CN1332892C - Normal temperature and normal pressure ClO2 catalyzed oxidation process of treating high concentration organic waste water - Google Patents
Normal temperature and normal pressure ClO2 catalyzed oxidation process of treating high concentration organic waste water Download PDFInfo
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- CN1332892C CN1332892C CNB2005100946103A CN200510094610A CN1332892C CN 1332892 C CN1332892 C CN 1332892C CN B2005100946103 A CNB2005100946103 A CN B2005100946103A CN 200510094610 A CN200510094610 A CN 200510094610A CN 1332892 C CN1332892 C CN 1332892C
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Abstract
The present invention relates to industrial waste water treatment, more specifically a normal temperature and normal pressure chlorine dioxide catalytic oxidation process for treating high concentration organic waste water, wherein a catalyst uses expanded graphite as carriers, metal oxide is used as active constituents and chlorine dioxide ClO2 is used as an oxydant. The process comprises the following steps: the catalyst with certain mass is filled in a catalytic oxidation reactor; waste water and ClO2 are added in the reactor after mixed; an air source is turned on to blast air for one-hour catalytic oxidation in order to remove organic matters in the waste water; after the reaction is ended, the air source is turned off, treated water is discharged from a water outlet, and the CODcr value is subsequently measured. The catalyst for the catalytic oxidation is composed of active constituents and carriers, the active constituents are oxide of one or more of Cu, Co and Ni, the carriers are expanded graphite, wherein the weight percentage content of metal is 0.1 to 5 per cent, and the rest is of carriers. The present invention is a normal temperature and pressure preparation process with good catalytic effect and is suitable for industrial popularization and application.
Description
Technical field
The present invention relates to Industrial Wastewater Treatment, specifically catalyzer is carrier with the expanded graphite, and metal oxide is an active ingredient, dioxide peroxide ClO
2Be oxygenant, normal temperature and normal pressure ClO 2 catalyzed oxidation process for the treatment of high concentration organic waste water.
Background technology
Fast development along with modern industry, various discharged waste water increase year by year, and mostly have concentration height, biological degradability difference even characteristics such as bio-toxicity are arranged, more strict standard is all paid much attention to and formulated in the comprehensive regulation of this type of high concentration hard-degraded organic waste water both at home and abroad.At present; the waste water that the part composition is simple, biological degradability omits, concentration is lower all can obtain by traditional technology handling; and the concentration height, be difficult to biodegradable waste water and be difficult to thoroughly be handled; and also exist very big economically because of difficulty; how to remove or transform the various toxic substances in this class waste water; being not only very active research direction of current domestic and international water treatment field, also is to press for one of difficult problem of solution in China's 21 century water problems.
Method for oxidation is a kind of " destructiveness " technology, and the organism effect is poisoned in the removal with wide spectrum, and oxidation style can be with the organic pollutant oxidation in the waste water or thoroughly removed.
Method for oxidation has at present: chemical oxidization method, photochemical oxidation method, catalytic wet air oxidation, supercritical water oxidation method, photochemical catalysis oxidation style, biological oxidation process etc.
Photochemical oxidation be by oxygenant under the radiation of light, produce the stronger free radical of oxidation capacity and carry out, the kind difference according to oxygenant can be divided into UV/H
2O
2, UV/O
3And UV/H
2O
2/ O
3Etc. system.
Photocatalytic oxidation is meant that mainly UV/Fenton reagent method and conductor photocatalysis oxidation, wet oxidation process (Wet AirOxidation is called for short WAO) are under High Temperature High Pressure, utilizes oxygenant that the oxidation operation in the waste water is carbonic acid gas and water.
Supercritical water oxidation technology a kind of novel oxidation technology that can thoroughly destroy organic constitution that to be the mid-80 proposed by American scholar Modell, its principle be under the state of supercritical water with waste water in contained organism resolve into simple harmless micromolecular compound such as water, carbonic acid gas rapidly with oxygenant.
Chemical oxidization method is poisoned organism by chemical reaction and is oxidized to little poison or nontoxic material, perhaps is converted into easily and the form of water sepn, because the difference of oxygenant can be divided into ozone, hydrogen peroxide, dioxide peroxide and potassium permanganate oxidation etc.
Photochemical oxidation and Treatment by Photocatalysis Oxidation low concentration wastewater effect are better, industrialization is complicated, practical engineering application is few, wet oxidation and Catalytic Wet Oxidation have the high-concentration hardly-degradable of making oxidation operation or coupling, the oxidation efficiency height, the advantage that decomposition rate is fast, but also have the catalyst costs height simultaneously, the reaction unit complexity needs high-temperature high-pressure apparatus and auxiliary facility, shortcomings such as anticorrosion difficulty, and investment is big.The supercritical water oxidation technology also is in laboratory stage at present, and the industrial application difficulty is bigger, and investment is big, the running cost height.
Because above the whole bag of tricks is for the very harsh and actual limitation of applying the aspect existence of the requirement of Pollutant Treatment condition, people have paid many effort for the method that exploitation is not influenced by the problems referred to above.In recent years, the room-temperature catalytic oxidation technology has been subjected to people's extensive concern.The research core of catalytic oxidation is to seek excellent property, catalyzer with wide spectrum katalysis, improve the catalytic effect of catalyzer, reduce the loss and the intoxicating phenomenon of catalyzer, it can be played a role in Industrial Wastewater Treatment better, catalytic oxidation is because its high oxidation susceptibility, and the oxidation operation that can make that many toxicity are big, difficult degradation and general oxidation style is difficult to prove effective decomposes, and has therefore caused domestic and international efforts at environmental protection person's extensive attention.
Dioxide peroxide is widely used in aspects such as senior textile bleaching, drinking water disinfection, food-processing, cooling tower water processing as sterilizing agent and SYNTHETIC OPTICAL WHITNER.In recent years, the strong oxidizing property of dioxide peroxide can receive various countries efforts at environmental protection persons' concern.Compare with chlorine oxidation, dioxide peroxide can prevent the formation of the haloform of carcinogenesis, can be economical and destroy the phenols of water effectively, and dioxide peroxide all has stronger oxidation capacity in the scope of pH broad, and the oxidation effectiveness longer duration.Their mutagenicity is lower, and HUMAN HEALTH is safe from harm, and is classified as A1 level product by the World Health Organization.Dioxide peroxide is compared with other oxygenant, and oxidation capacity is strong, and production process is simple, less investment, and price is low.
People's such as Yang Xu patent of invention CN1569679 " a kind of catalytic oxidation treatment methyl-phenoxide method for waste water " loads on Al to metal catalyst
2O
3Or on the gac, carry out catalyzed oxidation.It fails to realize the normal temperature and pressure preparation, and catalytic efficiency is on the low side.
Summary of the invention
The object of the present invention is to provide a kind of excellent catalytic effect, be applicable to the method for the normal temperature and normal pressure ClO 2 catalyzed oxidation processing organic waste water that industry is applied, catalyzer is carrier with the expanded graphite, and metal oxide is an active ingredient.
For achieving the above object, technical solution of the present invention is:
The catalyzer of certain mass is packed in the catalyst oxidation reactor into waste water and ClO
2Mix the back and add in the reactor, open source of the gas and blast air, catalyzed oxidation 1 hour is removed the organism in the waste water.Reaction is closed source of the gas after finishing, and the water of handling well is discharged from water outlet, then measures its CODcr value.
The catalyzer of described catalyzed oxidation is made up of active ingredient and carrier, and active ingredient is one or more a oxide compound in copper, cobalt, the nickel, and carrier is an expanded graphite; Wherein the weight percent content of metal is 0.1-5%.
Wherein, with the oxide compound of cobalt and nickel catalytic effect the best as active ingredient.
Described normal temperature and normal pressure ClO 2 catalyzed oxidation is handled in the waste water, and the dioxide peroxide add-on is a 0.1-1g/L waste water, and the mass ratio of waste water and catalyzer is 100-200.
Preparation catalyst for catalytic oxidation method is as follows:
Take by weighing 10g-100g 50 purpose natural flake graphites, vitriol oil 15-100g, concentrated nitric acid 5-15g and hydrogen peroxide 1-5g by the certain mass ratio, hydrogen peroxide is added the natural flake graphite oxidation, stirring makes and mixes, again graphite and hydrogen peroxide mixture are added the vitriol oil, stir simultaneously to make and mix.Stirring reaction added concentrated nitric acid and continues stirring reaction, because nitric acid volatilizees easily after for some time, a large amount of yellow smog is arranged this moment, the wall of container heating, because the oxygenizement crystalline flake graphite graduates into deep green by black, the crystalline flake graphite deliquescing in the container simultaneously becomes pasty state.After reaction finishes,, repeat repeatedly to pH=7 with distilled water wash reaction solution and suction filtration.
Take by weighing one or more the solution in the cupric nitrate, Xiao Suangu, nickelous nitrate of certain volumetric molar concentration 0.01-0.1mol/L.The graphite of handling well is put into solution soak, soak after 4 hours, reaction product was placed in the loft drier 120 ± 1 ℃ of dryings of temperature control 12 hours, obtain expansible black lead.Earlier chamber type electric resistance furnace is warming up to 1000 ℃.With quartz crucible preheating 2min in chamber type electric resistance furnace.The taking-up quartz crucible adds an amount of expansible black lead and puts back in the stove rapidly, and graphite expands rapidly, and volume increases gradually.Be not related to fire door and expanded about ten seconds, observe expanded graphite to the back of no longer continuing to expand and take out rapidly and be cooled to room temperature and get final product.
Normal temperature and pressure preparation of the present invention, requiring of Pollutant Treatment condition is low, and excellent catalytic effect is applicable to what industry was applied.Invest lessly, running cost is low.
Description of drawings
Fig. 1 catalytic oxidation treatment organic waste water device synoptic diagram
1. waste water source 2. catalyzer 3. water outlets 4. catalyst oxidation reactors 5. sources of the gas
Embodiment
Single Preparation of catalysts
Take by weighing natural flake graphite 10g (50 order), vitriol oil 35g, concentrated nitric acid 9g and hydrogen peroxide 1.2g by the certain mass ratio.Hydrogen peroxide is added the natural flake graphite oxidation, and stirring makes and mixes.Graphite and hydrogen peroxide mixture are added the vitriol oil, stir simultaneously to make and mix.Stirring reaction added concentrated nitric acid and continues stirring reaction after for some time, because the oxygenizement crystalline flake graphite graduates into deep green by black, the crystalline flake graphite deliquescing in the container simultaneously becomes pasty state.After reaction finishes,, repeat repeatedly to wash to filtrate pH=7 with distilled water wash reaction solution and suction filtration.
Get the Cu (NO of 0.0156mol/L
3)
2Solution 100ml.The graphite of oxide treatment is put into Cu (NO
3)
2Soaking and stirring in the solution was placed after 12 hours, with behind the reaction product suction filtration in loft drier 120 ℃ of dryings of temperature control 10 hours, obtain expansible black lead.Earlier chamber type electric resistance furnace is warming up to 1000 ℃.With quartz crucible preheating 2min in chamber type electric resistance furnace.The taking-up quartz crucible adds an amount of expansible black lead and puts back in the stove rapidly, and graphite expands rapidly, and volume increases gradually.Be not related to fire door and expanded about ten seconds, the observation expanded graphite is cooled to room temperature to no longer continuing rapid taking-up the in expansion back, and is standby in the product bag of packing into.Get catalyst A
1, catalyst A
1The weight percentage of middle metal component is: Cu is 1%, and all the other are the carrier expanded graphite; Same method is got the Cu (NO of 0.078mol/L
3)
2Solution 100ml, the preparation catalyst A
2, catalyst A
2The weight of middle metal component is that Cu is 5%, and all the other are the carrier expanded graphite.
Same method is got the Co (NO of 0.0169mol/L respectively
3)
2Solution 100ml, get the Co (NO of 0.0847mol/L
3)
2Solution 100ml, the preparation catalyst B
1, B
2Catalyst B
1The weight of middle metal component is that Co is 1%, B
2The weight Co of middle metal component is 5%.
Same method is got the NiNO of 0.0169mol/L respectively
3Solution 100ml, get the NiNO of 0.0847mol/L
3Solution 100ml.Preparation catalyzer C
1, C
2Catalyzer C
1The weight of middle metal component is that Ni is 1%, C
2The weight of middle metal component is Ni5%.
Single catalyzer is to the treatment effect of organic waste water
Catalyzer 10g is filled in as shown in Figure 1 the reactor, at normal temperatures and pressures, after organic waste water 300ml (the CODcr value is 430omg/L) and 1.5g dioxide peroxide mix, enter reactor from waste water source 1, open source of the gas 5 and blast air, catalyzed oxidation one hour is removed the organism in the waste water.Reaction is closed source of the gas after finishing, and the water of handling well is discharged from water outlet 3, adopts the mensuration dichromate titration (GB11914-89) of the aerobic amount of hydrochemistry to measure its CODcr value.Result sees Table 1.
Table 1 single metal catalytic oxidation treatment effect
| Catalyzer | Water outlet CODcr (mg/L) | Clearance % |
| A 1 | 1850 | 57.0 |
| A 2 | 1540 | 64.1 |
| B 1 | 1280 | 70.2 |
| B 2 | 1035 | 75.9 |
| C 1 | 1030 | 76.0 |
| C 2 | 750 | 82.6 |
The mixed catalyst preparation: for
Press embodiment 1, get the Cu (NO of 0.078mol/L
3)
2Co (the NO of solution 50ml and 0.0847mol/L
3)
2Solution 50ml mixes, preparation catalyzer D; The weight of metal component is among the catalyzer D: Cu:2.5%, Co:2.5%.
Press embodiment 1, get the Cu (NO of 0.078mol/L
3)
2The NiNO of solution 50ml and 0.0847mol/L
3Solution 50ml mixes, preparation catalyzer E; The weight of metal component is among the catalyzer E: Cu:2.5%, Ni:2.5%.
Press embodiment 1, get the Co (NO of 0.0847mol/L
3)
2The NiNO of solution 50ml and 0.0847mol/L
3Solution 50ml mixes, preparation catalyzer F; The weight of metal component is among the catalyzer F: Co:2.5%, Ni:2.5%.
Press embodiment 1, get the Cu (NO of 0.0156mol/L
3)
2Co (the NO of solution 50ml, 0.0169mol/L
3)
2The NiNO of solution 50ml and 0.0169mol/L
3Solution 100ml mixes, preparation catalyzer G.The weight of metal component is among the catalyzer G: Co:2.5%, Ni:2.5%, Cu:2.5%.
Press embodiment 2, investigate the treatment effect of mixed metal catalyst to organic waste water, result sees Table 2.
Table 2 hybrid metal catalytic oxidation treatment effect
| Catalyzer | Water outlet CODcr (mg/L) | Clearance % |
| D | 1510 | 64.9 |
| E | 1020 | 76.2 |
| F | 560 | 87.0 |
| G | 550 | 87.3 |
Experimental result by example draws, at normal temperatures and pressures, with dioxide peroxide as oxygenant, catalyzer with one or more oxide compound in copper, cobalt, the nickel as active ingredient, expanded graphite is a carrier, handles high concentrated organic wastewater, feeds air in certain amount, the CODcr clearance is higher, and treatment effect is better.Wherein, with the oxide compound of cobalt and nickel catalytic effect the best as active ingredient.
Claims (3)
1. normal temperature and normal pressure ClO 2 catalyzed oxidation process for the treatment of high concentration organic waste water is characterized in that the catalyzer of certain mass being packed in the catalyst oxidation reactor into waste water and ClO
2Mix the back and add in the reactor, open source of the gas and blast air, catalyzed oxidation 1 hour is removed the organism in the waste water; Reaction is closed source of the gas after finishing, and the water of handling well is discharged from water outlet, then measures its CODcr value; The catalyzer of described catalyzed oxidation is made up of active ingredient and carrier, and active ingredient is one or more a oxide compound in copper, cobalt, the nickel, and carrier is an expanded graphite; Wherein the weight percent content of metal is 0.1-5%; Wherein the dioxide peroxide add-on is a 0.1-1g/L waste water, and the mass ratio of waste water and catalyzer is 100-200.
2. normal temperature and normal pressure ClO 2 catalyzed oxidation process for the treatment of high concentration organic waste water according to claim 1 is characterized in that above-mentioned oxide compound with cobalt and nickel catalytic effect the best as active ingredient.
3. normal temperature and normal pressure ClO 2 catalyzed oxidation process for the treatment of high concentration organic waste water according to claim 1, the Preparation of catalysts method that it is characterized in that above-mentioned catalyzed oxidation is: take by weighing 10g-100g 50 purpose natural flake graphites, vitriol oil 15-100g, concentrated nitric acid 5-15g and hydrogen peroxide 1-5g by the certain mass ratio, hydrogen peroxide is added the natural flake graphite oxidation, stirring makes and mixes, again graphite and hydrogen peroxide mixture are added the vitriol oil, stir simultaneously to make and mix; Stirring reaction added concentrated nitric acid and continues stirring reaction after for some time, and graphite graduates into deep green by black, and the crystalline flake graphite deliquescing in the container simultaneously becomes pasty state; After reaction finishes,, repeat repeatedly to pH=7 with distilled water wash reaction solution and suction filtration;
Take by weighing one or more the solution in the cupric nitrate, Xiao Suangu, nickelous nitrate of certain volumetric molar concentration 0.01-0.1mol/L, the graphite of handling well is put into solution to be soaked, soak after 4 hours, reaction product was placed in the loft drier 120 ± 1 ℃ of dryings of temperature control 12 hours, obtain expansible black lead;
Earlier chamber type electric resistance furnace is warming up to 1000 ℃, with quartz crucible preheating 2min in chamber type electric resistance furnace, the taking-up quartz crucible adds an amount of expansible black lead and puts back in the stove rapidly, graphite expands rapidly, volume increases gradually, observes expanded graphite to the back of no longer continuing to expand and takes out rapidly and be cooled to room temperature and get final product.
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| CN100408170C (en) * | 2006-08-16 | 2008-08-06 | 哈尔滨工业大学 | Process for preparing CuO/gamma-Al2O3 used as catalyst for catalytic oxidation process by inducing ClO2 with microwave |
| CN101844828B (en) * | 2010-05-27 | 2011-12-14 | 南京工业大学 | Treatment method for efficient catalytic oxidation of chlor-alkali industrial wastewater |
| CN103787537B (en) * | 2012-10-30 | 2015-11-18 | 中国石油化工股份有限公司 | A kind for the treatment of process of sewage and application thereof |
| CN103071498B (en) * | 2013-01-14 | 2015-04-22 | 杜亚丽 | Preparation method of Cu2O compound photocatalyst |
| CN103641265A (en) * | 2013-12-24 | 2014-03-19 | 河南省邦源环保工程有限公司 | Method of treating high-concentration phenol-containing industrial wastewater by photo-catalytic oxidation |
| CN104193108B (en) * | 2014-09-16 | 2016-04-20 | 天津长芦汉沽盐场有限责任公司 | Produce the treatment process of washes in tetrabromo-bisphenol process |
| CN105417677A (en) * | 2015-12-25 | 2016-03-23 | 中国石油集团东北炼化工程有限公司吉林设计院 | Chlorine dioxide catalytically-oxidizing apparatus used for waste water treatment |
| CN111960527B (en) * | 2020-07-14 | 2021-07-09 | 中原环保知和(郑州)水环境科技有限公司 | ClO (ClO)2Method for deeply treating biochemical tail water of sewage by effervescent tablets |
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| CN1569679A (en) * | 2003-07-18 | 2005-01-26 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation treatment of anisole waste water |
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2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387350A (en) * | 1989-11-20 | 1995-02-07 | George L. Williamson | Method and apparatus for treating and disinfecting infectious wastes |
| JPH078975A (en) * | 1993-06-28 | 1995-01-13 | C M D:Kk | Treatment of waste solution |
| CN1569679A (en) * | 2003-07-18 | 2005-01-26 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation treatment of anisole waste water |
Non-Patent Citations (1)
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| 膨胀石墨的制备、结构和应用 陈志刚等，江苏大学学报（自然科学版），第26卷第3期 2005 * |
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Assignee: Changzhou Walldec Special New Materials Co., Ltd. Assignor: Jiangsu Polytechnic University Contract fulfillment period: 2008.11.20 to 2015.11.20 contract change Contract record no.: 2009320000028 Denomination of invention: Normal temperature and normal pressure ClO2 catalyzed oxidation process of treating high concentration organic waste water Granted publication date: 20070822 License type: Exclusive license Record date: 2009.1.22 |
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