CN104891713A - Catalytic ozonation process for treatment of organic wastewater - Google Patents
Catalytic ozonation process for treatment of organic wastewater Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a high-efficiency catalytic ozonation process which is particularly applicable to purification and treatment of water bodies with organic pollutants. Pretreated organic wastewater is mixed with ozone prior to entering a catalytic oxidation tower through a micronano bubble generation device, and the catalytic oxidation tower is filled with catalytic filler materials for catalyzed oxidative degradation of organics in wastewater. The catalytic filler materials in the catalytic oxidation tower are large in specific surface, ozone catalyzing capability can be enhanced by composite metals on the catalytic filler materials, and effective utilization rate of hydroxyl free radicals can be increased. Compared with traditional catalytic treatment processes and catalytic filler materials, the high-efficiency catalytic ozonation process has the advantage of high efficiency in elimination of toxic and harmful organics in the water bodies.
Description
Technical field
The present invention relates to the treatment process of organic waste water, particularly a kind of catalytic oxidation process for treating of ozone and catalystic material.
Background technology
Hardly degraded organic substance pollution problem and effective governing problem in water, one that has become that China's water surrounding work faces severe problem.Organic pollutant in water body mainly comprises macromole natural organic matter, micro quantity organic pollutant, stink substance, algae and meta-bolites thereof etc.These organism derive from the organic pollutant that the commercial runs such as organic chemical industry, petrochemical complex, medicine, sterilant and weedicide produce usually, have the advantages that concentration is low, toxicity is large, much carcinogenic, teratogenesis, mutagenic effect can be produced, very big to human health damage, and all difficult degradations of these organism, amplify its harm easily through food chain biomagnification, therefore need to adopt certain technique means it to be removed from water body.
Organism in waste water is difficult to directly adopt biochemical method process, needs to adopt physico-chemical process to carry out processing or pre-treatment; In addition, many high concentrated organic wastewaters are after biological second-stage treatment, and lingering section organism major part is refractory organic, causes waste water to be difficult to qualified discharge or reuse, also need to adopt physico-chemical process to carry out advanced treatment.
Chemical oxidization method is one of main method of water pollution control, and conventional oxygenant mainly comprises electronics, permanganate, chlorine, hydrogen peroxide and ozone etc. in the oxygen of wet oxidation, electrochemistry.Relative to other oxygenant, the oxidisability oxygenant more conventional than other of ozone strong, its standard potential is 2.07mV; In addition, ozone oxidation by product is few, is therefore widely used in Water purification, is mainly used to disinfection, except smelling, except algae and Organic substance in water.Closely during the last ten years, along with the manufacturing development of ozonizer, facility investment and the working cost of ozonization water treatment technique are minimized, and the investigation and application in sewage disposal also increases gradually.But the ozonation technology of application at present and equipment exist ozone utilization rate to be reduced, and oxidation effectiveness is poor, is difficult to the problem obtaining satisfied treatment effect in the treatment of waste water.
Ozone chemical conduct more complicated in aqueous, it can direct oxidation organism, or producing the impurity in hydroxy radical qiao oxidation removal water by chain reaction mechanism decomposition, research shows that some metallic elements can promote that ozone decomposed produces the hydroxyl radical free radical of strong oxidizing property; Therefore the usual selective catalysis ozonation technology when utilizing ozonize organic waste water.But in homogeneous catalytic oxidation, catalyzer mixes water-soluble, catalyzer easily runs off and not easily reclaims, and easily produces secondary pollution, and operation and maintenance cost is higher, increases processing cost, is difficult to apply in scale operation; And in heterogeneous catalytic oxidation, there is surperficial heterogeneity and the slower shortcoming of inner diffusing rate in solid catalyst, and oxidation effectiveness is easily subject to the impact of impurity in water body, reduce oxidation efficiency, also may generate by product bromate, result in secondary pollution of water, also HUMAN HEALTH is had an impact.Therefore be necessary to work out a kind of novel catalystic material and novel catalytic oxidation technique, to improve utilization ratio and the oxidation efficiency of ozone.
Summary of the invention
The present invention seeks to for the deficiencies in the prior art and defect, provide a kind of high efficiency catalytic ozonation treatment process, be particularly useful for the purification containing the water body of organic pollutant and process.
For achieving the above object, the technical solution used in the present invention is:
A kind of organic waste water catalytic ozonation treatment process, its key step comprises:
One, pretreated organic waste water is entered self-cleaning filter by vacuum primingpump lifting, in self-cleaning filter, remove most larger suspended substance in waste water, the product water after self-cleaning filter enters cartridge filter, removes the suspended substance in water and colloidalmaterial further;
Two, in step one, the product water of cartridge filter enters in cooling system, carries out heat exchange, the water temperature of sewage is reduced to about 25 DEG C with the recirculated cooling water of cooling system, and water coolant cools to less than 25 DEG C recycles through the cooling-water machine of cooling system simultaneously;
Three, the waste water after heat exchange heats up enters elevated tank, and the available water capacity of elevated tank controls at about 3.5 cubes;
Four, the water outlet of elevated tank mixes with ozone and enters in catalyzed oxidation tower by micro-nano bubble generator, and fill catalytic filler in catalyzed oxidation tower, remove the toxic organics in water after catalyzed oxidation, the ratio of its organics removal is O
3: △ COD>=1:2.0; ;
The tail gas of five, discharging through the outlet of catalyzed oxidation tower is filled with tail gas absorber, tail gas absorber thermal degradation ozone tail gas, ozone again in the thorough decomposed tail gas of catalyst layer, the tail gas after process can carry out in line according to practical situation or enter the exhaust treatment system of Iarge-scale system.
Wherein said catalytic filler is compound heterogeneous catalyst, described catalyzer comprises carrier, active ingredient, pore-creating agent, binding agent, lubricant and acid, wherein the weight percent of each component is carrier 50-80%, active ingredient 10-15%, pore-creating agent 3-8%, binding agent 3-7%, lubricant 1-4% and sour 1-2%, described carrier selects molecular sieve, mesoporous ceramic or diatomite, described active ingredient is composite Nano metal oxide compound or metallic solution, metal is wherein the composition of nano-titanium and zirconium, the mol ratio of titanium and zirconium is 10:1-3, described pore-creating agent is charcoal, biological starch or polyoxyethylene glycol, described binding agent is aluminum hydroxide gel, described lubricant is glycerine, described acid is nitric acid,
Catalytic filler of the present invention adopts following methods to prepare:
(1) titanium dioxide and zirconia particles are ground, prepare active metal composite nano oxide particle; Also can adopt the solion mixed preparing composition metal composition solution of titanium and zirconium, wherein in above-mentioned oxide particle or metal composites solution, the mol ratio of titanium and zirconium is 10:1-3.
(2) carrier powder is broken into the particle of particle diameter 10-100nm, floods with ethanol after carrier granule is mixed with the oxide particle of step 1, fully stir dipping 2-5h, dry at 100-150 DEG C after taking-up; Or by the metal composites solution of carrier granule direct impregnation in step 1, fully stir 2-5h, leave standstill elimination solution after 48 hours.
(3) mix obtaining particle and pore-creating agent, binding agent, lubricant and acid after drying in step 2 or filtering, mixing after product first dries 2h at 80 ~ 150 DEG C, after 400 ~ 600 DEG C of roastings 2 ~ 4 hours, pulverize and obtain carrier filler afterwards;
Catalytic ozonation technique of the present invention is applicable to the process of various organic waste water, comprises the tap water containing light concentration organic pollutant, is particularly useful for the organic waste water that organic pesticide, petroleum refining and the industry such as Coal Chemical Industry, pharmacy produce;
The present invention has following beneficial effect:
1) the present invention adopts micro-nano bubble generator to carry in the tower of falling catalyzed oxidation by the mixture of waste water and ozone, the scatter coefficient of ozone in waste water is high, with the organism in waste water and catalyst exposure more abundant, the hydroxyl radical free radical production rate of ozone is high, can remove the toxic organics in water body more efficiently, result shows technique of the present invention apparently higher than traditional ozonize technique to organic removal efficiency.
2) catalyst specific surface of the present invention's employing is comparatively large, and stable in properties, can be adsorbed with organic pollutants, increase pollutent and hydroxyl radical free radical contact area, the composition metal of load on it can strengthen the catalytic capability to ozone, promotes hydroxyl radical free radical effective rate of utilization, and effect is disposed in strengthening.
Accompanying drawing explanation
Fig. 1 represents the process flow sheet of process organic waste water of the present invention.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
As shown in Figure 1, the step of organic waste water catalytic ozonation treatment process of the present invention comprises:
One, pretreated organic waste water is entered self-cleaning filter by vacuum primingpump lifting, in self-cleaning filter, remove most larger suspended substance in waste water, the product water after self-cleaning filter enters cartridge filter, removes the suspended substance in water and colloidalmaterial further;
Two, in step one, the product water of cartridge filter enters in the interchanger of cooling system, heat exchange is carried out with the recirculated cooling water of cooling system, the water temperature of waste water is reduced to about 25 DEG C, and water coolant cools to less than 25 DEG C recycles through the cooling-water machine of cooling system simultaneously;
Three, the waste water after heat exchange heats up enters elevated tank, and the available water capacity of elevated tank controls at about 3.5 cubes;
Four, the water outlet of elevated tank mixes with the ozone that ozonizer produces, and enter into stable pipe by micro-nano pump and form stable nanometer gas-liquid mixed phase, then be transported in catalyzed oxidation tower, catalyst filling filler in catalyzed oxidation tower, toxic organics after catalyzed oxidation in water is removed, and its organic ratio removed is O
3: △ COD>=1:2.0(mass ratio);
The tail gas of five, discharging through the outlet of catalyzed oxidation top of tower enters tail gas absorber, tail gas absorber thermal degradation ozone tail gas, ozone again in the thorough decomposed tail gas of catalyst layer, the tail gas after process can carry out in line according to practical situation or enter the exhaust treatment system of Iarge-scale system.
Above-mentioned catalyst filling is compound heterogeneous catalyst, wherein the component of catalyzer comprises carrier, active ingredient, pore-creating agent, binding agent, lubricant and acid, the weight percent of each component is carrier 50-80%, active ingredient 10-15%, pore-creating agent 3-8%, binding agent 3-7%, lubricant 1-4% and sour 1-2%, described carrier selects molecular sieve, mesoporous ceramic or diatomite, described active ingredient is composite Nano metal oxide compound or metallic solution, metal is wherein the composition of nano-titanium and zirconium, the mol ratio of titanium and zirconium is 10:1-3, described pore-creating agent is charcoal, biological starch or polyoxyethylene glycol, described binding agent is aluminum hydroxide gel, described lubricant is glycerine, described acid is nitric acid,
Catalytic filler of the present invention adopts following methods to prepare:
(1) titanium dioxide and zirconia particles are ground, prepare active metal composite nano oxide particle; Also can adopt the solion mixed preparing composition metal composition solution of titanium and zirconium, wherein in above-mentioned oxide particle or metal composites solution, the mol ratio of titanium and zirconium is 10:1-3.
(2) carrier powder is broken into the particle of particle diameter 10-100nm, impregnated in ethanol after carrier granule is mixed with the oxide particle of step 1, after fully stirring, leave standstill 2-5h, dry at 100-150 DEG C after taking-up; Or by the metal composites solution of carrier granule direct impregnation in step 1, fully stir 2-5h, leave standstill elimination solution after 48 hours.
(3) mix obtaining particle and pore-creating agent, binding agent, lubricant and acid after drying in step 2 or filtering, mixing after product first dries 2h at 80 ~ 150 DEG C, after 400 ~ 600 DEG C of roastings 2 ~ 4 hours, pulverize and obtain catalyst filling afterwards;
Utilize treatment process process chemical plant of the present invention o-Xylol pollutant effluents, COD concentration in waste water is 1600mg/L, the technical process described in Fig. 1 is adopted to process above-mentioned waste water, the support of the catalyst selected is diatomite, supported titanium and zirconium active ingredient on it, consisting of of catalyst components: diatomite 70%, titanium and zirconium 15%, charcoal 5%, aluminum hydroxide gel 5%, glycerine 3% and nitric acid 2%, the flow of ozone is 2.5L/min, COD concentration in processed waste water is that 20mg/L, COD clearance reaches 98.75%.
It should be noted that; although the present invention's openly preferred embodiment; but they are not for limiting the present invention; any those skilled in the art; without departing from the scope of the present invention; various changes can be made and adjustment, and what therefore protection scope of the present invention should define with the claims of the application is as the criterion.
Claims (3)
1. an organic waste water catalytic ozonation treatment process, its key step comprises:
One, pretreated organic waste water is entered self-cleaning filter by vacuum primingpump lifting, in self-cleaning filter, remove most larger suspended substance in waste water, the product water after self-cleaning filter enters cartridge filter, removes the suspended substance in water and colloidalmaterial further;
Two, in step one, the product water of cartridge filter enters in cooling system, carries out heat exchange, the water temperature of sewage is reduced to about 25 DEG C with the recirculated cooling water of cooling system, and water coolant cools to less than 25 DEG C recycles through the cooling-water machine of cooling system simultaneously;
Three, the waste water after heat exchange heats up enters elevated tank, and the available water capacity of elevated tank controls at about 3.5 cubes;
Four, the water outlet of elevated tank mixes with ozone and enters in catalyzed oxidation tower by micro-nano bubble generator, and fill catalytic filler in catalyzed oxidation tower, remove the toxic organics in water after catalyzed oxidation, the ratio of its organics removal is O
3: △ COD>=1:2.0; ;
The tail gas of five, discharging through the outlet of catalyzed oxidation tower is filled with tail gas absorber, tail gas absorber thermal degradation ozone tail gas, ozone again in the thorough decomposed tail gas of catalyst layer, the tail gas after process can carry out in line according to practical situation or enter the exhaust treatment system of Iarge-scale system.
2. treatment process as claimed in claim 1, it is characterized in that: described catalytic filler is compound heterogeneous catalyst, described catalyzer comprises carrier, active ingredient, pore-creating agent, binding agent, lubricant and acid, wherein the weight percent of each component is carrier 50-80%, active ingredient 10-15%, pore-creating agent 3-8%, binding agent 3-7%, lubricant 1-4% and sour 1-2%, described carrier selects molecular sieve, mesoporous ceramic or diatomite, described active ingredient is composite Nano metal oxide compound or metallic solution, metal is wherein the composition of nano-titanium and zirconium, the mol ratio of titanium and zirconium is 10:1-3, described pore-creating agent is charcoal, biological starch or polyoxyethylene glycol, described binding agent is aluminum hydroxide gel, described lubricant is glycerine, described acid is nitric acid.
3. treatment process as claimed in claim 2, is characterized in that: the preparation method of described catalytic filler is as follows:
(1) titanium dioxide and zirconia particles are ground, prepare active metal composite nano oxide particle; Also can adopt the solion mixed preparing composition metal composition solution of titanium and zirconium, wherein in above-mentioned oxide particle or metal composites solution, the mol ratio of titanium and zirconium is 10:1-3;
(2) carrier powder is broken into the particle of particle diameter 10-100nm, floods with ethanol after carrier granule is mixed with the oxide particle of step 1, fully stir dipping 2-5h, dry at 100-150 DEG C after taking-up; Or by the metal composites solution of carrier granule direct impregnation in step 1, fully stir 2-5h, leave standstill elimination solution after 48 hours;
(3) mix obtaining particle and pore-creating agent, binding agent, lubricant and acid after drying in step 2 or filtering, mixing after product first dries 2h at 80 ~ 150 DEG C, after 400 ~ 600 DEG C of roastings 2 ~ 4 hours, pulverize and obtain catalytic filler afterwards.
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| CN105435795A (en) * | 2016-01-29 | 2016-03-30 | 于月光 | Method and application for preparing catalyst by using red mud as raw materials |
| CN105771969A (en) * | 2016-04-08 | 2016-07-20 | 北京今大禹环境技术股份有限公司 | Preparation method of targeted catalyst for treating hydrocarbon-containing wastewater |
| CN105854866A (en) * | 2016-04-08 | 2016-08-17 | 北京今大禹环境技术股份有限公司 | Preparation method of targeting catalyst used for treating heterocycle-containing compound wastewater |
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