CN101602537A - The treatment process of employing ozone for catalytic oxidation of sulphite water solution - Google Patents
The treatment process of employing ozone for catalytic oxidation of sulphite water solution Download PDFInfo
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- CN101602537A CN101602537A CNA2009100411262A CN200910041126A CN101602537A CN 101602537 A CN101602537 A CN 101602537A CN A2009100411262 A CNA2009100411262 A CN A2009100411262A CN 200910041126 A CN200910041126 A CN 200910041126A CN 101602537 A CN101602537 A CN 101602537A
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- sulphite
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Abstract
The invention discloses a kind of treatment process of employing ozone for catalytic oxidation of sulphite water solution, this method is in the atmospheric oxidation process that contains solubility sulphite waste water solution, use the catalyzer of ozone as atmospheric oxidation in air, ozone is 0.01-1% in the airborne weight percent concentration that is used for oxidation; Depress at a standard atmosphere, described air is 50-450 with the volume ratio that contains the sulphite waste water solution: 1.The present invention is in the process of the aqueous solution of atmospheric oxidation sulphite, in air, added small amount of ozone, make the oxidation rate of sulphite improve more than ten times with respect to atmospheric oxidation, the present invention utilizes the adding of ozone, not only participate in the oxidation of inferior sulfate radical directly, and increased the oxidation efficiency of oxygen in the air greatly.This method catalytic oxidation activity is than other metal ion catalyst commonly used, and the oxidation activity of metal oxide catalyst is much higher, and does not have secondary pollution.
Description
Technical field
The present invention relates to the sulphite wastewater treatment method, particularly relate to the treatment process of catalytic ozonation high density sulfite solution; Can be applicable to contain in the wastewater treatment or relevant fine chemistry industry building-up process of sulphite.
Background technology
Contain in the treatment process of SO 2 tail gas in processing, the most frequently used treatment process is with the sulfurous gas in the aqueous sodium hydroxide solution absorption tail gas, and the sulfurous gas in the gas is absorbed as sodium sulfite aqueous solution.Therefore, sulfite solution generally is to be absorbed by the aqueous solution of alkalescence and produced by sulfurous gas, and sulphite is because of its reductibility, and shows chemical oxygen demand (COD) (COD value), when its concentration is higher, can not reach discharging standards.
The oxidation research of sulphite is more.Report according to the study, the speed of reaction of sulfite oxidation reaction is extremely responsive to experiment condition, has been found that liquid composition (SO
3 2-Concentration, dissolved oxygen), the catalyzer (Co of pH value, temperature, trace
2+, Cu
2+, Mn
2+) and the existence of inhibitor (alcohols, phenols, Resorcinol), all affect speed of reaction very consumingly.By atmospheric oxidation,, also it can be oxidized to vitriol as long as the time is enough.As the sodium sulfite aqueous solution that absorbs, in the absorption tower,, still contain oxygen in the gas owing to constantly contact with gas, the part S-WAT can be oxidized into sodium sulfate.But because of the oxidation rate of S-WAT slower, under a lot of situations, the sodium hydroxide in the aqueous solution, all absorb when being converted into S-WAT, at this moment sodium sulfite aqueous solution must be discharged, to replenish fresh aqueous sodium hydroxide solution, in the waste water of discharging, still contain a large amount of S-WATs.S-WAT has reductibility, and this waste water embodies higher COD value, must be further processed and could discharge.
During the air oxidation process of prior art is handled, there are many technological processs just to use the simple air oxidation style, as use the sulfonation factory of sulphur as the raw material production tensio-active agent, sulfurous gas in its tail gas absorbs processing with sodium hydroxide exactly, oxygen in the tail gas is oxidized to sodium sulfate with the part S-WAT again, but its oxidation efficiency is low, when the sodium hydroxide in the water ran out of about 8 hours, having only seldom in the waste water, the part S-WAT is converted into sodium sulfate, S-WAT content in the discharge water is still higher, shows than higher COD value.Use some metal ions such as Co
2+, Cu
2+, Mn
2+Can improve the oxidation rate of S-WAT Deng institute's catalyzer, but oxidation rate is still undesirable, in addition, still has these heavy metal ion in the waste water after the processing, needs to handle further to remove and to discharge.Metal oxide such as MnO
2Also just play the catalysed oxidn of part, but catalytic capability is limited, also is difficult to satisfy industrial due requirement.
Chinese invention patent application CN200710066704.9 discloses the control method of SO 2 index in a kind of shrimps processing, this method is earlier shrimps to be cleaned, be that the water of 2mg/L～6mg/L carries out immersion treatment to shrimps in container with 4 ℃～21 ℃, ozone concn again, the time of immersion is 10min～30min.The raw produce content of sulfur dioxide is reduced to below the 100mg/kg, and cooked content of sulfur dioxide is reduced to below the 30mg/kg, and keeps original appearance color and local flavor.But this application is the control at sulfurous gas, and be that water ozoniferous is carried out immersion treatment to shrimps, the catalyzed oxidation effect is little, can only be used for the sulfur-containing waste water occasion of lower concentration, and can't handle the waste water solution that contains of the concentration 10000mg/L of S-WAT.
Summary of the invention
The objective of the invention is to overcome existing slow, the inefficient problem of wastewater processing technology oxidation catalysis that contains sulphite, a kind of oxidation efficiency height is provided, need not further to remove the treatment process of the employing ozone for catalytic oxidation of sulphite water solution of metal ion after the oxidation.
Principle of the present invention: in the process of the aqueous solution of atmospheric oxidation sulphite, in air, added small amount of ozone, make the oxidation rate of sulphite improve more than ten times with respect to atmospheric oxidation, the present invention utilizes the adding of ozone, not only participate in the oxidation of inferior sulfate radical directly, and increased the oxidation efficiency of oxygen in the air greatly.
Purpose of the present invention is achieved through the following technical solutions:
A kind of treatment process of employing ozone for catalytic oxidation of sulphite water solution: in the atmospheric oxidation process that contains solubility sulphite waste water solution, use the catalyzer of ozone as atmospheric oxidation in air, ozone is 0.01-1% in the airborne weight percent concentration that is used for oxidation; Depress at a standard atmosphere, described air is 50-450 with the volume ratio that contains the sulphite waste water solution: 1.
Described ozone adds by gas ozoniferous, and the gas of described ozone produces by ozonizer.
The described ozone gas that contains directly joins the airflow that is used for the oxidation sulfite solution by Y-tube.
Described sulphite is S-WAT.
The described concentration that contains the waste water solution of S-WAT is 25000mg/L～100000mg/L.
The described COD content that contains the waste water solution of S-WAT is 5100mg/L～20000mg/L.
The described pH value that contains the waste water solution of S-WAT is 6～9.
The present invention has following advantage and beneficial effect:
With the catalyzer of ozone as the sodium sulfite aqueous solution catalyzed oxidation, have the oxidation efficiency height, the trouble that does not have after the oxidation as need further remove with metal ion catalyst, it is extremely convenient to use.When the atmospheric oxidation sodium sulfite aqueous solution, add small amount of ozone, the oxidation rate of its sodium sulfite aqueous solution improves more than ten times, and catalytic oxidation activity is than other metal ion catalyst commonly used, the oxidation activity of metal oxide catalyst is much higher, and does not have secondary pollution.
Embodiment
For a better understanding of the present invention, the invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the scope that embodiment explains.
Embodiment 1
Certain contains the waste water solution of S-WAT, and the concentration 100000mg/L of S-WAT, COD content are 20000mg/L, the about 8-9 of pH value of solution, and the volume of waste water is 4 liters.Produce gas ozoniferous by ozonizer, its weight concentration ozoniferous is 1-2%, then with gas ozoniferous, to contain ozone gas by Y-tube and directly join the airflow that is used for the oxidation sulfite solution, then the concentration of ozone can be because of descending than different with Air mixing in the gas mixture, control ozone is 1% in the airborne weight percent concentration that is used for oxidation, a standard atmosphere is depressed, the ozone-containing air flow is 0.3 cubic metre/hour, with ozone-containing air to sodium sulfite solution aeration 6 hours, the concentration of S-WAT drops to 1200mg/L, the COD of water outlet is also from original 20000mg/L, drop to 280mg/L, near the emission standard of waste water.Therefore COD value, a part is that residual S-WAT offers, and another part is not have the organism of degrading in the water, and this waste water is again through the FENTON chemical oxidation treatment, and wherein COD is dropped to below 80, reaches national specified discharge standard.
Experiment shows that by add ozone in oxidation air, the amount of the oxidation S-WAT of ozone own is also few, but the utilization ratio of oxygen has improved more than ten times with respect to pure air catalysis in the air.Treatment time also shortens dramatically, and this example treatment time is 6 hours, but if there is not ozone, and often more than the twenty four hours, and effect is all undesirable.
Embodiment 2
Certain contains the waste water solution of S-WAT, and in volume was 5 cubic metres reaction vessel, the concentration 35000mg/L of S-WAT, COD content were 7000mg/L, the about 6-7 of pH value of solution, 4 cubic metres of the volumes of waste water.Produce gas ozoniferous by ozonizer, its weight concentration ozoniferous is 1-2%, then with gas ozoniferous, to contain ozone gas by Y-tube and directly join the airflow that is used for the oxidation sulfite solution, then the concentration of ozone can be because of descending than different with Air mixing in the gas mixture, control ozone is 0.05% in the airborne weight percent concentration that is used for oxidation, a standard atmosphere is depressed, 30 cubic metres/hour of the flows of ozone-containing air, 7 hours catalytic oxidation time, the concentration of S-WAT drops to 400mg/L, and the COD of water outlet is also from original 7000mg/L, drop to 90mg/L, reach the emission standard of waste water.
Experiment shows that by add ozone in oxidation air, the amount of the oxidation S-WAT of ozone own is also few, but the utilization ratio of oxygen has improved more than ten times with respect to pure air catalysis in the air.Treatment time also shortens dramatically, and this example treatment time is 7 hours, but if there is not ozone, and often more than the twenty four hours, and effect is all undesirable.
Embodiment 3
Certain contains the waste water solution of S-WAT, and in volume was 1 cubic metre reaction vessel, the concentration 25000mg/L of S-WAT, COD content were 5100mg/L, the about 7-8 of pH value of solution, 600 liters of the volumes of waste water.Produce gas ozoniferous by ozonizer, its weight concentration ozoniferous is 1-2%, then with gas ozoniferous, to contain ozone gas by Y-tube and directly join the airflow that is used for the oxidation sulfite solution, then the concentration of ozone can be because of descending than different with Air mixing in the gas mixture, control ozone is 0.01% in the airborne weight percent concentration that is used for oxidation, a standard atmosphere is depressed, 10 cubic metres/hour of the flows of air, 4 hours catalytic oxidation time, after testing, the concentration of S-WAT drops to 300mg/L, the COD of water outlet also from original 5100mg/L, drops to 70mg/L, reaches the emission standard of waste water.
Experiment shows that by add ozone in oxidation air, the amount of the oxidation S-WAT of ozone own is also few, but the utilization ratio of oxygen has improved more than ten times with respect to pure air catalysis in the air.Treatment time also shortens dramatically, and this example treatment time is 4 hours, but if there is not ozone, and often more than the twenty four hours, and effect is all undesirable.
Need to prove the inferior sulfate radical of the airborne dioxygen oxidation sulphite of ozone catalytic of the present invention, its oxidation object is a sulfite ion, far with positively charged ion, the foregoing description provides the example of the waste water that contains S-WAT, in fact, other contains the waste water that solubility contains sulphite all identical effect, promptly to by in air, adding ozone, the inferior sulfate radical oxidation rate improves more than ten times with respect to atmospheric oxidation, the present invention utilizes the adding of ozone, not only participate in the oxidation of inferior sulfate radical directly, and increased the oxidation efficiency of oxygen in the air greatly.
Claims (7)
1, a kind of treatment process of employing ozone for catalytic oxidation of sulphite water solution, it is characterized in that: in the atmospheric oxidation process that contains solubility sulphite waste water solution, use the catalyzer of ozone as atmospheric oxidation in air, ozone is 0.01-1% in the airborne weight percent concentration that is used for oxidation; Depress at a standard atmosphere, described air is 50-450 with the volume ratio that contains the sulphite waste water solution: 1.
2, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 1 is characterized in that: described ozone adds by gas ozoniferous, and the gas of described ozone produces by ozonizer.
3, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 2 is characterized in that: the described ozone gas that contains directly joins the airflow that is used for the oxidation sulfite solution by Y-tube.
4, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 1 is characterized in that: described sulphite is S-WAT.
5, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 4 is characterized in that: the described concentration that contains the waste water solution of S-WAT is 25000mg/L～100000mg/L.
6, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 4 is characterized in that: the described COD content that contains the waste water solution of S-WAT is 5100mg/L～20000mg/L.
7, the treatment process of employing ozone for catalytic oxidation of sulphite water solution according to claim 4 is characterized in that: the described pH value that contains the waste water solution of S-WAT is 6～9.
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| CN2009100411262A CN101602537B (en) | 2009-07-15 | 2009-07-15 | Processing method employing ozone for catalytic oxidation of sulphite water solution |
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| CN101602537B CN101602537B (en) | 2012-08-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885529A (en) * | 2010-06-11 | 2010-11-17 | 北京工业大学 | Method for treating high-COD waste water from production of heavy alkylbenzene sulfonate |
| CN102275955A (en) * | 2011-05-17 | 2011-12-14 | 湖南丽臣实业股份有限公司 | Method for preparing mirabilite by using sulfonated end gas absorption solution, and apparatus thereof |
| CN103172218A (en) * | 2013-03-06 | 2013-06-26 | 北京赛科康仑环保科技有限公司 | Method and device for recovery and purifying elemental sulfur from high-concentration sulfate wastewater |
| CN105936535A (en) * | 2016-05-23 | 2016-09-14 | 河海大学 | Catalytic ozonation water treatment method and apparatus thereof |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
| CN114291967A (en) * | 2021-12-21 | 2022-04-08 | 南京大学环境规划设计研究院集团股份公司 | Low-energy-consumption coking plant wastewater treatment process based on ozone catalytic oxidation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2818160B1 (en) * | 2000-12-20 | 2003-03-07 | Air Liquide | WET OXIDATION OR OZONATION OXIDATION PROCESS |
| CN100486677C (en) * | 2004-10-09 | 2009-05-13 | 财团法人工业技术研究院 | Method and apparatus for reducing content of ozone in waste-gas |
| CN101019680A (en) * | 2007-01-10 | 2007-08-22 | 浙江省海洋水产研究所 | Method of controlling SO2 index in processing shrimp |
| CN100558658C (en) * | 2007-02-09 | 2009-11-11 | 中国石油化工股份有限公司 | A kind of treatment process of sulfur-containing waste water |
| CN101200328A (en) * | 2007-11-01 | 2008-06-18 | 华侨大学 | Process for treating electroplating mixed wastewater by air oxidation method |
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2009
- 2009-07-15 CN CN2009100411262A patent/CN101602537B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885529A (en) * | 2010-06-11 | 2010-11-17 | 北京工业大学 | Method for treating high-COD waste water from production of heavy alkylbenzene sulfonate |
| CN102275955A (en) * | 2011-05-17 | 2011-12-14 | 湖南丽臣实业股份有限公司 | Method for preparing mirabilite by using sulfonated end gas absorption solution, and apparatus thereof |
| CN102275955B (en) * | 2011-05-17 | 2013-04-24 | 湖南丽臣实业股份有限公司 | Method for preparing mirabilite by using sulfonated end gas absorption solution, and apparatus thereof |
| CN103172218A (en) * | 2013-03-06 | 2013-06-26 | 北京赛科康仑环保科技有限公司 | Method and device for recovery and purifying elemental sulfur from high-concentration sulfate wastewater |
| CN103172218B (en) * | 2013-03-06 | 2015-03-25 | 北京赛科康仑环保科技有限公司 | Method and device for recovery and purifying elemental sulfur from high-concentration sulfate wastewater |
| CN105936535A (en) * | 2016-05-23 | 2016-09-14 | 河海大学 | Catalytic ozonation water treatment method and apparatus thereof |
| CN105936535B (en) * | 2016-05-23 | 2018-11-09 | 河海大学 | A kind of method for treating water and device of O3 catalytic oxidation |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
| CN110204123B (en) * | 2019-04-16 | 2022-04-12 | 南京工业大学 | Resource comprehensive utilization method for waste salt in fipronil production |
| CN114291967A (en) * | 2021-12-21 | 2022-04-08 | 南京大学环境规划设计研究院集团股份公司 | Low-energy-consumption coking plant wastewater treatment process based on ozone catalytic oxidation |
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| CN101602537B (en) | 2012-08-08 |
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