JP4607013B2 - Waste water treatment agent containing inorganic porous catalyst and waste water treatment method using the same - Google Patents

Description

  The present invention relates to a wet cracking catalyst. The present invention also relates to a method for detoxifying wastewater containing organic matter, particularly organic acid, using a wet cracking catalyst.

Wastewater discharged from the chemical industry, food factories or plating factories often contains a large amount of organic substances, especially organic acids. Discharge of wastewater containing organic matter causes over-nutrition of lakes, rivers or seas, causing eutrophication of water and causing environmental pollution. Therefore, it is necessary to decompose and remove organic matter contained in wastewater to make it harmless. Conventionally known methods for removing organic matter in wastewater include incineration methods, biological treatment methods, adsorption removal methods, and oxidation treatment methods. Conventionally, organic materials are removed by a combination of these methods. It is detoxified (Non-Patent Document 1).
The combustion treatment method has a problem in that a large amount of fossil fuel is combusted to treat the waste water, so that resources are wasted and treatment costs such as fuel costs are remarkably increased. In addition, the combustion treatment method may cause secondary pollution due to exhaust gas etc. discharged by combustion, and increases emissions of carbon dioxide, sulfurous acid gas, NOx, SOx, etc., which are the cause of global warming, etc. There was a problem.
In the biological treatment method, microorganisms and the like are killed due to fluctuations in water quality such as pH, salt concentration and organic matter concentration of the waste water and coexisting heavy metals, or the effect of the microorganisms is reduced because the microorganisms are weakened by heavy metals. In order to avoid such a problem, for example, it is necessary to adjust water quality such as removal of heavy metals, pH, and organic matter concentration before the treatment. In order to adjust the water quality, such as diluting wastewater or removing heavy metals, the equipment and operation become complicated this time, and the reaction rate is low because of the decomposition using microorganisms. The treatment method has a problem of requiring a large site area. Furthermore, when the biological treatment method is applied, surplus sludge is generated, and there is a detrimental effect that surplus sludge must be treated in addition to wastewater, which inevitably increases the treatment cost.
Although a method using a reverse osmosis membrane is theoretically possible, the membrane itself is expensive and the membrane is clogged during processing, so concentrated organic substances, heavy metals, etc. must be secondarily treated. In reality, it is difficult to implement.
In the case of the adsorption removal method using an adsorbent, for example, there is an organic substance adsorption removal method using activated carbon as one of representative examples. In this method, activated carbon is added to waste water containing organic matter, and the organic matter is adsorbed and removed by activated carbon. However, this method has a problem that a secondary treatment of the activated carbon to which the organic matter adhered by filtration is necessary is required.
The conventional oxidation treatment method using an oxidizing agent has a removal rate as low as 50% at the maximum, and since it is used in combination with the other treatment methods described above, it is very difficult to implement industrially advantageously. It was.
Further, a wet oxidation method for organic substances using a catalyst has been proposed (Patent Document 1). However, water or water vapor becomes a catalyst poison or has low activity, and it is difficult to completely decompose organic substances. There is no industrially practiced example since lower product organic products are produced.
JP 2003-10687 A December 20, 2000 "Water Treatment Technology", published by Ohm, Inc. 64-67

An object of this invention is to provide the detoxification method of the waste_water | drain containing organic substance using the wet decomposition catalyst excellent in the removal effect of the organic matter in waste_water | drain, especially organic acids, such as carboxylic acid and oxycarboxylic acid, and the catalyst.
As a result of intensive studies to achieve the above object, the present inventors have wet-decomposed organic substances, particularly organic acids, contained in wastewater in the presence of a catalyst comprising Fe or / and Ni supported on an inorganic porous material. It has been found that the wet decomposition of organic substances, especially organic acids, is surprisingly accelerated. Further, the present inventors can contact the organic substance composed of C, H and O with the catalyst of the present invention in the presence of an oxidizing agent, so that the organic substance can be decomposed into carbon dioxide and water, and the organic substance contains nitrogen. It has been found that it can be decomposed to NOx when it is, and that it can be decomposed to SOx if the organic substance contains sulfur. The present inventors have found that when an organic substance is brought into contact with the catalyst of the present invention in the absence of an oxidizing agent, the organic substance is cracked into a lower hydrocarbon.
Furthermore, when the present inventors wet-decompose organic matter-containing wastewater in the presence of an oxidizing agent and an organic wet-decomposition catalyst in which Fe or / and Ni is supported on an inorganic porous body, the organic matter contained in the wastewater, particularly organic matter, is obtained. It has been found that the acid can be efficiently wet-decomposed and, as a result, the cost for wastewater treatment can be kept low, and therefore the above-mentioned conventional problems have been solved at once.
After obtaining such various findings, the present inventors have further studied and completed the present invention.
That is, the present invention
(1) An organic wet decomposition catalyst characterized by comprising Fe or / and Ni supported on an inorganic porous material,
(2) The catalyst according to the above (1), wherein the inorganic porous material has an adsorption ability,
(3) The catalyst according to (1), wherein the inorganic porous material is alumina silicate, silica, porous material, or alumina,
(4) The catalyst according to (1), wherein the organic substance is an organic acid,
(5) The catalyst according to (4) above, wherein the organic acid is a carboxylic acid or an oxycarboxylic acid,
(6) A method for producing an organic wet decomposition catalyst, comprising adsorbing a metal salt of Fe or / and Ni to an inorganic porous material, and then firing the reaction product;
(7) A method for detoxifying an organic material, which comprises subjecting the organic material to wet decomposition in the presence of the catalyst according to (1),
(8) A method for detoxifying wastewater, characterized in that organic matter contained in wastewater is wet-decomposed in the presence of the catalyst according to (1),
(9) The detoxification method according to the above (7) or (8), which is further subjected to wet decomposition in the presence of an oxidizing agent.
(10) The method for detoxifying waste water according to (9), wherein the organic substance is an organic acid, and the oxidizing agent is air, oxygen, hydrogen peroxide, or ozone,
(11) The method for detoxifying waste water according to the above (8), characterized by wet decomposition under heating or / and pressurization,
(12) The waste water detoxification method according to (11), wherein the heating temperature is 100 ° C. or higher, and the heating time is 0.1 second to 1 week, and (13) The description (8) Drainage characterized by detoxification by the detoxification method of
About.

FIG. 1 shows the results of analysis by a capillary electrophoresis analyzer in Test Example 1, Test Example 2, Comparative Example 4 and Comparative Example 9. From this figure, it can be seen that the citric acid contained in the treatment liquid is effectively removed by the treatment of the present invention, and there is substantially no production of by-products. In the case of the Co ₂ O ₃ catalyst, it can be seen that not only citric acid remains but also various by-products are generated. Further, in the case of the Co—H-mordenite catalyst, citric acid is almost lost, but it can be seen that various products are generated.
FIG. 2 shows the analysis results of the capillary electrophoresis analyzers of Test Example 3, Test Example 4 and Comparative Example 19. In FIG. 2, there are three data. The top data shows the reaction solution of Comparative Example 19 and the absorbance of tartaric acid added during the analysis, and the bottom data shows the reaction solution and analysis of Test Example 4. The absorbance of tartaric acid added occasionally is shown, and the data located between these two data shows the absorbance of tartaric acid added in the reaction solution of Test Example 3 and the analysis. Further, in FIG. 2, a tartaric acid peak is observed every 9 minutes. In addition, the peak of tartaric acid in Test Example 3 and Test Example 4 is a peak of tartaric acid added at the time of analysis.
FIG. 3 shows the results of analysis by a capillary electrophoresis analyzer in Test Example 5 and Test Example 6. In the figure, data 1 indicates the absorbance of the ethylenediaminetetraacetic acid solution (hereinafter abbreviated as EDTA) before the reaction and EDTA added during the analysis of Test Examples 5 and 6, and the data 2 indicates the data of Test Examples 5 and 6. The absorbance of only EDTA added at the time of analysis is shown. The data of 3 shows the absorbance of the reaction solution of Test Example 5 and the EDTA added during the analysis, and the data of 4 shows the absorbance of the reaction solution of Test Example 6 and the EDTA added during the analysis. Further, in FIG. 3, an EDTA peak is observed every 10 minutes.

The present invention is an organic wet decomposition catalyst characterized in that Fe or / and Ni is supported on an inorganic porous material.
Examples of the inorganic porous material used in the present invention include porous inorganic oxides, and more specifically, for example, Y type zeolite, X type zeolite, T type zeolite, O type zeolite, β zeolite, ZSM-3, EMT, EMC-2, ZSM-5, ZSM-11, ZSM-18, ZK-5, FSM-16, L-type zeolite, shabazite, offretite, levinite, erionite, A-type zeolite, mordenite, clino Zeolite such as puchirolite, lomontite, philipsite, ferrierite, wailakite, gmelinite, crinotylolite, mazaite, faujasite X, faujasite Y, stilbite, clinoptilolite, hulandite or TS-1. Alumina silicate such as crystalline or amorphous alumina Silicate), alumina, CMS, silica (MCM-41, FSM-16, KSM-1, KSM-2, etc.), porous materials such as mesoporous zirconia or heteropolyacid cesium salt, silica-alumina, titania, alumina-titania, etc. Is mentioned. In the present invention, the inorganic porous material may be a clay mineral such as clay, kaolin, vermiculite, perlite, or bentonite. According to the present invention, the inorganic porous material is preferably alumina silicate, silica, porous material or alumina, and more preferably zeolite. Moreover, it is preferable that the said inorganic porous body has adsorption capability, and it is more preferable that it has ion exchange capability further.
The catalyst of the present invention is prepared by supporting Fe or / and Ni on the inorganic porous material. Such a preparation method may be any method as long as Fe or / and Ni can be supported on the inorganic porous material. For example, a method of adsorbing the inorganic porous material and a metal salt of Fe or / and Ni can be used. More specifically, for example, a supporting method using a known adsorption means such as an impregnation method or ion exchange may be used. According to the present invention, the product thus supported is preferably further calcined. The firing temperature is preferably about 350 ° C to 1300 ° C, more preferably about 450 ° C to 900 ° C. The firing time is preferably about 1 hour to 1 week, more preferably about 3 hours to 12 hours, and most preferably about 5 hours to 8 hours.
Examples of the metal salt of Fe include, for example, iron phosphate, iron nitrate, iron sulfate, ammonium sulfate iron, iron perchlorate, iron chloride, iron citrate, ammonium iron citrate, iron oxalate, iron iron oxalate, or ethylenediamine Examples thereof include iron chelate complex of tetraacetic acid.
Examples of the metal salt of Ni include nickel acetate tetrahydrate (Ni (CH ₃ COO) ₂ .4H ₂ O), nickel sulfate hexahydrate (NiSO ₄ .6H ₂ O), nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ · 6H ₂ O), nickel chloride hexahydrate (NiCl · 6H ₂ O), nickel chloride anhydrous salt (NiCl ₂ ) and the like.
The supported amount of Fe or / and Ni is usually 0.01 to 50% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the inorganic porous body. It is.
The catalyst of the present invention is used for wet decomposition of organic matter, particularly wet decomposition of waste water containing organic matter. By subjecting the catalyst of the present invention to wet decomposition treatment of organic matter-containing wastewater, the organic matter-containing wastewater can be rendered harmless. According to the invention, the above wet cracking means oxidative cracking or / and cracking in the presence of water or steam.
The waste water to be rendered harmless in the present invention may contain any organic substance, and may further contain an inorganic substance. Examples of the organic substance include organic acids, alcohols, amines, and hydrocarbons. Examples of the inorganic substance include heavy metals such as copper, zinc, zirconium, silver, cadmium, tin, niobium, antimony, hafnium, tantalum, mercury, thallium, bismuth, chromium, cobalt, cerium, vanadium, ruthenium, tungsten, and lead. And the inorganic substance may be in the form of heavy metal ions derived therefrom.
Examples of the organic acid include carboxylic acid or oxycarboxylic acid, and more specifically, maleic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, amino acids (for example, glycine). Or aspartic acid), enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, peptadecanoic acid, stearic acid, arachic acid, acrylic acid, crotonic acid 2-furoic acid, salicylic acid, succinic acid, aconitic acid, itaconic acid, citraconic acid, malonic acid, acetone dicarboxylic acid, adipic acid, fumaric acid, nicotinic acid, isonicotinic acid, citraconic acid, ethylenediaminetetraacetic acid (EDTA), Iminodiacetic acid, propiolic acid, gentisic acid, vanillin , Benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, methacrylic acid, oleic acid, caffeic acid, benzylic acid, anthranilic acid, glutaric acid, cinnamic acid, oxalic acid, malic acid, citric acid, tartaric acid, lactic acid, glycol Examples include acid, glyoxylic acid, coumaric acid, and gluconic acid. According to the present invention, the organic acid includes phenol or naphthalene. The organic acid may be an organic acid having a chelating ability.
Examples of the alcohol include aliphatic alcohols, aromatic alcohols, alicyclic alcohols, heterocyclic alcohols and polyhydric alcohols, and more specifically, methanol, ethanol, n-propanol, isopropanol, allyl alcohol. , Aliphatic alcohols such as crotyl alcohol, butanol, pentanol, hexanol or octanol, aromatic alcohols such as benzyl alcohol or p-chloro-benzyl alcohol, fats such as cyclohexanol, 4-methyl-cyclohexanol or cyclopentanol It is a heterocyclic alcohol such as cyclic alcohol or furfuryl alcohol, or a polyhydric alcohol such as ethylene glycol or glycerin.
Examples of the amine include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, and dihexylamine. , Diheptylamine, dioctylamine, dinonylamine, didecylamine, trimethylamine, triethylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, dimethylpentylamine, dimethylhexylamine, diethylpropylamine, diethylbutylamine, diethylpentylamine, diethylhexylamine, cyclohexyl Amine, methylcyclohexylamine, dimethylcyclohexyl An aliphatic amine such as min or triethanolamine, or aniline, fluoroaniline, chloroaniline, bromoaniline, iodoaniline, nitroaniline, xylidine, methylaniline, fluoromethylaniline, chloromethylaniline, bromomethylaniline, iodomethylaniline, Aromatic amines such as nitromethylaniline, methylaminophenol, toluylmethylamine or xylylmethylamine can be mentioned.
Examples of the hydrocarbon include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, and undecane.
Examples of the waste water include waste water discharged from various industrial plants such as chemical plants, electronic component manufacturing equipment, food processing equipment, metal processing equipment, metal plating equipment, printing plate making equipment, and photographic equipment. Furthermore, the waste water may be domestic waste water such as sewage and human waste, or waste water containing organic substances such as environmental hormones.
The method of the present invention may be performed in the presence of an oxidizing agent.
Examples of the oxidizing agent include air, oxygen, hydrogen peroxide, ozone, and the like. When the organic substance is a carboxylic acid or oxycarboxylic acid, the amount of the oxidizing agent is preferably about 0, which is an equivalent amount calculated on the assumption that all carboxylic acids and oxycarboxylic acids are oxidatively decomposed into carbon dioxide. The amount is 5 to 10 times, more preferably about 1 to 2 times, and most preferably about 1 to 1.5 times.
In the present invention, the wet decomposition is preferably performed in the presence of water or steam, and the wet decomposition is preferably performed under heating and / or pressure. The heating conditions can be appropriately set depending on the drainage or the catalyst, but preferably the heating temperature is about 100 ° C. or higher and the heating time is about 0.1 seconds or more, more preferably the heating temperature is about 100 to 500 ° C. and The heating time is about 0.1 seconds to 1 week, and most preferably the heating temperature is about 140 ° C. to 180 ° C. and the heating time is about 0.5 seconds to 30 minutes. The pressurizing pressure is preferably about 0.1 MPa to 10 MPa, more preferably about 0.1 to 1 MPa.

The 0.01 mol / dm ³ aqueous solution of nickel chloride 0.5 dm ³ was added to the mordenite 5g, and stirred for 3 days at 80 ° C.. The solution was filtered, washed with 5 dm ³ ion-exchanged water, dried at 100 ° C. overnight, and calcined at 800 ° C. for 5 hours to obtain a Ni—H-mordenite catalyst.

（試験例３）
０．０１ｍｏｌ／ｄｍ^３の酒石酸ナトリウムカリウム溶液１０ｃｍ^３、３５質量％過酸化水素水２ｃｍ^３および実施例１の触媒０．２ｇを、容量３０ｃｍ^３のバッチ式オートクレーヴに加え、１４０℃にて３０分間加熱し、反応させた。反応終了後、得られた溶液を濾過することにより触媒と反応溶液とに分離した。分離した反応溶液をキャピラリー電気泳動分析装置（ＣＡＰＩ−３３００、大塚電子株式会社製）で分析した。分析は、標準添加法を用いて酒石酸塩を定量することにより行われた。結果を第２表に示す。また、キャピラリー電気泳動分析装置による分析結果を第２図に示す。酒石酸のピークの値を計算したところ１００％の酒石酸が消失していた。このことより、これらのＮｉ−Ｈ−モルデナイトは酒石酸分解に有効な触媒であることがわかる。また、第２図から、Ｎｉ−Ｈ−モルデナイトでは酒石酸のピーク以外に何らかの生成物があり、酒石酸が分解し、より低級な炭化水素化合物に変化したことがわかる。
（試験例４）
実施例１の触媒を実施例２の触媒に代えて用いたこと以外、試験例３と同様にして試験・評価した。結果を第２表に示す。また、キャピラリー電気泳動分析装置による分析結果を第２図に示す。試験例３と同様に実施例２の触媒によって酒石酸が分解されたことがわかる。また、第２図に示すとおり実施例２の触媒では他の生成物ができている。このことから、酒石酸が分解し、より低級な炭化水素化合物に変化したことがわかる。
（比較例１８および１９）
実施例１の触媒を、比較例１８としてＰｔ／活性炭（和光純薬株式会社製）、比較例１９としてＷＯ_３に代えてそれぞれ用いたこと以外、試験例３と同様にして試験・評価した。結果を第２表に示す。Ｐｔ／活性炭では５１．７％、ＷＯ_３では５９．６％の酒石酸が消失していた。また、比較例１９のキャピラリー電気泳動分析装置による分析結果を第２図に示す。

（試験例５）
０．０５ｍｏｌ／ｄｍ^３のＥＤＴＡ溶液１０ｃｍ^３、３５質量％過酸化水素水２ｃｍ^３および実施例１の触媒０．２ｇを、容量３０ｃｍ^３のバッチ式オートクレーヴに加え、１４０℃にて３０分間加熱し、反応させた。反応終了後、得られた溶液を濾過することにより、触媒と反応溶液とに分離した。分離した反応溶液をキャピラリー電気泳動分析装置（ＣＡＰＩ−３３００、大塚電子株式会社製）で分析した。分析は、標準添加法を用いてＥＤＴＡを定量することにより行われた。結果を第３表に示す。なお、キャピラリー電気泳動分析装置による分析結果を第３図に示す。ＥＤＴＡのピークの値を計算したところ９５．８％のＥＤＴＡが消失していた。このことより、Ｎｉ−Ｈ−モルデナイトはＥＤＴＡ分解に有効な触媒であることがわかる。
（試験例６）
実施例１の触媒を実施例２の触媒に代えて用いた以外、試験例５と同様にして反応および分析した。結果を第３表に示す。また、キャピラリー電気泳動分析装置による分析結果を第３図に示す。試験例５と同様に実施例２の触媒によってＥＤＴＡが分解されたことがわかる。
（比較例２０）
実施例１の触媒を、比較例２０としてＰｔ／活性炭（和光純薬株式会社製）に代えて用いたこと以外、試験例５と同様にして試験・評価した。結果を第３表に示す。Ｐｔ／活性炭では３５．７％のＥＤＴＡが消失していた。

An Fe—H-mordenite catalyst was obtained in the same manner as in Example 1 except that the nickel chloride aqueous solution was used in place of the iron (II) chloride aqueous solution.
(Test Example 1)
The 0.1 mol / dm ³ of ammonium citrate solution 10 cm ^3, 35 wt% aqueous hydrogen peroxide 2 cm ³ and a catalyst 0.2g of Example 1, was added batchwise autoclave of capacity 30 cm ^3, 30 at 140 ° C. Heated for minutes. Since the reaction temperature was 140 ° C., which was higher than the boiling point of water, an autoclave was used. After completion of the reaction, the resulting solution was filtered to separate the catalyst and the solution. The separated solution was analyzed with a capillary electrophoresis analyzer (CAPI-3300, manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 1. From this analysis, it was confirmed that the product was converted to a lower decomposition product. The analysis results are shown in FIG. As shown in FIG. 1, the peak of citric acid of 98% or more before the reaction disappeared, and no new organic acid peak was found. Moreover, as a result of analyzing the solution after completion | finish of this reaction by H-NMR (made by Shimadzu Corporation), the peak of the carboxyl group and the hydroxyl group was not found.
(Test Example 2)
Analysis was conducted in the same manner as in Test Example 1 except that the catalyst of Example 1 was used instead of the catalyst of Example 2. The results are shown in Table 1. The results of capillary electrophoresis analysis are shown in FIG. In the same manner as in Test Example 1, it was confirmed that citric acid was converted to a lower decomposition product by the catalyst of Example 2.
(Comparative Examples 1-17)
The catalyst of Example 1 was Amberlyst (Rohm & Haas, registered trademark) as Comparative Example 1, Amberlite (Rohm & Haas, registered trademark) as Comparative Example 2, and Nafion-13 (fluorinated ion exchange as Comparative Example 3). Resin, manufactured by DuPont, registered trademark), Nafion NR-50 (fluorinated ion exchange resin, registered trademark, manufactured by DuPont) as Comparative Example 4, H-type mordenite as Comparative Example 5, Fe ₂ O ₃ as Comparative Example 6 WO ₃ as Comparative Example 7, NiO as Comparative Example 8, Co ₂ O ₃ as Comparative Example 9, Pt / activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) as Comparative Example 10, Pt / Al ₂ O ₃ as Comparative Example 11, Comparative Example 12 is CuO, Comparative Example 13 is CuCoOx, Comparative Example 14 is Co—H-mordenite, and Comparative Example 15 is Cu—H—. Rudenaito, CuCo- mordenite as a comparative example 16, except for using each in place of Mn-H- mordenite as Comparative Example 17, was similarly tested and evaluated as in Test Example 1. The results are shown in Table 1. With the Pt-based catalyst, the removal rate of oxycarboxylic acid was less than 50%. Similar results were obtained for other oxides. In the case of tungsten, metal components were lost. In addition, the analysis result by the capillary electrophoresis analyzer of the comparative example 4 and the comparative example 9 is shown in FIG.

(Test Example 3)
0.01 cm / dm ³ sodium potassium tartrate solution 10 cm ³ , 35% by weight hydrogen peroxide 2 cm ³ and 0.2 g of the catalyst of Example 1 were added to a batch type autoclave with a capacity of 30 cm ³ and added at 30 ° C. Heated for minutes and allowed to react. After completion of the reaction, the resulting solution was filtered to separate the catalyst and the reaction solution. The separated reaction solution was analyzed with a capillary electrophoresis analyzer (CAPI-3300, manufactured by Otsuka Electronics Co., Ltd.). Analysis was performed by quantifying tartrate using the standard addition method. The results are shown in Table 2. Further, FIG. 2 shows the analysis result by the capillary electrophoresis analyzer. When the peak value of tartaric acid was calculated, 100% of tartaric acid had disappeared. This shows that these Ni-H-mordenites are effective catalysts for tartaric acid decomposition. In addition, FIG. 2 shows that Ni-H-mordenite has some products other than the tartaric acid peak, and tartaric acid decomposes to become a lower hydrocarbon compound.
(Test Example 4)
Tests and evaluations were performed in the same manner as in Test Example 3 except that the catalyst of Example 1 was used instead of the catalyst of Example 2. The results are shown in Table 2. Further, FIG. 2 shows the analysis result by the capillary electrophoresis analyzer. It can be seen that tartaric acid was decomposed by the catalyst of Example 2 as in Test Example 3. Further, as shown in FIG. 2, other products are formed in the catalyst of Example 2. This indicates that tartaric acid was decomposed and changed to a lower hydrocarbon compound.
(Comparative Examples 18 and 19)
The catalyst of Example 1 was tested and evaluated in the same manner as in Test Example 3 except that Pt / activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was used as Comparative Example 18 and WO ₃ was used as Comparative Example 19, respectively. The results are shown in Table 2. 51.7% of tartaric acid was lost in Pt / activated carbon and 59.6% in WO ₃ . Moreover, the analysis result by the capillary electrophoresis analyzer of the comparative example 19 is shown in FIG.

(Test Example 5)
Add 0.05 cm / dm ³ of EDTA solution 10 cm ³ , 35 mass% hydrogen peroxide 2 cm ³ and 0.2 g of the catalyst of Example 1 to a batch type autoclave with a capacity of 30 cm ³ and heat at 140 ° C. for 30 minutes. And reacted. After completion of the reaction, the resulting solution was filtered to separate the catalyst and the reaction solution. The separated reaction solution was analyzed with a capillary electrophoresis analyzer (CAPI-3300, manufactured by Otsuka Electronics Co., Ltd.). Analysis was performed by quantifying EDTA using the standard addition method. The results are shown in Table 3. FIG. 3 shows the results of analysis using a capillary electrophoresis analyzer. When the peak value of EDTA was calculated, 95.8% of EDTA disappeared. This shows that Ni-H-mordenite is an effective catalyst for EDTA decomposition.
(Test Example 6)
The reaction and analysis were conducted in the same manner as in Test Example 5, except that the catalyst of Example 1 was used instead of the catalyst of Example 2. The results are shown in Table 3. Moreover, the analysis result by a capillary electrophoresis analyzer is shown in FIG. It can be seen that EDTA was decomposed by the catalyst of Example 2 as in Test Example 5.
(Comparative Example 20)
The catalyst of Example 1 was tested and evaluated in the same manner as in Test Example 5 except that Pt / activated carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was used as Comparative Example 20 instead of Pt / activated carbon. The results are shown in Table 3. With Pt / activated carbon, 35.7% of EDTA disappeared.

  The organic matter wet cracking catalyst of the present invention has strong activity against oxidative decomposition and cracking of organic matter, particularly organic acid. The wastewater detoxification method of the present invention can effectively decompose and remove organic substances in wastewater, particularly organic acids.

Claims (7)

A wastewater treatment agent for wastewater containing oxycarboxylic acid, glycine, or EDTA,
A wastewater treatment agent characterized by containing an organic wet decomposition catalyst produced by adsorbing a metal salt of Fe or / and Ni to an inorganic porous material made of alumina silicate, silica or alumina, and then firing it. 2. The wastewater treatment agent according to claim 1 , wherein the organic wet cracking catalyst is produced by adsorbing iron chloride and / or nickel chloride to alumina silicate, followed by firing.   A wastewater treatment method containing oxycarboxylic acid, glycine, or EDTA, wherein the wastewater treatment agent according to claim 1 is added to wastewater containing oxycarboxylic acid, glycine, or EDTA. . The wastewater treatment method according to claim 3 , further comprising adding an oxidizing agent to the wastewater. The wastewater treatment method according to claim 4 , wherein the oxidant is air, oxygen, hydrogen peroxide, or ozone. The wastewater treatment method according to claim 3 , wherein the wastewater after the wastewater treatment agent is added is heated or / and pressurized. The wastewater treatment method according to claim 6 , wherein the heating temperature is 100 ° C. or higher and the heating time is 0.1 second to 1 week.

Images