least one contaminant selected from the group consisting of an acid, an alkali and ammonia.   The method for treating water to be treated according to any one of claims 5 to 10, wherein the water to be treated is washing water in a chimney weir.   The water to be treated according to any one of claims 5 to 11, wherein the water to be treated contains at least one contaminant selected from the group consisting of nitrogen, nitrogen compounds, silicon, silicon compounds and ions thereof. How to handle   The method for treating treated water according to any one of claims 5 to 12, wherein as a pretreatment, a chemical treatment agent which is a reaction product of Greenlast and / or a dehydrogenase with a water-soluble organic substance is added The method for treating treated water according to any one of claims 5 to 12, wherein at least one selected from ammonia, nitrogen, nitrogen compounds, silicon, silicon compounds and ions thereof is oxidized and decomposed under acidic conditions.   In the method of treating treated water according to any one of claims 5 to 13, at least one metal selected from the group consisting of aluminum, yttrium, zinc, copper, tin, chromium and silicon obtained, The method for producing Greenlast according to claim 2, wherein the metal compound and / or the precipitate contained as the metal ferrite is used as the additive metal and / or the metal ferrite according to claim 2.