CN105668764A - Method for treating high-concentration degradation-resistant organic waste water through direct ozone oxidation - Google Patents
Method for treating high-concentration degradation-resistant organic waste water through direct ozone oxidation Download PDFInfo
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- CN105668764A CN105668764A CN201610232023.4A CN201610232023A CN105668764A CN 105668764 A CN105668764 A CN 105668764A CN 201610232023 A CN201610232023 A CN 201610232023A CN 105668764 A CN105668764 A CN 105668764A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a method for treating high-concentration degradation-resistant organic waste water through direct ozone oxidation. The method comprises the main steps that calcium oxide is added into the high-concentration degradation-resistant organic waste water, and the pH value of the waste water is adjusted through the alkali; the waste water is transferred into a device suitable for a gas-liquid reaction, ozone is introduced into the reaction vessel in the stirring state, and solid-liquid separation is conducted on the system after a certain reaction time; the pH of a liquid phase is adjusted to be 6-9 through acid, then up-to-standard release of the liquid phase can be achieved, and treatment of the high-concentration degradation-resistant organic waste water is completed. The invention provides the high-concentration degradation-resistant organic waste water treatment technology which is novel, efficient and low in cost. Meanwhile, the effects of reducing the COD of the high-concentration degradation-resistant organic waste water and eliminating color and odors are achieved.
Description
Technical field
The present invention relates to field of environment engineering, a kind of method that specifically ozone direct oxidation processes high concentration hard-degraded organic waste water.
Background technology
Along with the fast development of China's modern chemical industry, along be that " three wastes " are day by day serious to the pollution of environment. Wherein, organic wastewater with difficult degradation thereby is difficult to degrade because of it, and especially the pollution of environment is particularly acute with prominent by the nitrobenzene wastewater of high concentration.
Nitrobenzene compounds is listed in the row of 68 kinds of priority pollutants by China; Environmental Protection Agency USA is also classified as priority pollutant; it is mainly derived from the chemical industries such as petrochemical industry, pharmacy, explosive wastewater, dyestuff; the fields such as the production being widely used in dyestuff, medicine, pesticide, explosive wastewater, engineering plastics, other chemical products, have the features such as stable chemical nature, high toxicity, " three cause " effect. The wastewater toxicity of nitrobenzene-containing compounds is big, colourity is high, COD is high, difficult for biological degradation, and ecological environment has bigger harm.
At present, the method administering organic wastewater with difficult degradation thereby both at home and abroad specifically includes that Physical, chemical method and biological degradation method.
Physical is most commonly used that absorption method and extraction, although the processing technological flow of Physical is relatively easy, and investment and operating cost are not high. But, Physical, to the removal efficiency of hardly degraded organic substance is low and adsorbent is short for service life, long processing period, easily causes secondary pollution.
Bioanalysis is the wastewater treatment means of a kind of low energy consumption and non-secondary pollution. It can be difficult to process the organic wastewater of difficult degradation, the especially organic wastewater with difficult degradation thereby of high concentration. Its reason is: the stable chemical nature of the hardly degraded organic substance of high concentration, Ecotoxicology is big.
Ozonation in chemical method, thorough because having organics removal, the advantage that secondary pollution is controlled, it is a kind of method of environmentally friendly process high concentration hard-degraded organic waste water, is increasingly becoming study hotspot up-to-date both at home and abroad.
Research shows, it is better that ozone oxidation and some other physical method multiple techniques process organic wastewater ratio are used alone ozone direct oxidation technique effect. But, multiple techniques can increase processing cost, and makes complex treatment process. Therefore, research uses the method that ozone efficiently individually directly processes containing organic pollutant wastewater urgently to be resolved hurrily.
In prior art, there is one Ca (OH)2Making " catalyst ", " catalysis " ozone removes the method for waste water persistent organic pollutants. But, the organic wastewater that object is difficult degradation that this method requires, but the type of not clear and definite organic wastewater with difficult degradation thereby.
And this method for hardly degraded organic substance be: organic chloride class, organophosphorus pesticide class, aromatic nitro compound class, (different) quinoline woods class, pyridines etc. Wherein, aromatic nitro compound class (such as nitro (first) benzene class) Organic substance is one of Organic substance being most difficult to direct degradation treatment in waste water.
Prior art there is also a kind of method, but its concentration processing waste water is relatively low, it is common in situation, waste water COD maximum is lower than 1000mg/L, and the organic COD value of wherein difficult degradation is respectively less than 300mg/L; And the content of hardly degraded organic substance is not carried out requirement by these methods. And in these methods, it does not have the acid-base value of waste water is carried out requirement, it is impossible to obtain better effect;
And high concentration hard-degraded organic waste water COD is between 1000mg/L～3500mg/L, wherein, hardly degraded organic substance content is at more than 300mg/L. Therefore, the very difficult of method provided in prior art makes the COD of waste water, color and stink reach discharge standard.
Summary of the invention
Present invention aim to address in prior art, the problem that chemical method is difficult to make the organic wastewater high speed purifying of high concentration, difficult degradation.
Employed technical scheme comprise that such for realizing the purpose of the present invention, a kind of ozone direct oxidation processes the method for high concentration hard-degraded organic waste water, it is characterised in that comprise the following steps:
1) in high concentration hard-degraded organic waste water, add calcium oxide, obtain mixture A, the mass volume ratio (g L) of described calcium oxide and high concentration hard-degraded organic waste water range for 10 1～30 1;
2) in mixture A, add alkaline matter, make pH=12.0～13.5 of waste water, obtain mixture B;
3) mixture B is transferred in gas-liquid reaction apparatus, stirring, pass into ozone simultaneously, obtain mixture C; Described pass into ozone time range be: 0.5h～2h, ozone concentration range is: 20～120mg/L, and flow rates is 6～30L/L h. The COD of described mixture C, color and stink reach discharge standard;
4) mixture C is carried out solid-liquid separation, the liquid phase acidic materials adjustment after separating is discharged to pH=6～9.
Further, the COD of described high concentration hard-degraded organic waste water ranges for: 1000～3500mg/L; Wherein the content of organics of difficult degradation is more than 300mg/L, and the Organic substance of described difficult degradation specifically includes that organic chloride class, organophosphorus pesticide class, aromatic nitro compound class, (different) quinoline woods class and pyridines etc.
Further, described step 2) in alkaline matter be sodium hydroxide.
Further, described step 4) in acidic materials include sulphuric acid and hydrochloric acid.
Further, described step 3) in gas-liquid reaction apparatus be reactor prepared by resistance to ozone corrosion material.
Further, described step 3) in discharge standard be " People's Republic of China's integrated wastewater discharge standard " (GB8978--1996).
What deserves to be explained is, CaO (is converted into Ca (OH) in waste water, under operating condition2) as the solid phase of system, concrete function includes: maintenance system acid-base value, adsorbent and ozone dissipation medium, therefore, the clearance of COD and CaO or Ca (OH)2Amount have significant relation.
Employed technical scheme comprise that for realizing the object of the invention such, the invention have the advantages that
1) reaction system is gentle, all reacts at normal temperatures and pressures;
2) method is simple, workable, it is simple to popularization and application in practice;
3) quick and high efficient reaction, to hardly degraded organic substance content at the high-concentration hardly-degradable of more than 300mg/L organic degraded ratio more thoroughly, the clearance of COD is up to more than 97%;
4) Ca (OH) is adopted2As the solid phase of reaction system, alkaline matter regulates pH value of waste water, utilizes CaO/Ca (OH)2Maintain pH=12.0～13.5 of reaction system, dispersion ozone, absorption or sandwich nitrobenzene and catabolite thereof.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention and be only limitted to following embodiment. Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should include in protection scope of the present invention.
Embodiment 1:
Using the method that a kind of ozone direct oxidation of the present invention processes high concentration hard-degraded organic waste water, the high concentration Methylnitrobenzene class waste water that certain chemical plant produces the generation of toluene di-isocyanate(TDI) process processes.
The COD of this high concentration Methylnitrobenzene class waste water is 2576mg/L, and Methylnitrobenzene content is more than 500mg/L, and there is grease on upper strata, has abnormal flavour, and acidity is very big, and colourity is very big.
The method comprises the following steps:
1) taking 250mL Methylnitrobenzene class waste water in beaker, adding CaO solid masses is 7.17g (calcium oxide/waste water=28.68:1, g/L), stirs;
2) measuring its pH with pH meter is 12.33;
3) this waste water is proceeded in gas-liquid reaction device, pass into ozone 1h. Ozone concentration is: 90mg/L, and flow velocity is: 10.0L/L h.
4) by step 3) in the mixture that obtains carry out solid-liquid separation, by the liquid phase sulphuric acid (H after separating2SO4) regulate and discharge to pH=7.
Specific experiment effect such as following table:
From experimental result it can be seen that the present embodiment adopts the method to make the COD clearance of this waste water reach 98.37%, percent of decolourization is up to 99%, and free from extraneous odour, and waste water is fully achieved discharge standard.
Embodiment 2:
Using the method that a kind of ozone direct oxidation of the present invention processes high concentration hard-degraded organic waste water, the high concentration Methylnitrobenzene class waste water that certain chemical plant produces the generation of toluene di-isocyanate(TDI) process processes.
This high concentration Methylnitrobenzene class waste water COD is 2772mg/L, and Methylnitrobenzene content is more than 500mg/L, and there is grease on upper strata, has abnormal flavour, and acidity is very big, and colourity is very big.
1) taking 250mL Methylnitrobenzene class waste water in beaker, adding CaO solid masses is 6.98g (calcium oxide/waste water=27.92:1, g/L), stirs;
2) measuring its pH with pH meter is 12.11;
3) this waste water is proceeded in gas-liquid reaction device, pass into ozone 1h; Ozone concentration is: 90mg/L, and flow rates is: 10.0L/L h.
4) by step 3) in the mixture that obtains carry out solid-liquid separation, by the liquid phase sulphuric acid (H after separating2SO4) regulate and discharge to pH=7.
Specific experiment effect such as following table:
From experimental result it can be seen that the present embodiment adopts the method to make the COD clearance of this waste water reach 97.37%, percent of decolourization is up to 99%, and free from extraneous odour, and waste water is fully achieved discharge standard.
Embodiment 3:
Using the method that a kind of ozone direct oxidation of the present invention processes high concentration hard-degraded organic waste water, the high concentration Methylnitrobenzene class waste water that certain chemical plant produces the generation of toluene di-isocyanate(TDI) process processes.
This high concentration Methylnitrobenzene class waste water COD is 2576mg/L, and Methylnitrobenzene content is more than 500mg/L, and there is grease on upper strata, has abnormal flavour, and acidity is very big, and colourity is very big.
1) taking 250mL Methylnitrobenzene class waste water in beaker, adding CaO solid masses is 3.10g (calcium oxide/waste water=12.4:1, g/L), stirs;
2) under stirring, regulating the acid-base value of waste water with sodium hydroxide, wastewater pH is 12.11;
3) this waste water is proceeded in gas-liquid reaction device, pass into ozone 1h; Ozone concentration is: 90mg/L, and flow rates is: 10.0L/L h.
4) by step 3) in the mixture that obtains carry out solid-liquid separation, by the liquid phase sulphuric acid (H after separating2SO4) regulate and discharge to pH=7.
Specific experiment effect such as following table:
From experimental result it can be seen that the present embodiment adopts the method to make the COD clearance of this waste water reach 97.55%, percent of decolourization is up to 99%, and free from extraneous odour, and waste water is fully achieved discharge standard.
Claims (5)
1. the method that an ozone direct oxidation processes high concentration hard-degraded organic waste water, it is characterised in that comprise the following steps:
1) in high concentration hard-degraded organic waste water, add Powdered calcium oxide, obtain mixture A, the mass volume ratio (g L) of described calcium oxide and high concentration hard-degraded organic waste water range for 10 1～30 1;
2) in mixture A, add alkaline matter, make pH=12.0～13.5 of waste water, obtain mixture B;
3) mixture B is transferred in gas-liquid reaction apparatus, stirring, pass into ozone simultaneously, obtain mixture C; Described pass into ozone time range be: 0.5h～2h, ozone concentration range is: 20～120mg/L, and flow rates is 6～30L/L h. The COD of described mixture C, color and stink reach discharge standard;
4) mixture C is carried out solid-liquid separation, the liquid phase acidic materials adjustment after separating is discharged to pH=6～9.
2. the method that a kind of ozone direct oxidation according to claim 1 processes high concentration hard-degraded organic waste water, it is characterised in that: the COD of described high concentration hard-degraded organic waste water ranges for: 1000～3500mg/L; Wherein the content of organics of difficult degradation is more than 300mg/L, the Organic substance of described difficult degradation mainly includes machine chloride-based, organophosphorus pesticide class, and aromatic nitro compound class, aromatic series are the polycyclic compound of representative, (different) quinoline woods class and pyridines, the inertia Organic substance class that can not be degraded by microorganisms, dye class.
3. a kind of ozone direct oxidation according to claim 1 process high concentration hard-degraded organic waste water method, it is characterised in that: described step 2) in alkaline matter be sodium hydroxide.
4. a kind of ozone direct oxidation according to claim 1 process high concentration hard-degraded organic waste water method, it is characterised in that: described step 4) in acidic materials include sulphuric acid and hydrochloric acid.
5. a kind of ozone direct oxidation according to claim 1 process high concentration hard-degraded organic waste water method, it is characterised in that: described step 3) in gas-liquid reaction apparatus be reactor prepared by resistance to ozone corrosion material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5256752A (en) * | 1975-11-04 | 1977-05-10 | Hitachi Plant Eng & Constr Co Ltd | Process for purifying waste water |
| CN1948190A (en) * | 2006-11-07 | 2007-04-18 | 南京大学 | Treatment method of waste water in fluorofen production |
| CN101514063A (en) * | 2009-03-24 | 2009-08-26 | 郴州市勤鑫高科有限公司 | Advanced treatment method of biochemical tail water of coking wastewater |
| CN103351051A (en) * | 2013-07-30 | 2013-10-16 | 重庆理工大学 | Method for removing organic pollutants in waste water by taking Ca(OH)2 as catalyst of ozone |
| CN105366785A (en) * | 2015-12-18 | 2016-03-02 | 北京伟创力科技有限公司 | Method for improving utilization efficiency of ozone and reducing COD of wastewater |
-
2016
- 2016-04-14 CN CN201610232023.4A patent/CN105668764A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5256752A (en) * | 1975-11-04 | 1977-05-10 | Hitachi Plant Eng & Constr Co Ltd | Process for purifying waste water |
| CN1948190A (en) * | 2006-11-07 | 2007-04-18 | 南京大学 | Treatment method of waste water in fluorofen production |
| CN101514063A (en) * | 2009-03-24 | 2009-08-26 | 郴州市勤鑫高科有限公司 | Advanced treatment method of biochemical tail water of coking wastewater |
| CN103351051A (en) * | 2013-07-30 | 2013-10-16 | 重庆理工大学 | Method for removing organic pollutants in waste water by taking Ca(OH)2 as catalyst of ozone |
| CN105366785A (en) * | 2015-12-18 | 2016-03-02 | 北京伟创力科技有限公司 | Method for improving utilization efficiency of ozone and reducing COD of wastewater |
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