CN102910724A - Method for treating organic wastewater by oxidation of bicarbonate activated load-type metal catalysts - Google Patents
Method for treating organic wastewater by oxidation of bicarbonate activated load-type metal catalysts Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 23
- -1 bicarbonate-activated hydrogen peroxide Chemical class 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000010815 organic waste Substances 0.000 claims abstract 8
- 239000000654 additive Substances 0.000 claims description 10
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- 230000000996 additive effect Effects 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
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- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
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- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- VOULLQDGKZXPMY-UHFFFAOYSA-N carbonic acid hydrogen peroxide Chemical compound OO.OC(O)=O VOULLQDGKZXPMY-UHFFFAOYSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 239000010840 domestic wastewater Substances 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明公开了一种碳酸氢盐活化过氧化氢催化氧化处理有机废水的方法,将负载型过渡金属离子、碳酸氢盐活化的过氧化氢与有机废水混合并搅拌反应,待过氧化氢消耗完毕即结束;其中,负载型过渡金属离子作为催化剂,浓度为0.1-10wt%,用量为0.01-10 g/L,过氧化氢作为氧化剂,是由过氧化氢与碳酸氢盐配成水溶液形成,其中碳酸氢盐在混合物中的浓度为0.5-1000 mM/L,过氧化氢浓度为1-500 mM/L。本发明具有以下技术优势:(1)反应条件温和,对设备要求低,反应体系简单,投资小;(2)有机废水在中性偏微碱性条件下进行,环境友好,无二次污染;(3)适用范围广,处理成本低,可以大规模使用。The invention discloses a method for treating organic waste water by catalytic oxidation of bicarbonate-activated hydrogen peroxide, which comprises mixing loaded transition metal ions and bicarbonate-activated hydrogen peroxide with organic waste water and stirring for reaction until the hydrogen peroxide is completely consumed That is to end; wherein, the supported transition metal ion is used as a catalyst, the concentration is 0.1-10wt%, and the consumption is 0.01-10 g/L, and hydrogen peroxide is used as an oxidant, which is formed by preparing an aqueous solution of hydrogen peroxide and bicarbonate, wherein The concentration of bicarbonate in the mixture is 0.5-1000 mM/L, and the concentration of hydrogen peroxide is 1-500 mM/L. The present invention has the following technical advantages: (1) mild reaction conditions, low equipment requirements, simple reaction system, and low investment; (2) organic wastewater is carried out under neutral to slightly alkaline conditions, which is environmentally friendly and free of secondary pollution; (3) It has wide application range, low processing cost, and can be used on a large scale.
Description
技术领域 technical field
本发明属于废水处理技术,具体涉及一种采用碳酸氢盐活化负载型金属催化剂催化氧化处理有机废水的方法,该方法是以过氧化氢为氧化剂,碳酸氢盐为活化剂,采用负载型金属离子催化剂催化氧化降解有机废水。 The invention belongs to wastewater treatment technology, and in particular relates to a method for catalytic oxidation treatment of organic wastewater by using bicarbonate to activate a loaded metal catalyst. The catalyst catalyzes the oxidation degradation of organic wastewater. the
背景技术 Background technique
随着工业化程度及人民生活水平的提高,各种有机废水的降解处理压力越来越大。尤其是随着生产规模的不断扩大及工业技术的飞速发展,含有高浓度难降解、且有毒有害的有机废水污染源日益增多。目前处理各种废水的方法包括物理、生物及化学方法。其中物理法是将污染物加以收集与转移,而不是消除;生物法是目前使用最成功与广泛的方法,但处理周期较长且对可生化活性差及高生物毒性的污染物处理较难。化学法种类繁多,适合于快速处理高浓度废水,具有较好的应用前景,尤其是基于活化过氧化氢的Fenton技术(Pignatello JJ,Environment Science &Technology2006)及其改进体系,如光助Fenton(CN1636893),电Fenton(CN1789150),Fenton/O3(CN101311130),Fenton/超声波(CN1546395)等,已成为各方面关注的焦点。其特点是形成具有极高氧化能力的羟基自由基,对各种污染物进行快速、无选择性地氧化到二氧化碳和水。但这些催化技术在实际的工业应用中还存在一些技术难题,限制了它们在实际废水处理的大量应用。其中特别是负载型金属离子催化剂,尚有以下缺点:1)由于大量使用金属离子作为催化剂,随着反应的进行,反应介质逐渐酸化,同时由于较高的处理温度,金属离子大量溶出,形成二次污染(Mantzavinos D,WaterResearch,2009),2)反应受pH限制严重(如Fenton体系需要在pH 3-4 处理),3)设备投资大(如湿式氧化),因此限制了它们在实际废水处理的大量应用。为克服以上缺点,发明专利“一种活化双氧水氧化降解废水有机污染物的方法” (ZL 2009 1 0061122.0)开发了碳酸氢盐活化的双氧水体系来实现有机废水的有效降解,加入微量的水溶性过渡金属离子后会进一步提高其催化活性。但采用水溶性过渡金属离子为催化剂,同样造成二次污染,且金属催化剂难回收,成本较高。 With the improvement of the degree of industrialization and people's living standards, the pressure of degradation and treatment of various organic wastewater is increasing. Especially with the continuous expansion of production scale and the rapid development of industrial technology, the pollution sources of organic wastewater containing high concentration, refractory, toxic and harmful are increasing day by day. Current methods for treating various types of wastewater include physical, biological, and chemical methods. Among them, the physical method is to collect and transfer pollutants rather than eliminate them; the biological method is currently the most successful and widely used method, but the treatment cycle is long and it is difficult to treat pollutants with poor biochemical activity and high biological toxicity. There are many kinds of chemical methods, which are suitable for the rapid treatment of high-concentration wastewater, and have good application prospects, especially based on the Fenton technology (Pignatello JJ, Environment Science & Technology 2006) of activated hydrogen peroxide and its improved system, such as Guangzhu Fenton (CN1636893) , Electric Fenton (CN1789150), Fenton/O 3 (CN101311130), Fenton/Ultrasonic (CN1546395), etc., have become the focus of attention from all sides. It is characterized by the formation of hydroxyl radicals with extremely high oxidizing ability, which can quickly and non-selectively oxidize various pollutants to carbon dioxide and water. However, there are still some technical difficulties in the actual industrial application of these catalytic technologies, which limit their extensive application in actual wastewater treatment. Wherein especially supported metal ion catalyst, still has following shortcoming: 1) owing to using a large amount of metal ion as catalyst, along with the carrying out of reaction, reaction medium is gradually acidified, simultaneously because higher processing temperature, metal ion dissolves in a large amount, forms two Secondary pollution (Mantzavinos D, WaterResearch, 2009), 2) The reaction is severely limited by pH (such as the Fenton system needs to be treated at pH 3-4), 3) The investment in equipment is large (such as wet oxidation), thus limiting their use in actual wastewater treatment a large number of applications. In order to overcome the above shortcomings, the invention patent "A method for oxidatively degrading organic pollutants in wastewater by activating hydrogen peroxide" (ZL 2009 1 0061122.0) developed a hydrogen peroxide system activated by bicarbonate to achieve effective degradation of organic wastewater, adding a small amount of water-soluble transition Metal ions will further enhance its catalytic activity. However, the use of water-soluble transition metal ions as catalysts also causes secondary pollution, and the metal catalysts are difficult to recycle and the cost is high.
发明内容 Contents of the invention
本发明针对使用水溶性过渡金属离子为催化剂容易带来二次污染的缺陷,提供了一种碳酸氢盐活化负载型金属离子催化剂,过氧化氢为氧化剂的催化氧化处理有机废水的方法,实现有机废水的有效降解。 The present invention aims at the defect that the use of water-soluble transition metal ions as catalysts is likely to cause secondary pollution, and provides a bicarbonate-activated supported metal ion catalyst, a method for catalytic oxidation treatment of organic wastewater using hydrogen peroxide as an oxidant, realizing organic Effective degradation of wastewater. the
本发明提供的一种碳酸氢盐活化过氧化氢催化氧化处理有机废水的方法,将负载型过渡金属离子、碳酸氢盐活化的过氧化氢与有机废水混合并搅拌反应,待过氧化氢消耗完毕即结束;其中, The invention provides a method for treating organic wastewater by catalytic oxidation of bicarbonate-activated hydrogen peroxide, which comprises mixing loaded transition metal ions and bicarbonate-activated hydrogen peroxide with organic wastewater and stirring the reaction until the hydrogen peroxide is completely consumed ends; where,
所述负载型过渡金属离子作为催化剂,过渡金属离子在催化剂中的质量百分比浓度为0.1-10%,其用量为0.01-10g/L,所述过氧化氢作为氧化剂,所述碳酸氢盐活化的过氧化氢氧化剂是由过氧化氢与碳酸氢盐配成水溶液形成,其中碳酸氢盐在混合物中的浓度为0.5-1000mM/L,过氧化氢在混合物中的浓度为1-500mM/L。 The supported transition metal ion is used as a catalyst, the mass percent concentration of the transition metal ion in the catalyst is 0.1-10%, and its consumption is 0.01-10g/L, the hydrogen peroxide is used as an oxidant, and the bicarbonate-activated The hydrogen peroxide oxidizing agent is formed by preparing an aqueous solution of hydrogen peroxide and bicarbonate, wherein the concentration of bicarbonate in the mixture is 0.5-1000mM/L, and the concentration of hydrogen peroxide in the mixture is 1-500mM/L. the
作为上述技术方案的改进,所述负载型过渡金属离子为钴、铬、锰、铜、铁、镍、钒、钼和钨的一种或多种。 As an improvement of the above technical solution, the supported transition metal ion is one or more of cobalt, chromium, manganese, copper, iron, nickel, vanadium, molybdenum and tungsten. the
作为上述技术方案的进一步改进,在负载型过渡金属催化剂中加入添加物,所述催化剂的添加物是碱土金属离子或/和无氧化还原活性的过渡金属离子,添加物在催化剂中的质量百分比浓度为0.1-20wt%。 As a further improvement of the above-mentioned technical scheme, an additive is added to the supported transition metal catalyst, the additive of the catalyst is an alkaline earth metal ion or/and a transition metal ion without redox activity, and the mass percentage concentration of the additive in the catalyst is It is 0.1-20wt%. the
作为上述技术方案的再进一步改进,所述催化剂的添加物为镁、钙、钡、锶、钪、钇、锆和锌离子中的一种或多种。 As a further improvement of the above technical solution, the catalyst additive is one or more of magnesium, calcium, barium, strontium, scandium, yttrium, zirconium and zinc ions. the
作为上述技术方案的更进一步改进,所述碳酸氢盐的阳离子是碱金属 离子或/和碱土金属离子;所述碳酸氢盐的阳离子是锂、钠、钾、铯、镁、钙、钡、锶及铵离子中的一种或多种;所述催化剂的载体为三氧化二铝、二氧化钛、二氧化硅、硅藻土或蒙脱土。 As a further improvement of the above-mentioned technical scheme, the cation of the bicarbonate is an alkali metal ion or/and an alkaline earth metal ion; the cation of the bicarbonate is lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium and one or more of ammonium ions; the carrier of the catalyst is aluminum oxide, titanium dioxide, silicon dioxide, diatomaceous earth or montmorillonite. the
本发明采用负载型金属离子为催化剂,以碳酸氢盐活化的过氧化氢为氧化剂在近室温条件下实现了有机废水的高效降解,消除了水溶性金属离子带来的二次污染,并有效克服上述“Fenton类高级氧化技术”的缺陷。本发明所包含的技术具有反应条件温和、催化剂可循环使用、无二次污染及设备投资低的优势。 The present invention uses supported metal ions as catalysts and hydrogen peroxide activated by bicarbonate as an oxidant to achieve high-efficiency degradation of organic wastewater at near room temperature, eliminates secondary pollution caused by water-soluble metal ions, and effectively overcomes the Defects of the above-mentioned "Fenton-like advanced oxidation technology". The technology included in the invention has the advantages of mild reaction conditions, recyclable catalyst, no secondary pollution and low equipment investment. the
本发明的碳酸氢盐-过氧化氢-负载型金属离子催化技术适用于处理含染料废水,含农药废水,含酚废水,城市生活废水和各种垃圾渗透液。有机废水降解的评价标准是测定催化氧化结束后有机污染物的转化率及化学耗氧量的去除率。采用本发明技术,对所处理的有机废水能够实现完全脱色脱臭,COD去除率可以达到20-70%。 The bicarbonate-hydrogen peroxide-loaded metal ion catalytic technology of the invention is suitable for treating dye-containing wastewater, pesticide-containing wastewater, phenol-containing wastewater, urban domestic wastewater and various garbage permeates. The evaluation standard of organic wastewater degradation is to measure the conversion rate of organic pollutants and the removal rate of chemical oxygen demand after catalytic oxidation. By adopting the technology of the invention, the treated organic wastewater can be completely decolorized and deodorized, and the COD removal rate can reach 20-70%. the
总之,本发明具有以下技术优势:(1)反应条件温和,对设备要求低,反应体系简单,投资小;(2)有机废水在中性偏微碱性条件下进行,环境友好,无二次污染;(3)适用范围广,处理成本低,可以大规模使用。 In a word, the present invention has the following technical advantages: (1) mild reaction conditions, low equipment requirements, simple reaction system, and small investment; (2) organic wastewater is carried out under neutral and slightly alkaline conditions, which is environmentally friendly and has no secondary pollution; (3) wide application range, low treatment cost, and large-scale use. the
本发明采用负载型金属离子为催化剂,有效克服了现有碳酸氢盐活化双氧水、使用水溶性金属离子为催化剂所带来的二次污染及催化剂难回收的缺点(ZL 200910061122.0);并且与传统的负载型金属离子为催化剂相比,本发明所包含的催化技术中催化剂的用量更少,金属离子的流失率更低。 The present invention uses supported metal ions as catalysts, which effectively overcomes the secondary pollution caused by the existing hydrogen peroxide activated by bicarbonate and the use of water-soluble metal ions as catalysts, and the shortcomings of difficult recovery of catalysts (ZL 200910061122.0); and compared with traditional Compared with supporting metal ions as catalysts, the catalytic technology included in the present invention uses less catalyst and has lower loss rate of metal ions. the
具体实施方式 Detailed ways
本发明是将过氧化氢与碳酸氢盐配成水溶液形成碳酸氢盐活化的过氧化氢氧化剂,其中碳酸氢盐浓度为0.5-1000mM/L,过氧化氢浓度为1-500mM/L;将负载的过渡金属离子催化剂与有机废水及预配的氧化剂在反应池里混合搅拌,催化剂的用量为0.01-10g/L,过渡金属离子的负载量为0.1-10wt%,作为负载型过渡金属催化剂的添加物负载量为0.1-20wt%,反应温度 10-100℃;待过氧化氢消耗完毕(通常为1分钟~24小时)为反应结束。 The present invention prepares hydrogen peroxide and bicarbonate into an aqueous solution to form a bicarbonate-activated hydrogen peroxide oxidant, wherein the concentration of bicarbonate is 0.5-1000mM/L, and the concentration of hydrogen peroxide is 1-500mM/L; The transition metal ion catalyst, the organic wastewater and the pre-prepared oxidant are mixed and stirred in the reaction tank. The dosage of the catalyst is 0.01-10g/L, and the loading amount of the transition metal ion is 0.1-10wt%, as the addition of the supported transition metal catalyst The loading amount is 0.1-20wt%, and the reaction temperature is 10-100°C; the reaction ends when the hydrogen peroxide is completely consumed (usually 1 minute to 24 hours). the
活化过氧化氢的碳酸氢盐的阳离子是碱金属离子:锂、钠、钾、铯或碱土金属离子:镁、钙、钡、锶及铵离子中的一种或多种。 The cation of the bicarbonate for activating hydrogen peroxide is one or more of alkali metal ions: lithium, sodium, potassium, cesium or alkaline earth metal ions: magnesium, calcium, barium, strontium and ammonium ions. the
负载型的催化剂是过渡金属离子:钴、铬、锰、铜、铁、镍、钒、钼和钨的一种或多种; The supported catalyst is a transition metal ion: one or more of cobalt, chromium, manganese, copper, iron, nickel, vanadium, molybdenum and tungsten;
负载型催化剂的添加物是碱土金属离子:镁、钙、钡、锶离子和无氧化还原活性的过渡金属离子:钪、钇、锆和锌的一种或多种;催化剂的载体是:三氧化二铝、二氧化钛、二氧化硅、硅藻土和蒙脱土。 The additives of the supported catalyst are alkaline earth metal ions: magnesium, calcium, barium, strontium ions and transition metal ions without redox activity: one or more of scandium, yttrium, zirconium and zinc; the carrier of the catalyst is: trioxide Aluminum, titanium dioxide, silica, diatomaceous earth and montmorillonite. the
下面结合附表对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。 The specific embodiments of the present invention will be further described below in conjunction with the attached table. It should be noted here that the descriptions of these embodiments are used to help understand the present invention, but are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other. the
实施例1 Example 1
取配制好的反应液(I)24mL,加入30%过氧化氢0.2mL,让该混合液于25℃下恒温搅拌,反应5小时。反应完后,取样分析。结果如表1。其中反应液(I)为染料(亚甲基蓝或甲基橙)浓度50mg/L,硝酸钴浓度20μM,碳酸氢钠浓度25 mM的水溶液; Take 24 mL of the prepared reaction solution (I), add 0.2 mL of 30% hydrogen peroxide, let the mixture stir at 25° C., and react for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 1. Wherein reaction solution (I) is dyestuff (methylene blue or methyl orange) concentration 50mg/L, cobalt nitrate concentration 20 μ M, the aqueous solution of sodium bicarbonate concentration 25 mM;
实施例2 Example 2
取配制好的反应液(I)或(II)24mL,加入30%过氧化氢0.2mL,让该混合液于45℃下恒温搅拌,反应5小时。反应完后,取样分析。结果如表1。反应液有两类:(I)苯酚浓度50mg/L,硝酸钴浓度20μM,碳酸氢钠浓度25mM的水溶液;(II)苯酚浓度50mg/L,硝酸钴浓度20μM,用氢氧化钠调pH为8.7的水溶液。 Take 24 mL of the prepared reaction solution (I) or (II), add 0.2 mL of 30% hydrogen peroxide, let the mixture stir at 45° C., and react for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 1. The reaction solution has two types: (I) 50 mg/L phenol concentration, 20 μM cobalt nitrate concentration, and 25 mM sodium bicarbonate concentration; (II) 50 mg/L phenol concentration, 20 μM cobalt nitrate concentration, adjusted pH to 8.7 with sodium hydroxide of aqueous solution. the
实施例3 Example 3
取配制好的反应液(I)或(II)24mL,加入0.01g金属负载型催化剂(催化剂的负载量为1.7%)。之后,让该混合液于25℃下恒温搅拌,反应5小 时。反应完后,取样分析。结果如表2。反应液有两类:(I)染料浓度50mg/L,过氧化氢浓度80mM,碳酸氢钠浓度25mM的水溶液; (II)染料浓度50mg/L,过氧化氢浓度80mM的水溶液。结果如表2。反应完后,钴负载型催化剂中钴元素流失量为0.2ppm。 Take 24 mL of the prepared reaction solution (I) or (II), and add 0.01 g of metal-supported catalyst (the loading amount of the catalyst is 1.7%). Afterwards, the mixture was stirred at a constant temperature of 25° C. and reacted for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 2. There are two types of reaction solutions: (I) an aqueous solution with a dye concentration of 50 mg/L, a hydrogen peroxide concentration of 80 mM, and a sodium bicarbonate concentration of 25 mM; (II) an aqueous solution with a dye concentration of 50 mg/L and a hydrogen peroxide concentration of 80 mM. The results are shown in Table 2. After the reaction, the loss of cobalt element in the cobalt-loaded catalyst was 0.2ppm. the
实施例4 Example 4
取配制好的反应液(I)或(II)20mL,然后加入0.0117g Co(或Cu)负载型催化剂(金属元素在催化剂的中的质量分数为5%)。之后,让该混合液于45℃下恒温反应5小时。反应完后,取样分析。结果如表3。其中反应液分为两类:I和II。对于I,苯酚浓度为0.5mM,过氧化氢浓度为35mM,碳酸氢钠浓度44mM;而对于II,苯酚浓度为0.5mM,过氧化氢浓度为35mM,用氢氧化钠调节溶液PH为8.70。 Take the prepared reaction solution (I) or (II) 20mL, then add 0.0117g Co (or Cu) supported catalyst (the mass fraction of the metal element in the catalyst is 5%). Afterwards, the mixture was allowed to react at a constant temperature of 45° C. for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 3. Wherein the reaction solution is divided into two categories: I and II. For I, the phenol concentration was 0.5 mM, the hydrogen peroxide concentration was 35 mM, and the sodium bicarbonate concentration was 44 mM; while for II, the phenol concentration was 0.5 mM, the hydrogen peroxide concentration was 35 mM, and the pH of the solution was adjusted to 8.70 with sodium hydroxide. the
实施例5 Example 5
取配制好的反应液(I)或(II)20mL,然后加入0.0117g其他金属离子添加的Co负载型催化剂。之后,让该混合液于45℃下恒温反应5小时。反应完后,取样分析。结果如表4。其中反应液分为两类:I和II。对于I,苯酚浓度为0.5mM,过氧化氢浓度为35mM,碳酸氢钠浓度44mM;而对于II,苯酚浓度为0.5mM,过氧化氢浓度为35mM,用氢氧化钠调节溶液PH为8.70。 Take 20 mL of the prepared reaction solution (I) or (II), and then add 0.0117 g of Co-supported catalysts added with other metal ions. Afterwards, the mixture was allowed to react at a constant temperature of 45° C. for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 4. Wherein the reaction solution is divided into two categories: I and II. For I, the phenol concentration was 0.5 mM, the hydrogen peroxide concentration was 35 mM, and the sodium bicarbonate concentration was 44 mM; while for II, the phenol concentration was 0.5 mM, the hydrogen peroxide concentration was 35 mM, and the pH of the solution was adjusted to 8.70 with sodium hydroxide. the
表1 Table 1
表2 Table 2
从表-2可以看出,无论是染料的脱色率与COD去除率,负载型过渡金属催化剂在碳酸氢盐活化过氧化氢体系中的效果均明显好于直接使用过氧化氢氧化剂。与表-1直接使用水溶性的过渡金属离子相比,负载后的过渡金属催化剂在处理废水中的流失率也很低(0.2 ppm),避免了出现二次污染的技术难题。 It can be seen from Table-2 that regardless of the decolorization rate of the dye and the COD removal rate, the effect of the supported transition metal catalyst in the bicarbonate activated hydrogen peroxide system is significantly better than that of the direct use of hydrogen peroxide oxidant. Compared with the direct use of water-soluble transition metal ions in Table-1, the loss rate of the loaded transition metal catalyst in the wastewater treatment is also very low (0.2 ppm), which avoids the technical problem of secondary pollution. the
表3 table 3
在表-3中,对苯酚的降解也体现出相似的结果:使用各种载体及过渡金属离子负载的催化剂,在碳酸氢盐活化的过氧化氢体系中体现出来的苯酚降解率均高于相似pH条件下的过氧化氢体系,同时,其过渡金属离子的流失率也远低于无碳酸氢钠的体系。 In Table-3, the degradation of phenol also shows similar results: using various supports and catalysts supported by transition metal ions, the degradation rate of phenol reflected in the hydrogen peroxide system activated by bicarbonate is higher than that of similar The hydrogen peroxide system under the pH condition, meanwhile, the loss rate of its transition metal ion is also much lower than the system without sodium bicarbonate. the
表4 Table 4
表-4可以看出,在各种添加物的存在下,负载型过渡金属离子在碳酸氢盐活化的过氧化氢体系中的活性得到进一步的改善。 It can be seen from Table-4 that in the presence of various additives, the activity of supported transition metal ions in the bicarbonate-activated hydrogen peroxide system is further improved. the
以上所述为本发明的较佳实施例而已,但本发明不应该局限于该实施例所公开的内容。所以凡是不脱离本发明所公开的精神下完成的等效或修改,都落入本发明保护的范围。 The above description is only a preferred embodiment of the present invention, but the present invention should not be limited to the content disclosed in this embodiment. Therefore, all equivalents or modifications that do not deviate from the spirit disclosed in the present invention fall within the protection scope of the present invention. the
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0787689A2 (en) * | 1996-01-31 | 1997-08-06 | Kodak Limited | Method of treating waste effluent |
CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Wastewater Catalytic Oxidation Treatment Method |
US6010632A (en) * | 1996-03-22 | 2000-01-04 | Sri International | Hydrothermal oxidation of organic compounds with heterogenous neutralizing reagent |
CN101503241A (en) * | 2009-03-13 | 2009-08-12 | 华中科技大学 | Method for oxidation degradation of wastewater organic pollutant by activating hydrogen peroxide |
CN102464415A (en) * | 2010-10-29 | 2012-05-23 | 新奥科技发展有限公司 | Advanced treatment process of coal gasification wastewater |
-
2012
- 2012-10-09 CN CN201210380005.2A patent/CN102910724B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1194626A (en) * | 1995-08-29 | 1998-09-30 | 韩国科学技术研究院 | Wastewater Catalytic Oxidation Treatment Method |
EP0787689A2 (en) * | 1996-01-31 | 1997-08-06 | Kodak Limited | Method of treating waste effluent |
US6010632A (en) * | 1996-03-22 | 2000-01-04 | Sri International | Hydrothermal oxidation of organic compounds with heterogenous neutralizing reagent |
CN101503241A (en) * | 2009-03-13 | 2009-08-12 | 华中科技大学 | Method for oxidation degradation of wastewater organic pollutant by activating hydrogen peroxide |
CN102464415A (en) * | 2010-10-29 | 2012-05-23 | 新奥科技发展有限公司 | Advanced treatment process of coal gasification wastewater |
Cited By (12)
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