CN1559938A - Process for water supply deep treatment of catalyzing ozone oxydation by hydroxy ferric oxide as catalyst - Google Patents
Process for water supply deep treatment of catalyzing ozone oxydation by hydroxy ferric oxide as catalyst Download PDFInfo
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- CN1559938A CN1559938A CNA200410013597XA CN200410013597A CN1559938A CN 1559938 A CN1559938 A CN 1559938A CN A200410013597X A CNA200410013597X A CN A200410013597XA CN 200410013597 A CN200410013597 A CN 200410013597A CN 1559938 A CN1559938 A CN 1559938A
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Abstract
The invention is a drinking water advanced treatment method by ozone oxidation with iron oxide hydroxide as catalyst, relating to a drinking water treatment process of eliminating organic substances by ozone oxidation catalyzed by solid catalyst. The surface water is processed by coagulation, deposition, filtration, etc, and enters in an ozone contact tower, a catalyst bed, and a bio-activated carbon filter bed in turn to eliminate the organic substances, and finally enters in the network pipe after sterilized. The catalyste has the advantages of high catalyzing efficiency and completely weak digestion of metallic ions. The invention adopts a drinking water treatment process combining catalytic ozone oxidation and bio-activated carbon, improving the ability of ozone oxidation to eliminate organic substance in the water, the biochemical degrability of organic substances in the water, and ozone utilization ratio, and also helps eliminate metallic ions in the water. It has the advantages of low cost and high oxidizing efficiency.
Description
Technical field: the present invention relates to the catalysis of solid catalyst ozone oxidation and remove organic handling technology of water supply in the water, being specifically related to the hydrous iron oxide is that organic handling technology of water supply in the water is removed in the O3 catalytic oxidation of catalyzer.
Background technology: in recent years,, make the poisonous and harmful organic pollutant of a large amount of difficult degradations enter water body, caused the deterioration of source quality because the industrial or agricultural that continues is polluted.According to domestic and international relevant report, these organic pollutants almost can not be removed in the water technology of routine.In addition, because soil erosion, natural organic matter content raises in the water source, and natural organic matter is the antecedent of substance of disinfection by products, it is limited in one's ability that conventional water treatment process is removed natural organic matter, so natural organic matter content rising causing cholorination process chlorine demand raises and the cholorination by-product concentration raises.For the organism of removing in the water, ozone oxidation is a kind of approach, but ozone oxidation has very strong selectivity, can only oxidizing water in the easy organism of oxidation, ineffective to the degradation production of all kinds of agricultural chemicals and agricultural chemicals in the oxidizing water.The method that strengthens the ozonize ability impels ozone to decompose the strong oxidizing substance-hydroxyl radical free radical of generation intersexes exactly in water, perhaps utilizes solid surface absorption to cause organism and ozone molecule partial concn to raise and accelerates oxidation rate.Impel ozone in water, decompose the method that generates hydroxyl radical free radical comprise ultraviolet ray, hydrogen peroxide both one of with the coupling of ozone and the catalysis of homogeneous phase metal ion and heterogeneous metal oxide compound, wherein the organic approach of metal oxide oxidation catalyst ozone oxidation it is generally acknowledged two kinds, a kind ofly think that ozone decompose to generate active oxygen at metal oxide surface, as US6,149,820; Another kind thinks that thereby organic acid and metal oxide surface complexing of metal ion help it by ozone oxidation, as Andreozzi R. and Pines D..All there are some problems in these methods that promote ozone to decompose: a little less than the penetrativity of ultraviolet ray in water, the life-span of ultraviolet lamp is short, need regular maintenance, increased the technology cost, and promoted that the ozone decomposing efficiency is not high; There is residue problem in hydrogen peroxide, makes chlorine demand rising in the water treatment; Underwater gold belonged to the problem that ion is removed again after the introducing of metal ion can bring and handle; The metal oxide that the catalysis ozone in water decomposes mainly concentrates on some typical transition metal oxides (as Fe
2O
3, MnO
2, CuO, NiO, Co
3O
4, TiO
2, Al
2O
3Deng) and the noble heavy metal oxide (as Ru, Pd) of carrier model, studies show that, these catalyzer or catalytic efficiency is low, or have the problem of metal ion stripping.
Summary of the invention: the present invention is in order to solve the low deficiency of prior art ozone oxidation ability, providing a kind of is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, hydrous iron oxide can promote ozone to decompose the more hydroxyl radical free radical of generation in water, it can make the partial concn of reactant raise to the certain inrichment of organism, is a kind of water treatment method that can improve the ozone oxidation ability with organism in its O3 catalytic oxidation water.Of the present invention is that the O3 catalytic oxidation method for processing water supply depth of catalyzer carries out according to following step with the hydrous iron oxide: a, the drainage after handling through traditional water treating processess such as coagulation, precipitation, filtrations enter the ozone contact tower and carry out ozone oxidation reaction, and control ozone in water initial concentration is 0.5～1.0mgO
3/ (mgTOC), the residence time of water in the ozone contact tower is 10～20 minutes; B, the water that comes out from the ozone contact tower enter in the catalyst bed that inside is filled with hydrous iron oxide or carrier model hydrous iron oxide, and the control residence time of water in catalyst bed is 10～30 minutes; C, the water after oxidation enter the biological activity carbon filterbed, and the control residence time of water in the biological activity carbon filterbed is 10～20 minutes, further remove the organism in anhydrating; D, remove organic water and enter webmaster later on through chlorination.The present invention is that the approach of the difficult oxidation of organic compounds in the active ingredient O3 catalytic oxidation water is with the hydrous iron oxide: for the organism a little less than the adsorptivity, decompose the generation hydroxyl radical free radical by its surface hydroxyl group catalysis ozone and carry out oxidation; For adsorbable organism, improve oxidation rate by surface enrichment organism and ozone.Hydrous iron oxide has bigger specific surface area, more surface hydroxyl group (The adsorbed hydroxyl content reaches 0.32mmol/g) and stronger surface hydroxylation degree, in water, can promote ozone decompose to generate the hydroxyl radical free radicals with strong oxidation capacity, the difficult oxidation of organic compounds in can the efficient oxidation water more; Organism in the water there is certain inrichment; Can remove the pollution of heavy metal to the exclusive adsorption of metal ion.The hydrous iron oxide O3 catalytic oxidation has improved more than 40% than independent ozone oxidation the clearance of the difficult oxidation of organic compounds-oil of mirbane of trace in the water, removal to humic acid in the water has improved 30% than independent ozone oxidation, and it has high and very faint (the solubility product constant K of metal ion stripping of catalytic efficiency
Sp=1.3 * 10
-38) advantage.It is the catalysis of solid catalyst ozone oxidation of active ingredient and the water technology of biological activated carbon coupling that the present invention adopts with the hydrous iron oxide, this catalysis ozone metallization processes is saved energy, is not introduced other chemical agents, be particularly useful for containing the advanced treatment of the underground water and the natural surface water of chemical oxidation pollutent in distress, improved the biodegradability of difficult oxidation of organic compounds in this two classes water.O3 catalytic oxidation and biological active carbon treatment process are united use not only can improve the clearance of total organic carbon in the water, the toxicity of reduction water, and can reduce the concentration of organic pollutant and solvability natural organic matter in the water, reduced the chlorine demand in the subsequent disposal and the concentration of chlorine disinfectant product, it has the low and oxidation efficiency high advantage of cost.
Description of drawings: Fig. 1 is the process flow sheet of embodiment one, and Fig. 2 is the process flow sheet of embodiment two, and Fig. 3 is the process flow sheet of embodiment three.
Embodiment one: referring to Fig. 1, present embodiment is carried out according to following step: the drainage after traditional water treating processess such as a, process coagulation, precipitation, filtration are handled enters the ozone contact tower and carries out ozone oxidation reaction, and control ozone in water initial concentration is 0.5～1.0mgO
3/ (mgTOC), the residence time of water in the ozone contact tower is 10～20 minutes; B, the water that comes out from the ozone contact tower enter in the catalyst bed that inside is filled with hydrous iron oxide or carrier model hydrous iron oxide, and the control residence time of water in catalyst bed is 10～30 minutes; C, the water after oxidation enter the biological activity carbon filterbed, and the control residence time of water in the biological activity carbon filterbed is 10～20 minutes, further remove the organism in anhydrating; D, remove organic water and enter webmaster later on through chlorination.Wherein, hydrous iron oxide prepares according to following step: a, in iron nitrate aqueous solution the hydro-oxidation sodium solution, stir fast and make precipitation of iron ions complete, generate the brown precipitate thing; B, a step is had the sealing of sedimentary mixed solution, under 40～90 ℃ temperature, carry out ageing; C, after the brown precipitate thing becomes yellow mercury oxide, wash throw out repeatedly with distilled water; D, then with yellow mercury oxide dry below 300 ℃, obtain yellow hydroxyl oxidize iron powder.The carrier model hydrous iron oxide prepares according to following step: a, the dilute hydrochloric acid that carrier is put into pH=1～2 soaked 12 hours; Carrier after b, flushing are soaked, and then put into iron nitrate solution and soaked 24 hours; C, to wherein adding sodium hydroxide solution, iron ion is precipitated fully, generate the brown precipitate thing; D, the c step is had the sealing of sedimentary mixed solution, under 40～90 ℃ temperature, carry out ageing; E, after the brown precipitate thing becomes yellow mercury oxide, wash throw out repeatedly with distilled water; F, then with yellow mercury oxide dry below 300 ℃, obtain yellow carrier model hydroxyl oxidize iron powder.Described carrier is a kind of or any several mixture in granular carbon, natural zeolite, artificial zeolite, activated alumina, haydite and the molecular sieve, and the particle diameter of carrier is 0.5～5mm.
Embodiment two: referring to Fig. 2, what present embodiment and embodiment one were different is, a and b step are: a, the filtered water after handling through traditional water treating processess such as coagulations, precipitation, filtration enter the ozone contact tower that inside is filled with hydrous iron oxide or carrier model hydroxyl oxidize iron catalyst and carry out the O3 catalytic oxidation reaction, and control ozone in water initial concentration is 0.5～1.0mgO
3/ (mgTOC), the residence time of water in the ozone contact tower be 10～30 minutes; B, enter the residual ozone reactor to remove the residual ozone in the water through the water of O3 catalytic oxidation.Other steps are identical with embodiment one with processing condition.
Embodiment three: referring to Fig. 3, what present embodiment and embodiment one were different is, the a step is for adopting multistage ozone oxidation mode, contain the ozone of 0.3～0.8mg/L in the final outflow water of control multistage ozone contact tower, other steps are identical with embodiment one with processing condition.A part of organism is easy to be given full play to the organic ability of ozone direct oxidation and can save ozone dosage by independent ozone oxidation in the water, reaches and removes organic effect preferably.Present embodiment helps giving full play to the oxidation capacity of ozone, saves the throwing amount of ozone, reaches and removes organic effect preferably.
Claims (7)
1, with the hydrous iron oxide is the O3 catalytic oxidation method for processing water supply depth of catalyzer, it is characterized in that it carries out according to following step: a, the filtered water after handling through traditional water treating processess such as coagulation, precipitation, filtrations enter the ozone contact tower and carry out ozone oxidation reaction, and control ozone in water initial concentration is 0.5～1.0mgO
3/ (mgTOC), the residence time of water in the ozone contact tower be 10～20 minutes; B, the water that comes out from the ozone contact tower enter in the catalyst bed that inside is filled with hydrous iron oxide or carrier model hydrous iron oxide, and the control residence time of water in catalyst bed is 10～30 minutes; C, the water after oxidation enter the biological activity carbon filterbed, and the control residence time of water in the biological activity carbon filterbed is 10～20 minutes, further remove the organism in anhydrating; D, remove organic water and enter webmaster later on through chlorination.
2, according to claim 1 is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, it is characterized in that hydrous iron oxide prepares according to following step: a, hydro-oxidation sodium solution in iron nitrate aqueous solution, stirring makes precipitation of iron ions complete fast, generates the brown precipitate thing; B, a step is had the sealing of sedimentary mixed solution, under 40～90 ℃ temperature, carry out ageing; C, after the brown precipitate thing becomes yellow mercury oxide, wash throw out repeatedly with distilled water; D, then with yellow mercury oxide dry below 300 ℃, obtain yellow hydroxyl oxidize iron powder.
3, according to claim 1 is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, it is characterized in that the carrier model hydrous iron oxide prepares according to following step: a, the dilute hydrochloric acid that carrier is put into pH=1～2 soaked 12 hours; Carrier after b, flushing are soaked, and then put into iron nitrate solution and soaked 24 hours; C, to wherein adding sodium hydroxide solution, iron ion is precipitated fully, generate the brown precipitate thing; D, the c step is had the sealing of sedimentary mixed solution, under 40～90 ℃ temperature, carry out ageing; E, after the brown precipitate thing becomes yellow mercury oxide, wash throw out repeatedly with distilled water; F, then with yellow mercury oxide dry below 300 ℃, obtain yellow carrier model hydroxyl oxidize iron powder.
4, according to claim 3 is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, it is characterized in that carrier is a kind of or any several mixture in granular carbon, natural zeolite, artificial zeolite, activated alumina, haydite and the molecular sieve.
5, according to claim 3 or 4 described be the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, the particle diameter that it is characterized in that carrier is 0.5～5mm.
6, according to claim 1 is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, it is characterized in that a and b step are: a, water after filtering enter the ozone contact tower that inside is filled with hydrous iron oxide or carrier model hydroxyl oxidize iron catalyst and carry out the O3 catalytic oxidation reaction, and control ozone in water initial concentration is 0.5～1.0mgO
3/ (mgTOC), the residence time of water in the ozone contact tower is 10～30 minutes; B, enter the residual ozone reactor to remove the residual ozone in the water through the water of O3 catalytic oxidation.
7, according to claim 1 is the O3 catalytic oxidation method for processing water supply depth of catalyzer with the hydrous iron oxide, it is characterized in that a step for adopting multistage ozone oxidation mode, contains the ozone of 0.3～0.8mg/L in the final outflow water of control multistage ozone contact tower.
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