CN101602537B - Processing method employing ozone for catalytic oxidation of sulphite water solution - Google Patents
Processing method employing ozone for catalytic oxidation of sulphite water solution Download PDFInfo
- Publication number
- CN101602537B CN101602537B CN2009100411262A CN200910041126A CN101602537B CN 101602537 B CN101602537 B CN 101602537B CN 2009100411262 A CN2009100411262 A CN 2009100411262A CN 200910041126 A CN200910041126 A CN 200910041126A CN 101602537 B CN101602537 B CN 101602537B
- Authority
- CN
- China
- Prior art keywords
- ozone
- oxidation
- air
- sulfite
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 6
- 238000003672 processing method Methods 0.000 title 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 title 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 76
- 235000010265 sodium sulphite Nutrition 0.000 claims description 38
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000012545 processing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 241000143060 Americamysis bahia Species 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明公开了一种臭氧强化氧化亚硫酸盐水溶液的处理方法，该方法是在含可溶性亚硫酸盐废水溶液的空气氧化过程中，在空气中使用臭氧作为空气氧化的催化剂，臭氧在用于氧化的空气中的重量百分比浓度为0.01-1％；在一个标准大气压下，所述空气与含亚硫酸盐废水溶液的体积比为50-450∶1。本发明在空气氧化亚硫酸盐的水溶液的过程中，向空气中加入了少量臭氧，使亚硫酸盐的氧化速度相对于空气氧化提高十倍以上，本发明利用臭氧的加入，不仅直接参与了亚硫酸根的氧化，而且大大增加了空气中氧气的氧化效率。该方法催化氧化活性比其它常用的金属离子催化剂，金属氧化物催化剂的氧化活性高得多，且没有二次污染。The invention discloses a treatment method for ozone-enhanced oxidation of sulfite aqueous solution. The method is to use ozone in the air as a catalyst for air oxidation during the air oxidation process of wastewater containing soluble sulfite, and the ozone is used for oxidation The weight percent concentration in the air is 0.01-1%; under a standard atmospheric pressure, the volume ratio of the air to the sulfite-containing wastewater solution is 50-450:1. In the process of air oxidation of sulfite aqueous solution, the present invention adds a small amount of ozone to the air, so that the oxidation speed of sulfite is increased by more than ten times compared with air oxidation. Oxidation of sulfate, and greatly increased the oxidation efficiency of oxygen in the air. The catalytic oxidation activity of the method is much higher than that of other commonly used metal ion catalysts and metal oxide catalysts, and there is no secondary pollution.
Description
技术领域 technical field
本发明涉及亚硫酸盐废水的处理方法，特别是涉及臭氧催化氧化高浓度亚硫酸盐水溶液的处理方法；可应用于含亚硫酸盐的废水处理或相关精细化工合成过程中。The invention relates to a treatment method for sulfite wastewater, in particular to a treatment method for ozone catalytic oxidation of high-concentration sulfite aqueous solution; it can be applied to the treatment of wastewater containing sulfite or the synthesis process of related fine chemicals.
背景技术 Background technique
在处理含有二氧化硫尾气的处理工艺中，最常用的处理工艺是用氢氧化钠水溶液吸收尾气中的二氧化硫，将气体中的二氧化硫吸收为亚硫酸钠水溶液。因此，亚硫酸盐水溶液一般是由二氧化硫被碱性的水溶液吸收而产生的，亚硫酸盐因其还原性，而显现出化学需氧量(COD值)，当其浓度较高时，不能达到国家排放标准。In the treatment process of tail gas containing sulfur dioxide, the most commonly used treatment process is to absorb sulfur dioxide in the tail gas with aqueous sodium hydroxide solution, and absorb the sulfur dioxide in the gas into aqueous sodium sulfite solution. Therefore, the sulfite aqueous solution is generally produced by the absorption of sulfur dioxide by the alkaline aqueous solution. The sulfite exhibits chemical oxygen demand (COD value) due to its reducing property. When its concentration is high, it cannot reach the national level. Emission Standards.
亚硫酸盐的氧化研究较多。据研究报导，亚硫酸盐氧化反应的反应速率对实验条件极其敏感，已经发现，液相成分(SO3 2-浓度、溶解氧)、pH值、温度、痕量的催化剂(Co2+、Cu2+、Mn2+)和抑制剂(醇类、酚类、对苯二酚)的存在，都很强烈地影响着反应速率。通过空气氧化，只要时间足够，也可将其氧化为硫酸盐。如吸收的亚硫酸钠水溶液，在吸收塔中，由于不断与气体接触，气体中仍含有氧气，部分亚硫酸钠会氧化成为硫酸钠。但因亚硫酸钠的氧化速度较慢，很多情况下，当水溶液中的氢氧化钠，全部吸收转化为亚硫酸钠时，这时必须将亚硫酸钠水溶液排放，以补充新鲜的氢氧化钠水溶液，在排放的废水中，仍含有大量的亚硫酸钠。亚硫酸钠具有还原性，此废水体现出较高的COD值，必须进行进一步的处理才能排放。There are many studies on the oxidation of sulfite. According to research reports, the reaction rate of sulfite oxidation is extremely sensitive to experimental conditions. It has been found that the liquid phase composition (SO 3 2- concentration, dissolved oxygen), pH value, temperature, trace catalyst ( Co 2+ , Mn 2+ ) and the presence of inhibitors (alcohols, phenols, hydroquinone), all strongly affect the reaction rate. It can also be oxidized to sulfate by air oxidation, given sufficient time. Such as the absorbed sodium sulfite aqueous solution, in the absorption tower, due to continuous contact with the gas, the gas still contains oxygen, and part of the sodium sulfite will be oxidized into sodium sulfate. However, due to the slow oxidation rate of sodium sulfite, in many cases, when all the sodium hydroxide in the aqueous solution is absorbed and converted into sodium sulfite, the aqueous sodium sulfite solution must be discharged to supplement fresh aqueous sodium hydroxide solution. , still contains a large amount of sodium sulfite. Sodium sulfite is reducing, and the waste water shows a high COD value, which must be further treated before it can be discharged.
现有技术的空气氧化法处理中，有不少工艺过程就使用简单空气氧化法，如使用硫磺为原料生产表面活性剂的磺化厂，其尾气中的二氧化硫就是用氢氧化钠进行吸收处理，尾气中的氧再将部分亚硫酸钠氧化为硫酸钠，但其氧化效率低，当水中的氢氧化钠在8小时左右消耗完时，废水中只有很少部分亚硫酸钠转化为硫酸钠，排放水中的亚硫酸钠含量仍然较高，表现出比较高的COD值。使用一些金属离子如Co2+、Cu2+、Mn2+等所催化剂可提高亚硫酸钠的氧化速度，但氧化速度仍不理想，另外，处理后的废水中仍存在这些重金属离子，需要进一步地处理脱除才能排放。金属氧化物如MnO2也才起到部分的催化氧化作用，但催化能力有限，也难以满足工业应有的要求。In the air oxidation treatment of the prior art, many processes just use the simple air oxidation method, such as the sulfonation plant that uses sulfur as a raw material to produce surfactants, the sulfur dioxide in the tail gas is absorbed and treated with sodium hydroxide, The oxygen in the tail gas oxidizes part of the sodium sulfite to sodium sulfate, but the oxidation efficiency is low. When the sodium hydroxide in the water is consumed in about 8 hours, only a small part of the sodium sulfite in the wastewater is converted into sodium sulfate, and the sodium sulfite content in the discharged water Still higher, showing a relatively high COD value. Using some metal ions such as Co 2+ , Cu 2+ , Mn 2+ and other catalysts can increase the oxidation rate of sodium sulfite, but the oxidation rate is still not ideal. In addition, these heavy metal ions still exist in the treated wastewater, which needs further treatment Discharge can only be removed. Metal oxides such as MnO 2 also play a part in catalytic oxidation, but the catalytic ability is limited, and it is difficult to meet the due requirements of the industry.
中国发明专利申请CN200710066704.9公开了一种虾类加工中二氧化硫指标的控制方法，该方法是先对虾类进行清洗，再用4℃～21℃、臭氧浓度为2mg/L～6mg/L的水在容器中对虾类进行浸泡处理，浸泡的时间为10min～30min。可使原料产品二氧化硫含量降低到100mg/kg以下，熟制品二氧化硫含量降低到30mg/kg以下，并保持原有的外观颜色和风味。但是该申请是针对二氧化硫的控制，而且是将含臭氧的水对虾类进行浸泡处理，催化氧化效果小，只能用于低浓度的含硫废水场合，而对亚硫酸钠的浓度10000mg/L的含的废水溶液无法处理。Chinese invention patent application CN200710066704.9 discloses a control method of sulfur dioxide index in shrimp processing. The method is to wash the shrimp first, and then use water at 4°C-21°C and ozone concentration of 2mg/L-6mg/L The shrimps are soaked in the container, and the soaking time is 10 minutes to 30 minutes. It can reduce the sulfur dioxide content of raw materials to less than 100mg/kg, and the sulfur dioxide content of cooked products to less than 30mg/kg, and maintain the original appearance color and flavor. However, this application is aimed at the control of sulfur dioxide, and the shrimps are soaked in ozone-containing water, which has a small catalytic oxidation effect and can only be used in low-concentration sulfur-containing wastewater. Wastewater solutions cannot be disposed of.
发明内容 Contents of the invention
本发明的目的在于克服现有含亚硫酸盐的废水处理技术氧化催化慢、效率低的问题，提供一种氧化效率高，氧化后无需进一步脱除金属离子的臭氧强化氧化亚硫酸盐水溶液的处理方法。The purpose of the present invention is to overcome the problems of slow oxidation catalysis and low efficiency in the existing sulfite-containing wastewater treatment technology, and provide an ozone-enhanced treatment of sulfite aqueous solution with high oxidation efficiency and no need to further remove metal ions after oxidation method.
本发明的原理：空气氧化亚硫酸盐的水溶液的过程中，向空气中加入了少量臭氧，使亚硫酸盐的氧化速度相对于空气氧化提高十倍以上，本发明利用臭氧的加入，不仅直接参与了亚硫酸根的氧化，而且大大增加了空气中氧气的氧化效率。The principle of the present invention: in the process of air oxidation of sulfite aqueous solution, a small amount of ozone is added to the air, so that the oxidation speed of sulfite is increased by more than ten times relative to air oxidation. The present invention utilizes the addition of ozone, not only directly participates in It not only reduces the oxidation of sulfite, but also greatly increases the oxidation efficiency of oxygen in the air.
本发明的目的通过如下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种臭氧强化氧化亚硫酸盐水溶液的处理方法：在含可溶性亚硫酸盐废水溶液的空气氧化过程中，在空气中使用臭氧作为空气氧化的催化剂，臭氧在用于氧化的空气中的重量百分比浓度为0.01-1％；在一个标准大气压下，所述空气与含亚硫酸盐废水溶液的体积比为50-450∶1。A treatment method for ozone-enhanced oxidation of sulfite aqueous solution: in the air oxidation process containing soluble sulfite wastewater solution, ozone is used in the air as a catalyst for air oxidation, and the weight percentage concentration of ozone in the air used for oxidation 0.01-1%; under a standard atmospheric pressure, the volume ratio of the air to the sulfite-containing wastewater solution is 50-450:1.
所述臭氧通过含臭氧的气体加入，所述臭氧的气体通过臭氧发生器产生。The ozone is added by an ozone-containing gas generated by an ozone generator.
所述含臭氧气体通过三通管直接加入到用于氧化亚硫酸盐水溶液的空气流中。The ozone-containing gas was added directly to the air stream used to oxidize the aqueous sulfite solution through a tee.
所述亚硫酸盐为亚硫酸钠。Described sulfite is sodium sulfite.
所述含亚硫酸钠的废水溶液的浓度为25000mg/L～100000mg/L。The concentration of the sodium sulfite-containing wastewater solution is 25000mg/L˜100000mg/L.
所述含亚硫酸钠的废水溶液的COD含量为5100mg/L～20000mg/L。The COD content of the sodium sulfite-containing wastewater solution is 5100mg/L-20000mg/L.
所述含亚硫酸钠的废水溶液的pH值为6～9。The pH value of the sodium sulfite-containing wastewater solution is 6-9.
本发明具有如下的优点和有益效果：The present invention has following advantage and beneficial effect:
用臭氧作为亚硫酸钠水溶液催化氧化的催化剂，具有氧化效率高，氧化后没有如用金属离子催化剂需要进一步脱除的麻烦，使用极其方便。在空气氧化亚硫酸钠水溶液时，投加少量臭氧，其亚硫酸钠水溶液的氧化速度提高十倍以上，催化氧化活性比其它常用的金属离子催化剂，金属氧化物催化剂的氧化活性高得多，且没有二次污染。Using ozone as a catalyst for the catalytic oxidation of sodium sulfite aqueous solution has high oxidation efficiency, and there is no need for further removal after oxidation, which is extremely convenient to use. When the air oxidizes the sodium sulfite aqueous solution, add a small amount of ozone, the oxidation rate of the sodium sulfite aqueous solution is increased by more than ten times, and the catalytic oxidation activity is much higher than that of other commonly used metal ion catalysts, metal oxide catalysts, and there is no secondary pollution. .
具体实施方式 Detailed ways
为了更好的理解本发明，下面结合具体实施例对本发明作进一步说明，但本发明所要求保护的范围并不局限于实施例所表述的范围。In order to better understand the present invention, the present invention will be further described below in conjunction with specific examples, but the scope of protection claimed by the present invention is not limited to the scope expressed in the examples.
实施例1Example 1
某含亚硫酸钠的废水溶液，亚硫酸钠的浓度100000mg/L，COD含量为20000mg/L，溶液的pH值约8-9，废水的体积为4升。通过臭氧发生器产生含臭氧的气体，其含臭氧的重量浓度为1-2％，然后将含臭氧的气体，通过三通管将含臭氧气体直接加入到用于氧化亚硫酸盐水溶液的空气流中，则混合气中臭氧的浓度会因与空气的混合比不同而下降，控制臭氧在用于氧化的空气中的重量百分比浓度为1％，一个标准大气压下，含臭氧的空气流量为0.3立方米/小时，用含臭氧的空气对亚硫酸钠溶液曝气6个小时，亚硫酸钠的浓度降到1200mg/L，出水的COD也从原来的20000mg/L，下降到280mg/L，接近废水的排放标准。因此COD值，一部分是残留的亚硫酸钠供献的，另一部分是水中没有降解的有机物，此废水再经FENTON化学氧化处理，将其中的COD降到80以下，达到国家规定的排放标准。For a wastewater solution containing sodium sulfite, the concentration of sodium sulfite is 100000mg/L, the COD content is 20000mg/L, the pH value of the solution is about 8-9, and the volume of wastewater is 4 liters. Ozone-containing gas is generated by an ozone generator, and its ozone-containing weight concentration is 1-2%, and then the ozone-containing gas is directly added to the air flow for oxidizing the sulfite aqueous solution through a three-way pipe In the middle, the concentration of ozone in the mixed gas will decrease due to the different mixing ratio with the air. The weight percentage concentration of ozone in the air used for oxidation is controlled to be 1%. Under a standard atmospheric pressure, the flow rate of ozone-containing air is 0.3 cubic meters m/h, using ozone-containing air to aerate the sodium sulfite solution for 6 hours, the concentration of sodium sulfite drops to 1200mg/L, and the COD of the effluent also drops from the original 20000mg/L to 280mg/L, which is close to the discharge standard of wastewater. Therefore, part of the COD value is contributed by the residual sodium sulfite, and the other part is the undegraded organic matter in the water. The wastewater is then treated by FENTON chemical oxidation to reduce the COD to below 80, which meets the national discharge standards.
实验表明，通过在氧化空气中加入臭氧，臭氧本身氧化亚硫酸钠的量并不多，但空气中氧气的利用率相对于纯空气催化提高了十多倍。处理时间也大为缩短，本例处理时间为6小时，但若没有臭氧，往往二十四小时以上，且效果都不理想。Experiments have shown that by adding ozone to the oxidized air, the amount of sodium sulfite oxidized by ozone itself is not much, but the utilization rate of oxygen in the air is more than ten times higher than that of pure air. The processing time is also greatly shortened, and the processing time of this example is 6 hours, but if there is no ozone, it is often more than 24 hours, and the effect is not satisfactory.
实施例2Example 2
某含亚硫酸钠的废水溶液，在体积为5立方米的反应容器中，亚硫酸钠的浓度35000mg/L，COD含量为7000mg/L，溶液的pH值约6-7，废水的体积4立方米。通过臭氧发生器产生含臭氧的气体，其含臭氧的重量浓度为1-2％，然后将含臭氧的气体，通过三通管将含臭氧气体直接加入到用于氧化亚硫酸盐水溶液的空气流中，则混合气中臭氧的浓度会因与空气的混合比不同而下降，控制臭氧在用于氧化的空气中的重量百分比浓度为0.05％，一个标准大气压下，含臭氧的空气的流量30立方米/小时，催化氧化反应时间7小时，亚硫酸钠的浓度降到400mg/L，出水的COD也从原来的7000mg/L，下降到90mg/L，达到废水的排放标准。For a wastewater solution containing sodium sulfite, in a reaction vessel with a volume of 5 cubic meters, the concentration of sodium sulfite is 35000 mg/L, the COD content is 7000 mg/L, the pH value of the solution is about 6-7, and the volume of wastewater is 4 cubic meters. Ozone-containing gas is generated by an ozone generator, and its ozone-containing weight concentration is 1-2%, and then the ozone-containing gas is directly added to the air flow for oxidizing the sulfite aqueous solution through a three-way pipe In the middle, the concentration of ozone in the mixed gas will decrease due to the different mixing ratio with the air. The weight percentage concentration of ozone in the air used for oxidation is controlled to be 0.05%. Under a standard atmospheric pressure, the flow rate of ozone-containing air is 30 cubic meters m/hour, the catalytic oxidation reaction time is 7 hours, the concentration of sodium sulfite drops to 400mg/L, and the COD of the effluent also drops from the original 7000mg/L to 90mg/L, meeting the discharge standard of wastewater.
实验表明，通过在氧化空气中加入臭氧，臭氧本身氧化亚硫酸钠的量并不多，但空气中氧气的利用率相对于纯空气催化提高了十多倍。处理时间也大为缩短，本例处理时间为7小时，但若没有臭氧，往往二十四小时以上，且效果都不理想。Experiments have shown that by adding ozone to the oxidized air, the amount of sodium sulfite oxidized by ozone itself is not much, but the utilization rate of oxygen in the air is more than ten times higher than that of pure air. The processing time is also greatly shortened, and the processing time of this example is 7 hours, but if there is no ozone, it is often more than 24 hours, and the effect is not satisfactory.
实施例3Example 3
某含亚硫酸钠的废水溶液，在体积为1立方米的反应容器中，亚硫酸钠的浓度25000mg/L，COD含量为5100mg/L，溶液的pH值约7-8，废水的体积600升。通过臭氧发生器产生含臭氧的气体，其含臭氧的重量浓度为1-2％，然后将含臭氧的气体，通过三通管将含臭氧气体直接加入到用于氧化亚硫酸盐水溶液的空气流中，则混合气中臭氧的浓度会因与空气的混合比不同而下降，控制臭氧在用于氧化的空气中的重量百分比浓度为0.01％，一个标准大气压下，空气的流量10立方米/小时，催化氧化反应时间4小时，经检测，亚硫酸钠的浓度降到300mg/L，出水的COD也从原来的5100mg/L，下降到70mg/L，达到废水的排放标准。For a wastewater solution containing sodium sulfite, in a reaction vessel with a volume of 1 cubic meter, the concentration of sodium sulfite is 25000 mg/L, the COD content is 5100 mg/L, the pH value of the solution is about 7-8, and the volume of wastewater is 600 liters. Ozone-containing gas is generated by an ozone generator, and its ozone-containing weight concentration is 1-2%, and then the ozone-containing gas is directly added to the air flow for oxidizing the sulfite aqueous solution through a three-way pipe In the middle, the concentration of ozone in the mixed gas will decrease due to the different mixing ratio with the air. The weight percentage concentration of ozone in the air used for oxidation is controlled to be 0.01%. Under a standard atmospheric pressure, the air flow rate is 10 cubic meters per hour , The catalytic oxidation reaction time is 4 hours. After testing, the concentration of sodium sulfite dropped to 300mg/L, and the COD of the effluent also dropped from the original 5100mg/L to 70mg/L, meeting the discharge standard of wastewater.
实验表明，通过在氧化空气中加入臭氧，臭氧本身氧化亚硫酸钠的量并不多，但空气中氧气的利用率相对于纯空气催化提高了十多倍。处理时间也大为缩短，本例处理时间为4小时，但若没有臭氧，往往二十四小时以上，且效果都不理想。Experiments have shown that by adding ozone to the oxidized air, the amount of sodium sulfite oxidized by ozone itself is not much, but the utilization rate of oxygen in the air is more than ten times higher than that of pure air. The processing time is also greatly shortened, and the processing time of this example is 4 hours, but if there is no ozone, it is often more than 24 hours, and the effect is not satisfactory.
需要说明的是本发明的臭氧催化空气中的氧气氧化亚硫酸盐的亚硫酸根，其氧化对象为亚硫酸根离子，与阳离子关系不密切，上述实施例提供的是含亚硫酸钠的废水的例子，事实上，其它含可溶性含亚硫酸盐的废水都有相同的效果，即对通过在空气中加入臭氧，亚硫酸根氧化速度相对于空气氧化提高十倍以上，本发明利用臭氧的加入，不仅直接参与了亚硫酸根的氧化，而且大大增加了空气中氧气的氧化效率。It should be noted that the sulfite radical of the oxygen oxidation sulfite in the ozone catalyzed air of the present invention, its oxidation object is sulfite ion, not closely related with cation, what above-mentioned embodiment provides is the example of the waste water containing sodium sulfite, In fact, other waste water containing soluble sulfite has the same effect, that is, by adding ozone in the air, the sulfite oxidation rate is increased by more than ten times relative to air oxidation. The addition of ozone in the present invention not only directly Participated in the oxidation of sulfite, and greatly increased the oxidation efficiency of oxygen in the air.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100411262A CN101602537B (en) | 2009-07-15 | 2009-07-15 | Processing method employing ozone for catalytic oxidation of sulphite water solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100411262A CN101602537B (en) | 2009-07-15 | 2009-07-15 | Processing method employing ozone for catalytic oxidation of sulphite water solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101602537A CN101602537A (en) | 2009-12-16 |
| CN101602537B true CN101602537B (en) | 2012-08-08 |
Family
ID=41468455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100411262A Expired - Fee Related CN101602537B (en) | 2009-07-15 | 2009-07-15 | Processing method employing ozone for catalytic oxidation of sulphite water solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101602537B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885529A (en) * | 2010-06-11 | 2010-11-17 | 北京工业大学 | A kind of treatment method of high COD waste water produced by heavy alkylbenzene sulfonate |
| 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 |
| 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 |
| 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 |
| CN110204123B (en) * | 2019-04-16 | 2022-04-12 | 南京工业大学 | A kind of resource comprehensive utilization method of fipronil production waste 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2818160A1 (en) * | 2000-12-20 | 2002-06-21 | Air Liquide | PROCESS FOR WET OR OZONATION OXIDATION TYPE OXIDATION |
| CN1757429A (en) * | 2004-10-09 | 2006-04-12 | 财团法人工业技术研究院 | Method and device for reducing ozone concentration 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 |
| CN101200328A (en) * | 2007-11-01 | 2008-06-18 | 华侨大学 | Air Oxidation Process for Treating Electroplating Mixed Wastewater |
| CN101239758A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for treating sulfur-containing waste water |
-
2009
- 2009-07-15 CN CN2009100411262A patent/CN101602537B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2818160A1 (en) * | 2000-12-20 | 2002-06-21 | Air Liquide | PROCESS FOR WET OR OZONATION OXIDATION TYPE OXIDATION |
| CN1757429A (en) * | 2004-10-09 | 2006-04-12 | 财团法人工业技术研究院 | Method and device for reducing ozone concentration 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 |
| CN101239758A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for treating sulfur-containing waste water |
| CN101200328A (en) * | 2007-11-01 | 2008-06-18 | 华侨大学 | Air Oxidation Process for Treating Electroplating Mixed Wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101602537A (en) | 2009-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9169141B2 (en) | Water treatment method by catalyzing ozone with a persulfate | |
| CN101602537B (en) | Processing method employing ozone for catalytic oxidation of sulphite water solution | |
| CN106976949A (en) | A kind of oxidation treatment method of Leachate site biological treatment water outlet | |
| CN110117115A (en) | A kind of processing method and equipment of industrial waste salt recycling | |
| CN101774674B (en) | Method for processing refractory organic wastewater by persulfate | |
| CN101601998A (en) | A preparation method of a catalyst for catalytic oxidation treatment of high-concentration organic wastewater | |
| CN108059229A (en) | A kind of method of iron carbon activation persulfate processing high-concentration hardly-degradable alkaline waste liquor | |
| CN102219323B (en) | Method for simultaneously removing organic pollutants and ammonia in waste water and reactor | |
| CN103787537B (en) | A kind for the treatment of process of sewage and application thereof | |
| CN110372085A (en) | A kind of organic wastewater catalytic ozonation processing system and method | |
| CN102329023A (en) | Processing method of garbage leachate | |
| CN101774673B (en) | Processing method of hardly degraded organic substance | |
| CN103224308B (en) | Ferrous ion reduction and catalytic oxidation cooperation for reinforcing waste water biological treatment technology | |
| CN106745658A (en) | One kind promotes aeration to remove Mn in water removal using sulphite2+Method | |
| CN107252686A (en) | A kind of processing method of phenol wastewater | |
| CN102417258B (en) | Device and method for treating pulping wastewater by catalyst and ozone | |
| Chaohui et al. | Remove of ammoniacal nitrogen wastewater by ultrasound/Mg/Al2O3/O3 | |
| CN110316807A (en) | A kind of method for treating water using ultraviolet collaboration persulfate catalysis ozone | |
| CN204251408U (en) | Ozone catalytic oxidation effluent treatment plant | |
| CN107055738A (en) | A kind of method that Zero-valent Iron activation persulfate removes Taste and odor compounds in water removal | |
| CN108178448A (en) | A kind of method for reducing tricyclazole agricultural chemicals waste water COD | |
| CN106955686A (en) | Preparation method and application of ozone oxidation catalyst of diatomite-loaded multi-metal oxide | |
| CN103933968A (en) | Preparation method and application of polymanganese silicate doped hydroxy manganese oxide catalyst | |
| CN207805343U (en) | Pass through the device of redox reaction degradation ozone and organic mixed waste gas | |
| CN105107506A (en) | Preparation method for modified activated carbon used for catalysis of hydrogen peroxide oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120808 Termination date: 20180715 |