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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- CN102910724A CN102910724A CN2012103800052A CN201210380005A CN102910724A CN 102910724 A CN102910724 A CN 102910724A CN 2012103800052 A CN2012103800052 A CN 2012103800052A CN 201210380005 A CN201210380005 A CN 201210380005A CN 102910724 A CN102910724 A CN 102910724A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title abstract description 6
- 239000002184 metal Substances 0.000 title abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 27
- -1 bicarbonate-activated hydrogen peroxide Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
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- 239000007864 aqueous solution Substances 0.000 claims description 8
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 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
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- 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 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
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 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
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- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 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
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
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- 230000007547 defect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000012239 silicon dioxide Nutrition 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 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
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for treating organic wastewater by oxidation of bicarbonate activated load-type metal catalysts. Load-type transition metal ions and bicarbonate-activated hydrogen peroxide are mixed with the organic wastewater with stirring for reaction, and reaction is finished when the hydrogen peroxide is consumed totally. The load-type transition metal ions serve as the catalysts, the concentration of the load-type transition metal ions in the catalysts is 0.1-10wt%, the dosage of the load-type transition metal ions is 0.01-10g/L, the hydrogen peroxide serves as oxidant which is formed by preparing the hydrogen peroxide and the bicarbonate into water solution, the concentration of the bicarbonate in the mixture is 0.5-1000mM/L, and the concentration of the hydrogen peroxide in the mixture is 1-500mM/L. The method has the technical advantages that the method is moderate in reaction conditions, low in equipment requirements, simple in reaction system and less in investment; the organic wastewater reacts in the condition of neutrality and patricidal alkalescence, so that the method is environment-friendly and free of secondary pollution; and the method is wide in application range, low in treatment cost and can be used on a large scale.
Description
Technical Field
The invention belongs to a wastewater treatment technology, and particularly relates to a method for treating organic wastewater by catalytic oxidation of a bicarbonate activated supported metal catalyst.
Background
Along with the improvement of the industrialization degree and the living standard of people, the degradation treatment pressure of various organic wastewater is higher and higher. Particularly, with the continuous expansion of production scale and the rapid development of industrial technology, the pollution sources of organic wastewater containing high concentration, difficult degradation and toxic and harmful substances are increasing day by day. Current methods for treating various waste waters include physical, biological and chemical methods. Wherein the physical method is to collect and transfer the contaminants rather than eliminate them; biological methods are currently the most successful and widespread method used, but the treatment cycle is long and the treatment of pollutants with poor biochemical activity and high biological toxicity is difficult. The chemical method has various varieties, is suitable for rapidly treating high-concentration wastewater, has better application prospect, and particularly relates to a Fenton technology (Pignatello JJ, environmental Science) based on activated hydrogen peroxide&Technology2006) and improved systems thereof, such as photo-assisted Fenton (CN1636893), electro-Fenton (CN1789150), Fenton/O3(CN101311130), Fenton/ultrasonic (CN1546395), and the like have been the focus of attention in various aspects. Its characteristic is forming toolThe hydroxyl radical with extremely high oxidation capacity can rapidly and nonselectively oxidize various pollutants into carbon dioxide and water. However, these catalytic techniques have technical difficulties in practical industrial applications, which limit their large-scale application in practical wastewater treatment. Among them, the supported metal ion catalyst has the following disadvantages: 1) because a large amount of metal ions are used as a catalyst, a reaction medium is gradually acidified along with the reaction, and simultaneously, because of higher treatment temperature, a large amount of metal ions are dissolved out to form secondary pollution (Mantzavinos D, Waterresearch, 2009), 2) the reaction is seriously limited by pH (such as a Fenton system needs to treat at pH 3-4), and 3) the equipment investment is large (such as wet oxidation), so that the large amount of application of the metal ions in the actual wastewater treatment is limited. In order to overcome the defects, the invention patent 'a method for oxidizing and degrading organic pollutants in wastewater by using activated hydrogen peroxide' (ZL 200910061122.0) develops a hydrogen peroxide system activated by bicarbonate to realize effective degradation of organic wastewater, and the catalytic activity of the organic wastewater can be further improved after trace water-soluble transition metal ions are added. However, the water-soluble transition metal ions are used as the catalyst, which also causes secondary pollution, and the metal catalyst is difficult to recover and has higher cost.
Disclosure of Invention
The invention provides a method for treating organic wastewater by catalytic oxidation by using a bicarbonate activated supported metal ion catalyst and hydrogen peroxide as an oxidant, aiming at the defect that secondary pollution is easily caused by using water-soluble transition metal ions as the catalyst, so as to realize effective degradation of the organic wastewater.
The invention provides a method for treating organic wastewater by catalytic oxidation of hydrogen carbonate activated hydrogen peroxide, which comprises the steps of mixing and stirring load-type transition metal ions, hydrogen peroxide activated by hydrogen carbonate and organic wastewater for reaction, and finishing the reaction when the hydrogen peroxide is completely consumed; wherein,
the supported transition metal ion is used as a catalyst, the mass percentage concentration of the transition metal ion in the catalyst is 0.1-10%, the dosage of the supported transition metal ion is 0.01-10g/L, the hydrogen peroxide is used as an oxidizing agent, and the hydrogen peroxide oxidizing agent activated by the bicarbonate is formed by preparing hydrogen peroxide and bicarbonate into an aqueous solution, wherein the concentration of the bicarbonate in the mixture is 0.5-1000mM/L, and the concentration of the hydrogen peroxide in the mixture is 1-500 mM/L.
As an improvement of the technical scheme, the supported transition metal ions are one or more of cobalt, chromium, manganese, copper, iron, nickel, vanadium, molybdenum and tungsten.
As a further improvement of the technical proposal, the additive is added into the supported transition metal catalyst, the additive of the catalyst is alkaline earth metal ions or/and transition metal ions without redox activity, and the mass percentage concentration of the additive in the catalyst is 0.1 to 20 weight percent.
As a further improvement of the above technical solution, the additive of the catalyst is one or more of magnesium, calcium, barium, strontium, scandium, yttrium, zirconium and zinc ions.
As a further improvement of the above technical solution, the cation of the bicarbonate is an alkali metal ion or/and an alkaline earth metal ion; the cation of the bicarbonate is one or more of lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium and ammonium ions; the carrier of the catalyst is aluminum oxide, titanium dioxide, silicon dioxide, diatomite or montmorillonite.
The invention adopts the supported metal ions as the catalyst and hydrogen peroxide activated by bicarbonate as the oxidant to realize the high-efficiency degradation of organic wastewater at the condition of near room temperature, eliminates the secondary pollution caused by water-soluble metal ions and effectively overcomes the defects of the Fenton advanced oxidation technology. The technology of the invention has the advantages of mild reaction conditions, recyclable catalyst, no secondary pollution and low equipment investment.
The bicarbonate-hydrogen peroxide-supported metal ion catalysis technology is suitable for treating dye-containing wastewater, pesticide-containing wastewater, phenol-containing wastewater, urban domestic wastewater and various garbage penetrating fluids. The evaluation standard of the organic wastewater degradation is to measure the conversion rate of organic pollutants and the removal rate of chemical oxygen demand after the catalytic oxidation is finished. By adopting the technology of the invention, the treated organic wastewater can be completely decolorized and deodorized, and the removal rate of COD can reach 20-70%.
In summary, the present invention has the following technical advantages: (1) the reaction condition is mild, the requirement on equipment is low, the reaction system is simple, and the investment is small; (2) the organic wastewater is carried out under the neutral slightly alkaline condition, so that the method is environment-friendly and has no secondary pollution; (3) wide application range, low treatment cost and large-scale application.
The invention adopts the supported metal ions as the catalyst, effectively overcomes the defects of secondary pollution and difficult catalyst recovery (ZL 200910061122.0) caused by the prior bicarbonate activated hydrogen peroxide and the use of water-soluble metal ions as the catalyst; compared with the traditional catalyst with supported metal ions, the catalyst in the catalytic technology has the advantages of less dosage and lower metal ion loss rate.
Detailed Description
The invention prepares hydrogen peroxide and bicarbonate into aqueous solution to form bicarbonate activated hydrogen peroxide oxidant, wherein the concentration of the bicarbonate is 0.5-1000mM/L, and the concentration of the hydrogen peroxide is 1-500 mM/L; mixing and stirring a loaded transition metal ion catalyst, organic wastewater and a prepared oxidant in a reaction tank, wherein the dosage of the catalyst is 0.01-10g/L, the loading capacity of the transition metal ion is 0.1-10 wt%, the loading capacity of an additive serving as the loaded transition metal catalyst is 0.1-20 wt%, and the reaction temperature is 10-100 ℃; the reaction is complete when the hydrogen peroxide is consumed (typically 1 minute to 24 hours).
The cation of the hydrogen carbonate salt which activates hydrogen peroxide is an alkali metal ion: lithium, sodium, potassium, cesium or alkaline earth metal ions: one or more of magnesium, calcium, barium, strontium and ammonium ions.
The supported catalyst is a transition metal ion: one or more of cobalt, chromium, manganese, copper, iron, nickel, vanadium, molybdenum, and tungsten;
the additive of the supported catalyst is 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: alumina, titanium dioxide, silicon dioxide, diatomite and montmorillonite.
The following description will further explain embodiments of the present invention with reference to the accompanying tables. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
24mL of the prepared reaction solution (I) was added to 0.2mL of 30% hydrogen peroxide, and the mixture was stirred at a constant temperature of 25 ℃ for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 1. Wherein the reaction solution (I) is an aqueous solution of 50mg/L dye (methylene blue or methyl orange), 20 mu M cobalt nitrate and 25mM sodium bicarbonate;
example 2
24mL of the prepared reaction solution (I) or (II) was added with 0.2mL of 30% hydrogen peroxide, and the mixture was stirred at a constant temperature of 45 ℃ 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) an aqueous solution of phenol at a concentration of 50mg/L, cobalt nitrate at a concentration of 20. mu.M, and sodium bicarbonate at a concentration of 25 mM; (II) an aqueous solution of 50mg/L phenol and 20. mu.M cobalt nitrate adjusted to pH 8.7 with sodium hydroxide.
Example 3
To 24mL of the prepared reaction solution (I) or (II), 0.01g of a metal-supported catalyst (the supported amount of the catalyst is 1.7%) was added. Then, the mixture was stirred at a constant temperature of 25 ℃ and reacted for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 2. The reaction solution has two types: (I) an aqueous solution of dye concentration 50mg/L, hydrogen peroxide concentration 80mM, sodium bicarbonate concentration 25 mM; (II) an aqueous solution of 50mg/L dye and 80mM hydrogen peroxide. The results are shown in Table 2. After the reaction, the loss of the cobalt element in the cobalt-supported catalyst was 0.2 ppm.
Example 4
20mL of the prepared reaction solution (I) or (II) was taken, and then 0.0117g of Co (or Cu) supported catalyst (the mass fraction of the metal element in the catalyst was 5%) was added. Thereafter, the mixture was allowed to react at a constant temperature of 45 ℃ for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 3. Wherein the reaction liquid is divided into two types: i and II. For I, the phenol concentration was 0.5mM, the hydrogen peroxide concentration was 35mM, and the sodium bicarbonate concentration was 44 mM; for II, the phenol concentration was 0.5mM, the hydrogen peroxide concentration was 35mM, and the solution pH was adjusted to 8.70 with sodium hydroxide.
Example 5
20mL of the prepared reaction solution (I) or (II) was taken, and then 0.0117g of Co-supported catalyst added with other metal ions was added. Thereafter, the mixture was allowed to react at a constant temperature of 45 ℃ for 5 hours. After the reaction, samples were taken for analysis. The results are shown in Table 4. Wherein the reaction liquid is divided into two types: i and II. For I, the phenol concentration was 0.5mM, the hydrogen peroxide concentration was 35mM, and the sodium bicarbonate concentration was 44 mM; for II, the phenol concentration was 0.5mM, the hydrogen peroxide concentration was 35mM, and the solution pH was adjusted to 8.70 with sodium hydroxide.
TABLE 1
TABLE 2
As can be seen from Table-2, the effect of the supported transition metal catalyst in the bicarbonate-activated hydrogen peroxide system is significantly better than that of the hydrogen peroxide oxidant directly used, regardless of the decolorization rate and the COD removal rate of the dye. Compared with the method of directly using water-soluble transition metal ions in the table-1, the loss rate of the loaded transition metal catalyst in wastewater treatment is low (0.2 ppm), and the technical problem of secondary pollution is avoided.
TABLE 3
In Table-3, similar results were also shown for the degradation of phenol: the phenol degradation rate in the hydrogen peroxide system activated by bicarbonate is higher than that in the hydrogen peroxide system under the similar pH condition by using various carriers and catalysts loaded by transition metal ions, and meanwhile, the loss rate of the transition metal ions is far lower than that in the system without the sodium bicarbonate.
TABLE 4
Table-4 shows that the activity of the supported transition metal ions in the bicarbonate-activated hydrogen peroxide system is further improved in the presence of various additives.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention should not be limited by the disclosure of the preferred embodiments. Therefore, it is intended that all equivalents and modifications which do not depart from the spirit of the invention disclosed herein are deemed to be within the scope of the invention.
Claims (7)
1. A method for treating organic wastewater by hydrogen carbonate activated hydrogen peroxide catalytic oxidation is characterized in that load type transition metal ions, hydrogen peroxide activated by hydrogen carbonate and organic wastewater are mixed and stirred for reaction, and the reaction is finished when the hydrogen peroxide is completely consumed; wherein,
the supported transition metal ion is used as a catalyst, the mass percentage concentration of the transition metal ion in the catalyst is 0.1-10%, the dosage of the supported transition metal ion is 0.01-10g/L, the hydrogen peroxide is used as an oxidizing agent, and the hydrogen peroxide oxidizing agent activated by the bicarbonate is formed by preparing hydrogen peroxide and bicarbonate into an aqueous solution, wherein the concentration of the bicarbonate in the mixture is 0.5-1000mM/L, and the concentration of the hydrogen peroxide in the mixture is 1-500 mM/L.
2. The method for the catalytic oxidation treatment of organic wastewater by hydrogen carbonate activated hydrogen peroxide according to claim 1, wherein the supported transition metal ions are one or more of cobalt, chromium, manganese, copper, iron, nickel, vanadium, molybdenum and tungsten.
3. The method for the catalytic oxidation treatment of organic wastewater by hydrogen carbonate activated hydrogen peroxide as claimed in claim 1, wherein an additive is added to the supported transition metal catalyst, the additive of the catalyst is alkaline earth metal ions or/and transition metal ions without redox activity, and the mass percentage concentration of the additive in the catalyst is 0.1-20 wt%.
4. The method for the catalytic oxidation treatment of organic wastewater by using hydrogen carbonate activated hydrogen peroxide as claimed in claim 3, wherein the additive of the catalyst is one or more of magnesium, calcium, barium, strontium, scandium, yttrium, zirconium and zinc ions.
5. The method for the catalytic oxidation treatment of organic wastewater with hydrogen carbonate activated hydrogen peroxide according to any one of claims 1 to 4, wherein the cation of the hydrogen carbonate is an alkali metal ion or/and an alkaline earth metal ion.
6. The method for the catalytic oxidation treatment of organic wastewater with hydrogen carbonate activated hydrogen peroxide according to any one of claims 1 to 4, wherein the cation of the hydrogen carbonate is one or more of lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium and ammonium ions.
7. The method for treating organic wastewater by using hydrogen carbonate activated hydrogen peroxide for catalytic oxidation as claimed in any one of claims 1 to 4, wherein the carrier of the catalyst is alumina, titanium dioxide, silica, diatomite or montmorillonite.
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| CN103193361A (en) * | 2013-03-18 | 2013-07-10 | 哈尔滨工程大学 | Advanced treatment, regeneration and reuse device and method of domestic sewage from ships |
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| CN113830834A (en) * | 2021-08-31 | 2021-12-24 | 天津大学 | Method for removing sulfamethoxazole by activating peroxybicarbonate with manganese dioxide |
| CN116037122A (en) * | 2022-11-11 | 2023-05-02 | 北京师范大学 | Bimetal-loaded carbon nanofiber catalyst and preparation method and application thereof |
| CN115779953A (en) * | 2022-12-19 | 2023-03-14 | 中南大学 | Copper-loaded carbon-based single-atom material and preparation method and application thereof |
| CN115745137A (en) * | 2022-12-20 | 2023-03-07 | 成都理工大学 | Method for treating alkaline wastewater by Fenton system |
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| CN116375171B (en) * | 2023-04-07 | 2024-05-03 | 中复神鹰碳纤维股份有限公司 | Continuous catalytic oxidation process for DMSO-containing industrial wastewater |
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