CN113003819B - Method for treating organic wastewater by using advanced oxidation system based on semidry flue gas desulfurization ash - Google Patents
Method for treating organic wastewater by using advanced oxidation system based on semidry flue gas desulfurization ash Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 36
- 230000023556 desulfurization Effects 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003546 flue gas Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000005416 organic matter Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
本发明属于固体废弃物资源化利用和废水高级氧化处理技术领域，具体涉及一种基于半干式钙法烟气脱硫灰的高级氧化体系处理有机废水的方法，该体系是由紫外光或可见光、纳米过渡金属氧化物、溶解氧、缓释SO3 ‑的脱硫灰组成。该体系在紫外光或可见光照射且通氧（含有溶解氧）的条件下，由SO3 ‑经过光照活化产生的SO3 ·‑与溶解氧O2作用，可产生强氧化性的硫酸根自由基SO4 ·‑，破坏废水中有机的化学键，从而将污染物降解并提高废水可生化性。本发明对废水中有机物具有较好的去除效果，同时也实现了半干法脱硫灰的源化利用，达到以废治废的目的。The invention belongs to the technical field of resource utilization of solid waste and advanced oxidation treatment of wastewater, and specifically relates to a method for treating organic wastewater with an advanced oxidation system based on semi-dry calcium flue gas desulfurization ash. The system is composed of ultraviolet light or visible light, Desulfurization ash composed of nano-transition metal oxides, dissolved oxygen, and slow-release SO 3 ‑ . Under the condition of ultraviolet light or visible light irradiation and oxygen (containing dissolved oxygen), the SO 3 ‑ generated by SO 3 ‑ which is activated by light reacts with dissolved oxygen O 2 to generate strong oxidative sulfate radicals SO 4 ·‑ , breaks the organic chemical bonds in the wastewater, thereby degrading the pollutants and improving the biodegradability of the wastewater. The invention has a good removal effect on organic matter in waste water, and also realizes the source utilization of semi-dry desulfurization ash, and achieves the purpose of treating waste with waste.
Description
技术领域technical field
本发明属于固体废弃物资源化利用和废水高级氧化处理技术领域，具体涉及一种基于半干法烟气脱硫灰的高级氧化体系处理有机废水的方法。The invention belongs to the technical field of resource utilization of solid waste and advanced oxidation treatment of waste water, and in particular relates to a method for treating organic waste water with an advanced oxidation system based on semi-dry flue gas desulfurization ash.
背景技术Background technique
半干法烟气脱硫技术其基本原理与传统湿式石灰-石膏法类似，是以石灰浆液为吸收剂，在吸收塔中与烟气充分接触，从而将烟气中的SO2吸收。该工艺该脱硫的同时伴随着颗粒干燥过程，因此其脱硫产物呈干粉状，无废水产生。半干法烟气脱硫灰含有大量亚硫酸钙、碳酸钙及氧化钙，成分波动较大，呈强碱性且易分解，综合利用非常困难。The basic principle of the semi-dry flue gas desulfurization technology is similar to that of the traditional wet lime-gypsum method. The lime slurry is used as the absorbent to fully contact the flue gas in the absorption tower, thereby absorbing the SO 2 in the flue gas. The desulfurization process of this process is accompanied by the particle drying process, so the desulfurization product is in the form of dry powder, and no waste water is produced. Semi-dry flue gas desulfurization ash contains a large amount of calcium sulfite, calcium carbonate and calcium oxide. The composition fluctuates greatly. It is strongly alkaline and easy to decompose. It is very difficult to comprehensively utilize it.
高级氧化技术是利用化学反应过程中产生的强氧化基团如羟基自由基（OH·）及硫酸根自由基（SO4 ·-）等，经过一系列链式反应将有机物氧化分解成小分子直至降解矿化的过程。羟基自由基（OH·）和硫酸根自由基（SO4 ·-）都具有极强的氧化能力，可以有效去除水中的难降解且稳定性较强的有机物，将大分子有机物分解为小分子生物可利用有机物，有效改善污水的可生化性。Advanced oxidation technology uses strong oxidizing groups such as hydroxyl radicals (OH · ) and sulfate radicals (SO 4 ·- ) generated during chemical reactions to oxidize and decompose organic matter into small molecules through a series of chain reactions until The process of degrading mineralization. Hydroxyl radicals (OH · ) and sulfate radicals (SO 4 ·- ) both have extremely strong oxidizing ability, which can effectively remove refractory and stable organic substances in water, and decompose macromolecular organic substances into small molecular biological substances. Organic matter can be used to effectively improve the biodegradability of sewage.
发明内容Contents of the invention
本发明提供一种基于半干法烟气脱硫灰的高级氧化体系处理有机废水的方法，该体系是由紫外光或可见光、纳米过渡金属氧化物、溶解氧、缓释SO3 -的脱硫灰组成。该体系在紫外光或可见光照射且通氧（含有溶解氧）的条件下，由SO3 -经过光活化产生的SO3 ·-与溶解氧O2作用，可产生强氧化性的硫酸根自由基SO4 ·-，破坏废水中有机的化学键，从而将污染物降解并提高废水可生化性。值得注意的是，半干法脱硫灰可以在水中缓释SO3 -避免了与污染物竞争所导致SO4 ·-的不必要消耗，提高该体系的处理效率。本发明对废水中有机物及脱硫会无害化处理的同时，实现废弃物的高附加值资源化利用，达到以废治废的目的，具有显著的经济效益、社会效益及环境效益。The invention provides a method for treating organic wastewater based on an advanced oxidation system of semi-dry flue gas desulfurization ash. The system is composed of desulfurization ash of ultraviolet light or visible light, nano-transition metal oxides, dissolved oxygen, and slow-release SO 3 - . Under the condition of ultraviolet light or visible light irradiation and oxygen (containing dissolved oxygen), the SO 3 - generated by photoactivation of SO 3 - reacts with dissolved oxygen O 2 to generate strong oxidative sulfate radicals. SO 4 ·- , destroys the organic chemical bonds in the wastewater, thereby degrading the pollutants and improving the biodegradability of the wastewater. It is worth noting that the semi-dry desulfurization ash can release SO 3 - in water slowly, avoiding unnecessary consumption of SO 4 ·- caused by competition with pollutants, and improving the treatment efficiency of the system. The invention can harmlessly treat the organic matter and desulfurization in the waste water, realize the high value-added resource utilization of the waste, achieve the purpose of treating the waste with waste, and have remarkable economic, social and environmental benefits.
1. 一种基于半干法烟气脱硫灰的高级氧化体系处理有机废水的方法，其特征在于按以下步骤进行：1. A method based on the advanced oxidation system of semi-dry flue gas desulfurization ash to process organic waste water, it is characterized in that carry out according to the following steps:
（1）将取自稳定运行的半干式钙法烟气脱硫系统产生的废弃物经过研磨过80目筛子，取筛下的粉末装袋待用；(1) Grind the waste from the semi-dry calcium flue gas desulfurization system in stable operation through an 80-mesh sieve, and bag the powder under the sieve for use;
（2）取一定量的有机废水置于反应池中，加入一定量预处理后的脱硫灰及纳米金属氧化物催化剂，并缓慢通入空气；(2) Take a certain amount of organic wastewater and put it in the reaction tank, add a certain amount of pretreated desulfurization ash and nano-metal oxide catalyst, and slowly introduce air;
（3）调节体系pH=5.0-9.0，持续搅拌，采用氙灯（可见光）或低压汞灯（紫外光），持续照射15-180 min；(3) Adjust the pH of the system to 5.0-9.0, keep stirring, and use xenon lamp (visible light) or low-pressure mercury lamp (ultraviolet light) to continuously irradiate for 15-180 min;
（4）将处理后的废水调节pH=6.0-7.0，过滤出水。(4) Adjust the pH of the treated wastewater to 6.0-7.0, and filter the water.
所述的脱硫渣为半干式钙法烟气脱硫工艺所产生的废弃物，且在水溶液中可以缓慢释放亚硫酸根。The desulfurization residue is the waste produced by the semi-dry calcium flue gas desulfurization process, and can slowly release sulfite in the aqueous solution.
所述的纳米金属氧化物催化剂为纳米级TiO2、ZnO及Fe2O3中的一种或几种。The nanometer metal oxide catalyst is one or more of nanoscale TiO 2 , ZnO and Fe 2 O 3 .
所述的反应池中投加的脱硫灰质量约为废水中有机物质量的30-100倍，并控制反应pH=5.0-9.0。The mass of desulfurized ash added to the reaction pool is about 30-100 times the mass of organic matter in the waste water, and the reaction pH is controlled to be 5.0-9.0.
所述的光源采用氙灯（可见光）或低压汞灯（紫外光），持续照射15-180 min。The light source adopts a xenon lamp (visible light) or a low-pressure mercury lamp (ultraviolet light), and continuously irradiates for 15-180 min.
所述的该体系是由紫外光或可见光、过渡金属氧化物催化剂、溶解氧及缓释SO3 -的脱硫灰组成的高级氧化体系。The said system is an advanced oxidation system composed of ultraviolet light or visible light, transition metal oxide catalyst, dissolved oxygen and slow-release SO 3 - desulfurization ash.
与现有技术相比，本发明的特点和有益效果是：Compared with prior art, feature and beneficial effect of the present invention are:
本发明对废水中有机物去除效果好，且实现烟气脱硫灰的低成本高附加值利用，达到以废治废的目的，具有显著的经济效益、社会效益及环境效益。The invention has good effect on removing organic matters in waste water, realizes low-cost and high-value-added utilization of flue gas desulfurization ash, achieves the purpose of treating waste with waste, and has remarkable economic, social and environmental benefits.
附图说明Description of drawings
图1为本发明实施例中所使用的半干法脱硫灰照片。Fig. 1 is the photo of semi-dry method desulfurization ash used in the embodiment of the present invention.
图2为本发明实施例中所使用的半干法脱硫灰XRD图。Fig. 2 is the XRD diagram of the semi-dry method desulfurization ash used in the embodiment of the present invention.
具体实施方式Detailed ways
下面通过实例对本发明所述的方法和技术加以说明，实际应用中，不限于此。The method and technology described in the present invention will be illustrated by examples below, and the actual application is not limited thereto.
实施例1Example 1
本实施案例所述的一种基于半干法烟气脱硫灰的高级氧化体系处理有机废水的方法，需按以下步骤进行：A method for treating organic wastewater based on the advanced oxidation system of semi-dry flue gas desulfurization ash described in this implementation case needs to be carried out according to the following steps:
（1）将取自稳定运行的半干式钙法烟气脱硫系统产生的废弃物经研磨过80目筛子，取筛下的粉末装袋待用；(1) Grind the waste from the semi-dry calcium flue gas desulfurization system in stable operation through an 80-mesh sieve, and take the powder under the sieve and bag it for use;
（2）取200mL浓度10mg/L的玫瑰红B废水于反应池中，加入5mg纳米α-Fe2O3粉体及0.25g脱硫灰充分搅拌混合，并以0.08 L/min通入空气；(2) Take 200mL of Rose Bengal B wastewater with a concentration of 10mg/L in the reaction tank, add 5mg of nanometer α-Fe 2 O 3 powder and 0.25g of desulfurization ash, stir and mix thoroughly, and let air flow in at 0.08 L/min;
（3）调节pH=7.0，持续搅拌，采用300W的氙灯（模拟日光）作为光源，持续照射90min；(3) Adjust pH=7.0, keep stirring, use 300W xenon lamp (simulated sunlight) as the light source, and continue to irradiate for 90 minutes;
处理后废水经测定其玫瑰红B去除率可达90%以上。The removal rate of rose bengal B in the treated wastewater can reach more than 90%.
实施例2Example 2
本实施案例所述的一种基于半干法烟气脱硫灰的高级氧化体系处理有机废水的方法，需按以下步骤进行：A method for treating organic wastewater based on the advanced oxidation system of semi-dry flue gas desulfurization ash described in this implementation case needs to be carried out according to the following steps:
（1）将取自稳定运行的半干式钙法烟气脱硫系统产生的废渣经过研磨过80目筛子，取筛下的粉末装袋待用；(1) Grind the waste residue from the semi-dry calcium flue gas desulfurization system in stable operation through an 80-mesh sieve, and bag the powder under the sieve for use;
（2）取200mL浓度30mg/L的三氯苯酚废水于反应池中，加入6 mg纳米TiO2粉体及0.6g脱硫灰充分搅拌混合，并以0.8 L/min通入空气；(2) Take 200 mL of trichlorophenol wastewater with a concentration of 30 mg/L in the reaction tank, add 6 mg of nano-TiO 2 powder and 0.6 g of desulfurization ash, stir and mix thoroughly, and pass air at 0.8 L/min;
（3）调节pH=8.0，持续搅拌，采用低压汞灯（UVC波段）作为光源，持续照射180min；(3) Adjust the pH to 8.0, keep stirring, use a low-pressure mercury lamp (UVC band) as the light source, and continue to irradiate for 180 minutes;
处理后废水经测定其三氯苯酚脱氯率可达90%以上。After treatment, the dechlorination rate of trichlorophenol can reach more than 90%.
以上所述，仅为本发明较佳的具体实施案例，但本发明的保护范围并不局限于此，The above are only preferred specific implementation cases of the present invention, but the protection scope of the present invention is not limited thereto.
任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其Any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical scheme of the present invention and its
发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。Any equivalent replacement or change of the inventive concept shall fall within the protection scope of the present invention.
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