CN116282701A - Advanced treatment method for biochemical effluent of coal chemical industry and application thereof - Google Patents
Advanced treatment method for biochemical effluent of coal chemical industry and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000003245 coal Substances 0.000 title claims abstract description 68
- 239000000126 substance Substances 0.000 title claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 124
- 230000003647 oxidation Effects 0.000 claims abstract description 121
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 239000002351 wastewater Substances 0.000 claims abstract description 99
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 68
- 239000007800 oxidant agent Substances 0.000 claims abstract description 46
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 238000006243 chemical reaction Methods 0.000 claims description 32
- 230000001699 photocatalysis Effects 0.000 claims description 30
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- 239000012141 concentrate Substances 0.000 claims description 18
- 230000010718 Oxidation Activity Effects 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
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- 238000001223 reverse osmosis Methods 0.000 claims description 12
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- 238000001728 nano-filtration Methods 0.000 claims description 10
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- 239000000243 solution Substances 0.000 claims description 6
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- 238000000108 ultra-filtration Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
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- 150000002739 metals Chemical class 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 12
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- 230000001276 controlling effect Effects 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 125000001477 organic nitrogen group Chemical group 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- -1 iron modified titanium dioxide Chemical class 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
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- 238000006731 degradation reaction Methods 0.000 description 4
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- 241000894006 Bacteria Species 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
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- 235000003891 ferrous sulphate Nutrition 0.000 description 2
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- 238000001640 fractional crystallisation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
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- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The application discloses a coal chemical industry biochemical effluent advanced treatment method and application thereof, belonging to the technical field of sewage treatment. Aiming at the problems that ammonia nitrogen of biochemical effluent in common coal chemical industry can reach the standard stably, but total nitrogen and COD cannot reach the standard stably, the advanced treatment method adopts the combination of ultraviolet irradiation, an oxidant and a catalyst to carry out advanced oxidation, and selects and sets specific oxidation methods and conditions according to different indexes of the ammonia nitrogen and the total nitrogen of the influent water so as to ensure that the removal efficiency of the total nitrogen and the COD is improved to the greatest extent on the basis of reducing energy consumption. The advanced treatment method is further applied to the coal chemical wastewater, so that the zero emission of the coal chemical wastewater can be realized. After the advanced treatment is carried out on the biochemical effluent by the method, the treated wastewater is recycled to the coal chemical production process, so that economic benefits are created for enterprises, and zero emission of wastewater is realized.
Description
Technical Field
The application belongs to the technical field of coal chemical wastewater treatment, and particularly relates to a coal chemical biochemical effluent advanced treatment method and application thereof.
Background
The raw material used in the coal chemical production is coal, and the wastewater produced in the industry has the characteristics of large drainage, high pollutant concentration, high hardness, high turbidity and the like due to the particularity of the production process. At present, physicochemical and biochemical combined process treatment is generally adopted for treating wastewater in coal chemical industry, ammonia nitrogen in biochemical effluent after biochemical process treatment can often meet emission requirements, but COD and total nitrogen removal efficiency are not high, and the total nitrogen in biochemical effluent is nitrate which is not thoroughly denitrified, and the total nitrogen in biochemical effluent is organic nitrogen which cannot be oxidized, so that the total nitrogen in the effluent exceeds standard.
In the related art, for example, chinese patent publication No. CN105439311A describes a method for advanced treatment of biochemical effluent water waste water of coal chemical industry by using two-stage ozone oxidation and active carbon adsorption as main bodies, wherein two-stage ozone catalytic oxygen is adoptedThe advanced oxidative decomposition of refractory organic matters can be realized, the treatment effect of the effluent is improved, meanwhile, the adsorption effect of the activated carbon is combined, the stability of the effluent quality is guaranteed to reach the emission standard and the recycling standard, the impact load resistance of the device is high, the device can be used for advanced treatment of refractory wastewater, but the activated carbon generated in the method is used as dangerous waste or is required to be matched with an activated carbon regeneration device, and the investment and the operation cost of enterprises are increased intangibly. The advanced treatment system comprises a fluidized reaction bed, a coagulation reaction tank, a sedimentation tank, a COD degradation agent dosing device and a PAM dosing device which are sequentially communicated, wherein the COD degradation agent dosing device is communicated with the fluidized reaction bed, the PAM dosing device is communicated with the coagulation reaction tank, and a sludge outlet of the sedimentation tank is communicated with the fluidized reaction bed; the invention utilizes COD degradation agent to decompose COD in the coal chemical wastewater, and the suspended matters and COD in the wastewater are removed by coagulating sedimentation, thereby achieving the purpose of advanced treatment of the coal chemical wastewater, meeting the national relevant emission standard, but still having the problems of secondary pollution caused by adding the agent, and the like. Further, as disclosed in Chinese patent publication No. CN105645506A, a system for advanced treatment of wastewater from coal chemical industry by photo-Fenton catalytic oxidation and a method for treating wastewater from coal chemical industry by using sunlight in TiO are disclosed 2 Under the catalysis of the like, not only part of organic matters can be directly decomposed, but also the hydroxy complex of the iron serving as a catalyst has better light absorption performance and absorbs photolysis, more OH is generated, the reaction speed is high, and the Fe can be enhanced by sunlight illumination 3+ To improve Fe 2+ The concentration of the catalyst is favorable for the catalytic decomposition of OH, so that the pollutant removal effect is improved, the removal rate of COD and ammonia nitrogen by the process is more than 90%, and the chromaticity is also greatly removed; however, the method adopts sunlight as a light source, and has the problems of low utilization rate, secondary pollution after the light Fenton is added with ferrous ions, and the like.
The problem that the COD of biochemical effluent in the coal chemical industry does not meet the national relevant emission standard or the problem that the total nitrogen in biochemical wastewater exceeds the standard is ignored in the prior art. The treatment of biochemical effluent in coal chemical industry still has the problems of low denitrification efficiency, difficult thorough removal of organic matters, immature technical route of zero emission and the like. Therefore, on the basis of reducing the COD of biochemical effluent of the coal chemical industry, how to further improve the total nitrogen removal efficiency in the wastewater of the coal chemical industry, especially nitrate nitrogen and organic nitrogen, and the problem of zero discharge of the wastewater of the coal chemical industry is to be solved because secondary pollution is not generated as much as possible.
Furthermore, the applicant has found that the efficiency of advanced oxidation varies greatly for different water qualities, different types of organic matter and different concentrations of coal chemical industry wastewater, even under the same conditions. However, it is impractical and difficult to be applied in engineering if advanced oxidation conditions adapted to different kinds of organic matters are individually established according to different water qualities to improve advanced oxidation efficiency of the organic matters in such wastewater.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that ammonia nitrogen of biochemical effluent in coal chemical wastewater treatment can reach the standard stably, but total nitrogen and COD cannot reach the standard stably, the application provides a coal chemical biochemical effluent advanced treatment method and application thereof, wherein the advanced treatment method adopts a mode of combining ultraviolet irradiation, an oxidant and a catalyst mutually to carry out advanced oxidation. On the other hand, aiming at the problem of treatment under what oxidation conditions are adopted, a method for selecting and setting specific oxidation methods and conditions according to different indexes of ammonia nitrogen and total nitrogen in the inlet water is provided, and the removal efficiency of total nitrogen and COD in the wastewater is effectively improved through the combination of oxidation means. The advanced treatment method is further applied to the coal chemical wastewater, so that the zero emission of the coal chemical wastewater can be realized. After the biochemical effluent in the coal chemical wastewater treatment is subjected to advanced treatment by the method, the treated wastewater is reused in the coal chemical production process, so that zero discharge of wastewater is realized while the treatment cost is reduced for enterprises.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the application is as follows:
the application provides a advanced treatment method for biochemical effluent in coal chemical industry, which selectively adopts one or more combined advanced oxidation modes of ultraviolet irradiation, oxidant addition and catalyst addition according to different indexes of influent ammonia nitrogen and total nitrogen, and specifically comprises the following steps:
s1: measuring ammonia nitrogen and total nitrogen of biochemical effluent of coal chemical industry;
s2: the advanced oxidation mode and conditions are selected according to the following conditions,
(i) When C Ammonia nitrogen /C Total nitrogen When the value is between 0.5 and 1, performing advanced oxidation by adopting ultraviolet irradiation and oxidant addition at normal temperature;
(ii) When C Ammonia nitrogen /C Total nitrogen When the value is between 0.3 and 0.5, performing advanced oxidation by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under heating conditions, wherein the catalyst is a catalyst with photocatalytic oxidation activity;
(iii) When C Ammonia nitrogen /C Total nitrogen When the value is between 0 and 0.3, the sectional type advanced oxidation is carried out by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under the heating condition, wherein the sectional type advanced oxidation comprises the front-stage advanced oxidation and the rear-stage advanced oxidation, the wastewater firstly enters a front-stage advanced oxidation section for reaction, the change of ammonia nitrogen and total nitrogen content is dynamically monitored in the reaction process, and when C Ammonia nitrogen /C Total nitrogen When the value is increased from 0 to 0.3 to 0.6 to 0.8, the catalyst is immediately transferred to a rear-stage advanced oxidation working section, the front-stage advanced oxidation catalyst is a catalyst with photocatalytic oxidation activity, and the rear-stage advanced oxidation catalyst is a catalyst with photocatalytic reduction activity.
Further, the ammonia nitrogen content in the inflow water is between 0 and 20mg/L.
Further, the catalyst having photocatalytic oxidation activity includes: titanium dioxide modified by metals such as iron, platinum and the like.
Further, the catalyst having photocatalytic reduction activity includes: titanium dioxide modified by silver metal.
Further, the catalyst with photocatalytic oxidation activity is an iron-modified titanium dioxide catalyst, and after being irradiated and excited by an ultraviolet lamp, the surface of the catalyst can generate a hollow electron pair, so that carriers can be effectively separated, the photocatalytic oxidation activity is improved, the removal rate of organic matters in wastewater is enhanced, and organic nitrogen in the wastewater is converted into ammonia nitrogen and nitrate nitrogen.
Further, the catalyst with photocatalytic reduction activity is a silver-modified titanium dioxide catalyst, and the silver-modified titanium dioxide catalyst prepared by adopting a photocatalytic reduction method is successfully doped into a titanium dioxide crystal phase, and can still exist in a simple substance silver form, so that the catalyst has stronger reducibility, can well realize the aim of reducing nitrate nitrogen, and enhances the effect of removing the nitrate nitrogen in wastewater.
Further, the catalyst in the front-stage advanced oxidation in the step (iii) is an iron modified titanium dioxide catalyst, and after being irradiated and excited by an ultraviolet lamp, the surface of the catalyst can generate a blank pair of electrons so that carriers can be effectively separated, thereby improving the photocatalytic oxidation activity, enhancing the removal rate of organic matters in the wastewater, and converting organic nitrogen in the wastewater into ammonia nitrogen and nitrate nitrogen; the middle catalyst in the later-stage advanced oxidation is a silver-modified titanium dioxide catalyst, the silver-modified titanium dioxide catalyst prepared by adopting a photocatalytic reduction method is successfully doped into a titanium dioxide crystal phase, and the silver is probably still in the form of elemental silver, so that the catalyst has stronger reducibility, can well realize the aim of reducing nitrate nitrogen, and enhances the effect of removing the nitrate nitrogen in wastewater.
Further, the addition amount of the catalyst is 0.1 to 0.3 percent of the mass of the sewage.
Further, the ultraviolet irradiation intensity is 20 to 150mw/cm 2 The wavelength of the ultraviolet irradiation was 254nm.
Further, the oxidant is one or more of hydrogen peroxide, sodium hypochlorite solution and sodium persulfate solution. Further, the oxidant is one or more of 28wt% hydrogen peroxide, 8wt% sodium hypochlorite solution and 1mol/L sodium persulfate solution.
Further, the oxidant adopts a one-time adding mode, and the adding amount of the oxidant is 0.1-0.3% of the sewage mass.
Further, in the above (ii) and (iii), the heating condition is heating to 30 to 60 ℃, and under the temperature condition, the rate and the efficiency of the advanced oxidation reaction can be considered; when the reaction temperature is higher than 60 ℃, the economic value in practical application is not high, and when the reaction temperature is lower than 30 ℃, the effect of the treated wastewater is found in practical application, and the treated wastewater is difficult to reach the recycling requirement although the effect is better than the effect at normal temperature.
Further, the reaction pH value of the advanced treatment is between 6 and 9, and the pH value does not need to be regulated in the reaction process.
The application also provides application of the advanced treatment method for the biochemical effluent of the coal chemical industry in treatment of the biochemical effluent of the coal chemical industry.
Further, the application is a treatment method for zero emission of biochemical effluent of coal chemical industry, which comprises the following steps:
(1) Advanced treatment of biochemical effluent, which is to carry out advanced treatment on biochemical wastewater by adopting any one of the advanced treatment methods for biochemical effluent in coal chemical industry, wherein COD and ammonia nitrogen in the treated wastewater are respectively controlled within 30mg/L and 5 mg/L;
(2) Reclaimed water is recycled, the wastewater subjected to advanced treatment in the step (1) is treated again by adopting a double-membrane method of ultrafiltration and reverse osmosis, membrane clear liquid after treatment is recycled, and membrane concentrate (strong brine) enters subsequent crystallization and salt separation treatment; on the one hand, ultrafiltration can remove part of organic matters in the wastewater, reduce chromaticity, entrap part of colloid, bacteria and other impurities, and prolong the service life of the subsequent reverse osmosis membrane; the reverse osmosis membrane can remove most of salt in water, and has extremely high removal effect on hardness, COD and the like, so that the quality of the recycled water is ensured;
(3) The crystallization and salt separation are carried out, the membrane concentrate (reverse osmosis concentrate) adopts nanofiltration to carry out salt separation, wherein the nanofiltration concentrate mainly contains monovalent salts such as sodium chloride, sodium nitrate and the like, the nanofiltration concentrate contains salts such as sodium chloride, sodium nitrate, sodium sulfate and the like, the nanofiltration clear liquid and the concentrate are respectively subjected to high-power concentration by high-pressure reverse osmosis, the concentrate is respectively subjected to thermal method fractional crystallization, the salts are recycled, and the condensate is recycled.
The application also provides a treatment system of biochemical effluent zero release of coal industry, and this system is including the advanced treatment unit, reuse of reclaimed water unit and the strong brine crystallization divides salt unit that are connected in proper order, and advanced treatment unit is including realizing the advanced oxidation treatment mode of above-mentioned ultraviolet irradiation, additive oxidant, the combination of additive catalyst three simultaneously.
3. Advantageous effects
Compared with the prior art, the application has the beneficial effects that:
(1) The advanced treatment method for biochemical effluent of the coal chemical industry provided by the application is that on the basis of a large number of actual advanced oxidation treatment works of the industrial coal chemical industry, the advanced oxidation conditions are controlled according to different water inflow indexes by exploring the degradation rule of organic matters, so that the advanced oxidation process can be performed with high efficiency. According to different indexes of ammonia nitrogen and total nitrogen of the inflow water, a high-grade oxidation mode of one or more of ultraviolet irradiation, oxidant addition and catalyst addition is selectively adopted, when the total nitrogen concentration of the inflow water is low, the synergistic effect of the oxidant and ultraviolet is mainly adopted, and when the total nitrogen concentration of the inflow water is high, the synergistic effect of the combination of the ultraviolet irradiation, the oxidant and the catalyst is adopted, sectional oxidation is adopted, and different types of catalysts can be adopted according to requirements. When the removal rate of organic matters in the wastewater needs to be enhanced and organic nitrogen is converted into ammonia nitrogen and nitrate nitrogen, an iron modified titanium dioxide catalyst can be adopted; when the nitrate nitrogen in the wastewater needs to be removed, a silver-modified titanium dioxide catalyst can be used. The catalyst can effectively improve the removal efficiency of COD of organic matters in the wastewater on one hand and can improve the removal efficiency of ammonia nitrogen in the wastewater on the other hand.
(2) According to the advanced treatment method for the biochemical effluent in the coal chemical industry, provided by the application, according to the detection index of the biochemical effluent as the standard of the high-grade oxidation difficulty degree of the balance, different high-grade oxidation conditions are adopted for the monitoring indexes in different areas, so that the high-grade oxidation efficiency of organic matters in wastewater can be effectively improved, and the problems that the high-grade oxidation mode is difficult to select, so that the resource waste and the treatment cost are high are solved.
(3) The application provides a coal chemical industry biochemical effluent advanced treatment method, adopts ultraviolet + oxidant + catalyst combination technology to be used for coal chemical industry waste water treatment to remove the effect contrast with Fenton, ozone, oxidant + ozone and ultraviolet + oxidant technology, the advanced oxidation efficiency of this application is showing and is improving.
Drawings
FIG. 1 is a process flow diagram of an embodiment 1.
Detailed Description
The present application is further described below in connection with specific embodiments.
The terms such as "upper", "lower", "left", "right", "middle" and the like referred to in the present specification are also for convenience of description, and are not intended to limit the scope of the present invention, but rather to limit the scope of the present invention, and the changes or modifications of the relative relationship are considered to be within the scope of the present invention without substantial modification of the technical content.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, metric or value. The degree of flexibility of a particular variable can be readily determined by one skilled in the art.
As used herein, the term "is intended to be synonymous with" one or more of ". For example, "at least one of A, B and C" expressly includes a only, B only, C only, and respective combinations thereof.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limits of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principles apply to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all such values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.
Example 1
The embodiment provides a coal chemical industry biochemical effluent advanced treatment method, which specifically comprises the following steps:
s1: measuring the ammonia nitrogen, total nitrogen and COD content of biochemical effluent of the coal chemical industry;
s2: the advanced oxidation mode and conditions are selected according to the following conditions,
(i) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.5 and 1, performing advanced oxidation by adopting ultraviolet irradiation and oxidant addition at normal temperature;
(ii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.3 and 0.5, performing advanced oxidation by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under heating conditions, wherein the catalyst is a catalyst with photocatalytic oxidation activity;
(iii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0 and 0.3, the sectional type advanced oxidation is carried out by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under the heating condition, wherein the sectional type advanced oxidation comprises the front-stage advanced oxidation and the rear-stage advanced oxidation, the wastewater firstly enters a front-stage advanced oxidation section for reaction, the change of ammonia nitrogen and total nitrogen content is dynamically monitored in the reaction process, and when C Ammonia nitrogen /C Total nitrogen When the value is increased from 0 to 0.3 to 0.6 to 0.8, the process is immediately transferred to a post-stage advanced oxidation working section, and the front stage is highThe catalyst in the stage oxidation is a catalyst with photocatalytic oxidation activity, and the catalyst in the later stage advanced oxidation is a catalyst with photocatalytic reduction activity.
The sample is biochemical effluent from a coal chemical biochemical unit of an enterprise, and the detected biochemical effluent comprises COD=92.5 mg/L, ammonia nitrogen=10.8 mg/L, total nitrogen=19.2 mg/L and C Ammonia nitrogen /C Total nitrogen Because of this, advanced oxidation was performed by (i), i.e., ultraviolet irradiation at room temperature and addition of an oxidizing agent, was performed. The method comprises the following steps:
the advanced oxidation unit is ultraviolet irradiation with wavelength of 254nm and oxidant, and the ultraviolet irradiation intensity is controlled to be 20mw/cm in the whole process 2 The adding amount of the oxidant (hydrogen peroxide) is controlled to be 0.2 percent (mass ratio), and the advanced oxidation reaction time is 15 minutes. After treatment, COD is reduced to 27.1mg/L, ammonia nitrogen is reduced to 4.4mg/L, and total nitrogen is reduced to 9.8mg/L (meeting the requirement of a treatment unit of a subsequent reclaimed water recycling production process, COD is less than or equal to 30mg/L, and ammonia nitrogen is less than or equal to 5 mg/L). The effluent after advanced oxidation enters a subsequent reclaimed water recycling treatment unit for resource utilization, so that zero emission of the wastewater in the coal chemical industry is realized.
Comparative example 1A
In contrast, other treatment conditions were the same as in example 1, except that the same wastewater was treated: the Fenton process is adopted to replace the advanced oxidation step in the embodiment 1 for treatment, and the specific steps and conditions are as follows: adding hydrochloric acid into the wastewater, regulating the pH of the effluent to 3, wherein the adding amount of hydrogen peroxide is 0.2% (mass ratio) and the adding amount of ferrous sulfate is 100mg/L, stirring in a bottom aeration mode, and controlling the pH of the wastewater to be about 3 in the whole reaction process by adding HCl or liquid alkali, wherein the reaction time is 90min. After the reaction is finished, adding liquid caustic soda into the mixture to adjust the pH of the wastewater to about 9, aerating for 30min, and standing to obtain supernatant for detection.
After the Fenton technology in the comparative example is adopted to carry out advanced oxidation treatment on the wastewater, COD is reduced to 58.5mg/L, ammonia nitrogen is reduced to 6.5mg/L, and total nitrogen is reduced to 14.1mg/L.
Comparative example 1B
In contrast, other treatment conditions were the same as in example 1, except that the same wastewater was treated: the ozone process is adopted to replace the advanced oxidation step in the embodiment 1 for treatment, and the specific steps and conditions are as follows: the pH value of the wastewater is regulated to 8, and the pH value of the wastewater is controlled to be about 8 in the whole process of adding HCl or liquid alkali in the reaction process. The yield of the ozone is controlled to be 30mg/min, and the reaction time is controlled to be 30min.
After the advanced oxidation treatment is carried out on the wastewater by adopting the ozone oxidation technology in the comparative example, the COD is reduced to 47.3mg/L, the ammonia nitrogen is reduced to 5.6mg/L, and the total nitrogen is reduced to 11.2mg/L.
Comparative example 1C
In contrast, other treatment conditions were the same as in example 1, except that the same wastewater was treated: the combined process of oxidant and ozone is adopted to replace the advanced oxidation step in the embodiment 1 for treatment, and the specific steps and conditions are as follows: the pH value of the wastewater is regulated to 8, and the pH value of the wastewater is controlled to be about 8 in the whole process of adding HCl or liquid alkali in the reaction process. Controlling the adding amount of hydrogen peroxide to be 0.2% (mass ratio), controlling the yield of the introduced ozone to be 30mg/min, and controlling the reaction time to be 30min;
through detection, after the advanced oxidation treatment is carried out on the wastewater by adopting the combined technology of the oxidant and the ozone in the comparative example, the COD of the wastewater is reduced to 43.5mg/L, the ammonia nitrogen is reduced to 5.2mg/L, and the total nitrogen is reduced to 10.5mg/L.
Example 2
The embodiment provides a coal chemical industry biochemical effluent advanced treatment method, which specifically comprises the following steps:
s1: measuring the ammonia nitrogen, total nitrogen and COD content of biochemical effluent of the coal chemical industry;
s2: the advanced oxidation mode and conditions are selected according to the following conditions,
(i) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.5 and 1, performing advanced oxidation by adopting ultraviolet irradiation and oxidant addition at normal temperature;
(ii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.3 and 0.5, the high-grade oxidation is carried out under the heating condition by adopting the modes of ultraviolet irradiation, adding an oxidant and adding a catalyst, wherein the catalyst has the following characteristics ofA catalyst having photocatalytic oxidation activity;
(iii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0 and 0.3, the sectional type advanced oxidation is carried out by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under the heating condition, wherein the sectional type advanced oxidation comprises the front-stage advanced oxidation and the rear-stage advanced oxidation, the wastewater firstly enters a front-stage advanced oxidation section for reaction, the change of ammonia nitrogen and total nitrogen content is dynamically monitored in the reaction process, and when C Ammonia nitrogen /C Total nitrogen When the value is increased from 0 to 0.3 to 0.6 to 0.8, the catalyst is immediately transferred to a rear-stage advanced oxidation working section, the front-stage advanced oxidation catalyst is a catalyst with photocatalytic oxidation activity, and the rear-stage advanced oxidation catalyst is a catalyst with photocatalytic reduction activity.
The sample is biochemical effluent from a coal chemical biochemical unit of an enterprise, and the detected biochemical effluent comprises COD=162.5 mg/L, ammonia nitrogen=14.8 mg/L, total nitrogen=43.2 mg/L and C Ammonia nitrogen /C Total nitrogen 0.3426, advanced oxidation is performed by (ii), i.e. under heating, using ultraviolet irradiation, adding an oxidant, adding a catalyst, which is a catalyst having photocatalytic oxidation activity, specifically:
ultraviolet irradiation, oxidant (hydrogen peroxide) and titanium dioxide modified by adding iron are adopted as catalysts at 30 ℃ to carry out advanced oxidation unit treatment: the advanced oxidation unit is simultaneously carried out by ultraviolet irradiation with wavelength of 254nm and oxidant (hydrogen peroxide), and the ultraviolet irradiation intensity is controlled to be 30mw/cm in the whole process 2 The adding amount of hydrogen peroxide is controlled to be 0.3 percent (mass ratio), and the catalyst adopts titanium dioxide modified by iron, so as to enhance the removal rate of organic matters in the wastewater and convert organic nitrogen in the wastewater into ammonia nitrogen and nitrate nitrogen; the reaction is carried out for 30min at 30 ℃, the COD is reduced to 28.5mg/L, the ammonia nitrogen is reduced to 3.2mg/L, and the total nitrogen is reduced to 16.8mg/L (meeting the requirement of a treatment unit of the subsequent reclaimed water recycling production process, the COD is less than or equal to 30mg/L, and the ammonia nitrogen is less than or equal to 5 mg/L) after the treatment.
The effluent after advanced oxidation enters a subsequent reclaimed water recycling treatment unit for resource utilization, so that zero emission of the wastewater in the coal chemical industry is realized.
Comparative example 2A
In contrast, other treatment conditions were the same as in example 2, except that the same wastewater was treated: the Fenton process is adopted to replace the advanced oxidation step in the embodiment 2 for treatment, and the specific steps and conditions are as follows: adding hydrochloric acid into the wastewater, regulating the pH of the effluent to 3, wherein the adding amount of hydrogen peroxide is 0.3% (mass ratio) and the adding amount of ferrous sulfate is 150mg/L, stirring in a bottom aeration mode, and controlling the pH of the wastewater to be about 3 in the whole reaction process by adding HCl or liquid alkali, wherein the reaction time is 45min. After the reaction is finished, adding liquid caustic soda into the mixture to adjust the pH of the wastewater to about 9, aerating for 45min, and standing to obtain supernatant for detection.
Through detection, the Fenton technology in the comparative example is adopted to reduce COD to 108.5mg/L and ammonia nitrogen to 9.5mg/L and total nitrogen to 33.6mg/L after advanced oxidation treatment is carried out on the wastewater.
Comparative example 2B
In contrast, other treatment conditions were the same as in example 2, except that the same wastewater was treated: the ozone oxidation is adopted to replace the advanced oxidation step in the embodiment 2 for treatment, and the specific steps and conditions are as follows: the pH value of the wastewater is regulated to 8, and the pH value of the wastewater is required to be controlled to be about 8 in the whole process by adding HCl or liquid alkali in the reaction process. The yield of the ozone is controlled to be 30mg/min, and the reaction time is controlled to be 45min.
Through detection, the COD is reduced to 64.5mg/L, the ammonia nitrogen is reduced to 8.5mg/L and the total nitrogen is reduced to 30.7mg/L after the advanced oxidation treatment of the wastewater by adopting the ozone oxidation technology in the comparative example.
Comparative example 2C
In contrast, other treatment conditions were the same as in example 2, except that the same wastewater was treated: the combined oxidant and ozone process is adopted to replace the advanced oxidation step in the embodiment 2, and the specific steps and conditions are as follows: the pH value of the wastewater is regulated to 8, and the pH value of the wastewater is controlled to be about 8 in the whole process of adding HCl or liquid alkali in the reaction process. Controlling the adding amount of hydrogen peroxide to be 0.2 percent (mass ratio); the yield of the ozone is controlled to be 30mg/min, and the reaction time is controlled to be 45min.
After the wastewater is treated by adopting the combined technology of the oxidant and the ozone in the comparative example, the COD of the wastewater is reduced to 55.5mg/L, the ammonia nitrogen is reduced to 6.5mg/L, and the total nitrogen is reduced to 27.5mg/L.
Comparative example 2D
In contrast, other treatment conditions were the same as in example 2, except that the same wastewater was treated: no catalyst is added. At 30 ℃, the ultraviolet irradiation intensity is 30mw/cm 2 After the reaction is finished, the COD of the wastewater is reduced to 28.5mg/L, the ammonia nitrogen is reduced to 8.1mg/L and the total nitrogen is reduced to 24.8mg/L by controlling the adding amount of the hydrogen peroxide to be 0.3% (mass ratio).
Example 3
The embodiment provides a coal chemical industry biochemical effluent advanced treatment method, which specifically comprises the following steps:
s1: measuring the ammonia nitrogen, total nitrogen and COD content of biochemical effluent of the coal chemical industry;
s2: the advanced oxidation mode and conditions are selected according to the following conditions,
(i) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.5 and 1, performing advanced oxidation by adopting ultraviolet irradiation and oxidant addition at normal temperature;
(ii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0.3 and 0.5, performing advanced oxidation by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under heating conditions, wherein the catalyst is a catalyst with photocatalytic oxidation activity;
(iii) When the ammonia nitrogen content is between 0 and 20mg/L, C Ammonia nitrogen /C Total nitrogen When the value is between 0 and 0.3, the sectional type advanced oxidation is carried out by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under the heating condition, wherein the sectional type advanced oxidation comprises the front-stage advanced oxidation and the rear-stage advanced oxidation, the wastewater firstly enters a front-stage advanced oxidation section for reaction, the change of ammonia nitrogen and total nitrogen content is dynamically monitored in the reaction process, and when C Ammonia nitrogen /C Total nitrogen When the value is increased from 0 to 0.3 to 0.6 to 0.8, the catalyst is transferred to a post-stage advanced oxidation section, and the catalyst in the front-stage advanced oxidation section is provided withThe catalyst with photocatalytic oxidation activity and the catalyst in the later stage advanced oxidation is a catalyst with photocatalytic reduction activity.
The sample is biochemical effluent from a coal chemical biochemical unit of an enterprise, and the detected biochemical effluent comprises COD=222.5 mg/L, ammonia nitrogen=16.8 mg/L, total nitrogen=64.3 mg/L and C Ammonia nitrogen /C Total nitrogen 0.2612, therefore (iii), i.e., performing staged advanced oxidation by ultraviolet irradiation, adding hydrogen peroxide, and adding a catalyst under heating conditions, the staged advanced oxidation includes a front stage advanced oxidation and a rear stage advanced oxidation, wherein the front stage advanced oxidation catalyst is a catalyst having photocatalytic oxidation activity, and the rear stage advanced oxidation catalyst is a catalyst having photocatalytic reduction activity, specifically:
advanced oxidation unit treatment: the advanced oxidation unit is simultaneously operated by three modes of ultraviolet irradiation with 254nm wavelength, hydrogen peroxide and catalyst, and the ultraviolet irradiation intensity is controlled to be 40mw/cm in the whole process 2 Controlling the addition amount of the oxidant to be 0.3 percent (mass ratio) L, adding catalysts for sectional oxidation, and adding catalysts for front-stage oxidation and rear-stage oxidation, wherein the catalysts for the front-stage oxidation adopt titanium dioxide modified by iron, so that the removal rate of organic matters in wastewater is enhanced, and when organic nitrogen is converted into ammonia nitrogen and nitrate nitrogen, C is as follows Ammonia nitrogen /C Total nitrogen When the value is increased to 0.65 from the initial 0.2612, the titanium dioxide is immediately transferred to a rear-stage advanced oxidation working section, and silver-modified titanium dioxide used by a catalyst in the rear-stage reaction enhances the effect of removing nitrate nitrogen in wastewater; the adding amount of the catalyst is 0.2% of the mass of the wastewater; the whole system temperature is controlled to be 45 ℃, and the advanced oxidation reaction time is 30min. Through the treatment, the COD is reduced to 26.5mg/L, the ammonia nitrogen is reduced to 3.2mg/L, and the total nitrogen is reduced to 15.3mg/L (meeting the requirement of a treatment unit of the subsequent reclaimed water recycling production process, the COD is less than or equal to 30mg/L, and the ammonia nitrogen is less than or equal to 5 mg/L).
The effluent after advanced oxidation enters a subsequent reclaimed water recycling treatment unit for resource utilization, so that zero emission of the wastewater in the coal chemical industry is realized.
Comparative example 3A
In contrast, other treatment conditions were the same as in example 3, except that the same wastewater was treated: the process of combining ozone and hydrogen peroxide is adopted to replace the advanced oxidation step in the embodiment 3 for treatment, and the specific steps and conditions are as follows: the pH value of the wastewater is regulated to 8, and the pH value of the wastewater is controlled to be about 8 in the whole process of adding HCl or liquid alkali in the reaction process. Controlling the adding amount of hydrogen peroxide to be 0.3% (mass ratio), controlling the yield of the introduced ozone to be 30mg/min, and controlling the reaction time to be 45min;
after the wastewater is treated by adopting the process of combining ozone and oxidant in the comparative example, the COD of the wastewater is reduced to 50.5mg/L, the ammonia nitrogen is reduced to 11.5mg/L and the total nitrogen is reduced to 53.5mg/L.
Comparative example 3B
In contrast, other treatment conditions were the same as in example 3, except that the same wastewater was treated: on the premise of no catalyst, ultraviolet and hydrogen peroxide are adopted to treat the wastewater. With the same reaction time as in example 3, the wastewater was subjected to the front-stage oxidation and then to the rear-stage oxidation.
Through the treatment, COD is reduced to 62.9mg/L, ammonia nitrogen is reduced to 12.8mg/L and total nitrogen is reduced to 47.5mg/L. The result shows that the wastewater treatment is difficult to meet the requirement without adding a catalyst, and the removal effect of COD and ammonia nitrogen is mainly improved due to the existence of the catalyst.
Comparative example 3C
In contrast, other treatment conditions were the same as in example 3, except that the same wastewater was treated: only iron modified titanium dioxide catalyst is added in the whole process.
After the reaction was completed, COD was reduced to 28.5mg/L, ammonia nitrogen was reduced to 5.1mg/L and total nitrogen was reduced to 31.3mg/L. The result shows that only the iron modified titanium dioxide catalyst is added, and the wastewater treatment is difficult to meet the requirement, mainly because the iron modified titanium dioxide catalyst is singly adopted as a photocatalytic oxidation active catalyst, and the removal effect of COD and ammonia nitrogen is only increased. The COD, ammonia nitrogen and total nitrogen in the water cannot be removed to a higher degree without the help of the photocatalytic reduction active catalyst.
Example 4
The application also provides a treatment system for zero emission of biochemical effluent of coal chemical industry, as shown in figure 1.
The system comprises a deep treatment unit, a reclaimed water recycling unit and a concentrated brine crystallization and salt separation unit which are sequentially connected, wherein the deep treatment unit can realize ultraviolet irradiation, oxidant addition and catalyst addition simultaneously to perform advanced oxidation, and the deep treatment unit comprises the following components:
(1) Advanced treatment of biochemical effluent, which is to carry out advanced treatment on biochemical wastewater by adopting any one of the advanced treatment methods for biochemical effluent in coal chemical industry, wherein COD and ammonia nitrogen in the treated wastewater are respectively controlled within 30mg/L and 5 mg/L;
(2) Reclaimed water is recycled, the wastewater subjected to advanced treatment in the step (1) is treated again by adopting a double-membrane method of ultrafiltration and reverse osmosis, membrane clear liquid after treatment is recycled, and membrane concentrate (strong brine) enters subsequent crystallization and salt separation treatment; on the one hand, ultrafiltration can remove part of organic matters in the wastewater, reduce chromaticity, entrap part of colloid, bacteria and other impurities, and prolong the service life of the subsequent reverse osmosis membrane; the reverse osmosis membrane can remove most of salt in water, and has extremely high removal effect on hardness, COD and the like, so that the quality of the recycled water is ensured;
(3) The crystallization and salt separation are carried out, the membrane concentrate (reverse osmosis concentrate) adopts nanofiltration to carry out salt separation, wherein the nanofiltration concentrate mainly contains monovalent salts such as sodium chloride, sodium nitrate and the like, the nanofiltration concentrate contains salts such as sodium chloride, sodium nitrate, sodium sulfate and the like, the nanofiltration clear liquid and the concentrate are respectively subjected to high-power concentration by high-pressure reverse osmosis, the concentrate is respectively subjected to thermal method fractional crystallization, the salts are recycled, and the condensate is recycled.
The above embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, such as the various combinations of the embodiments in examples 1 to 4, and any other changes, modifications, substitutions, and combinations without departing from the spirit and principles of the present invention should be equivalent and are within the scope of the present invention.
Claims (10)
1. A advanced treatment method for biochemical effluent in coal chemical industry is characterized in that the advanced treatment method selectively adopts one or more advanced oxidation modes of ultraviolet irradiation, oxidant addition and catalyst addition according to different indexes of influent ammonia nitrogen and total nitrogen, and specifically comprises the following steps:
s1: measuring ammonia nitrogen and total nitrogen of biochemical effluent of coal chemical industry;
s2: the advanced oxidation mode and conditions are selected according to the following conditions,
(i) When C Ammonia nitrogen /C Total nitrogen When the value is between 0.5 and 1, performing advanced oxidation by adopting ultraviolet irradiation and oxidant addition at normal temperature;
(ii) When C Ammonia nitrogen /C Total nitrogen When the value is between 0.3 and 0.5, performing advanced oxidation by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under heating conditions, wherein the catalyst is a catalyst with photocatalytic oxidation activity;
(iii) When C Ammonia nitrogen /C Total nitrogen When the value is between 0 and 0.3, the sectional type advanced oxidation is carried out by adopting ultraviolet irradiation, adding an oxidant and adding a catalyst under the heating condition, wherein the sectional type advanced oxidation comprises the front-stage advanced oxidation and the rear-stage advanced oxidation, the wastewater firstly enters a front-stage advanced oxidation section for reaction, the change of ammonia nitrogen and total nitrogen content is dynamically monitored in the reaction process, and when C Ammonia nitrogen /C Total nitrogen When the value is increased from 0 to 0.3 to 0.6 to 0.8, the catalyst is immediately transferred to a rear-stage advanced oxidation working section, the front-stage advanced oxidation catalyst is a catalyst with photocatalytic oxidation activity, and the rear-stage advanced oxidation catalyst is a catalyst with photocatalytic reduction activity.
2. The method for deeply treating biochemical effluent of coal chemical industry according to claim 1, wherein the catalyst with photocatalytic oxidation activity is one or more of titanium dioxide modified by metals such as iron and platinum; the catalyst with photocatalytic reduction activity is a silver-modified titanium dioxide catalyst.
3. The advanced treatment method for biochemical effluent of coal chemical industry according to claim 1 or 2, wherein the ammonia nitrogen content in the influent water is 0-20 mg/L.
4. The method for deeply treating biochemical effluent of coal chemical industry according to claim 3, wherein the addition amount of the catalyst is 0.1-0.3%.
5. The method for advanced treatment of biochemical effluent in coal chemical industry according to claim 4, wherein the ultraviolet irradiation intensity is 20-150 mw/cm 2 The wavelength of ultraviolet irradiation is 254nm; the oxidant is one or more of hydrogen peroxide, sodium hypochlorite solution and sodium persulfate solution.
6. The advanced treatment method for biochemical effluent of coal chemical industry according to claim 5, wherein the addition amount mass ratio of the oxidant is 0.1-0.3%.
7. The method for advanced treatment of biochemical effluent in coal chemical industry according to claim 6, wherein the heating conditions in (ii) and (iii) are heating to 30 to 60 ℃.
8. Use of a method for advanced treatment of biochemical effluent from coal industry according to any one of claims 1 to 7 for treating biochemical effluent from coal industry.
9. The method for treating the biochemical effluent of the coal chemical industry with zero emission is characterized by comprising the following steps of:
(1) Advanced treatment of biochemical effluent, wherein the advanced treatment method of biochemical effluent in coal chemical industry is adopted to carry out advanced treatment on biochemical wastewater, and COD and ammonia nitrogen in the treated wastewater are controlled within 30mg/L and 5mg/L respectively;
(2) Reclaimed water is recycled, the wastewater subjected to advanced treatment in the step (1) is treated again by adopting a double-membrane method of ultrafiltration and reverse osmosis, membrane clear liquid after treatment is recycled, and membrane concentrate enters subsequent crystallization and salt separation treatment;
(3) Crystallizing and separating salt, separating salt from the film concentrate by nanofiltration, concentrating the nanofiltration clear liquid and the concentrate respectively by high-pressure reverse osmosis, separating the concentrate by a thermal method, recycling the salt, and recycling the condensate.
10. The system is characterized by comprising a deep treatment unit, a reclaimed water recycling unit and a concentrated brine crystallization and salt separation unit which are sequentially connected, wherein the deep treatment unit comprises a treatment mode capable of simultaneously realizing advanced oxidation by combining ultraviolet irradiation, oxidant addition and catalyst addition in the deep treatment method of biochemical effluent of the coal chemical industry according to any one of claims 1-7.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117361738A (en) * | 2023-09-22 | 2024-01-09 | 太通建设有限公司 | Risk control and denitrification method and system for dissolved oxygen in sewage |
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