CN115093047B - Treatment method of byproduct high-salt wastewater - Google Patents
Treatment method of byproduct high-salt wastewater Download PDFInfo
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- CN115093047B CN115093047B CN202210708964.6A CN202210708964A CN115093047B CN 115093047 B CN115093047 B CN 115093047B CN 202210708964 A CN202210708964 A CN 202210708964A CN 115093047 B CN115093047 B CN 115093047B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 80
- 239000006227 byproduct Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000012267 brine Substances 0.000 claims abstract description 122
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 122
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 35
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 238000003672 processing method Methods 0.000 claims abstract description 5
- 239000008394 flocculating agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000007800 oxidant agent Substances 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 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 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007255 decyanation reaction Methods 0.000 abstract description 7
- 230000009615 deamination Effects 0.000 abstract description 3
- 238000006481 deamination reaction Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/76—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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
- C02F2101/30—Organic compounds
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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
- 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
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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- 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
- C02F2209/16—Total nitrogen (tkN-N)
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- 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
- C02F2209/20—Total organic carbon [TOC]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to the technical field of wastewater treatment, and particularly discloses a method for treating byproduct high-salt wastewater. The processing method comprises the following steps: adding a flocculating agent into the byproduct high-salt wastewater, and filtering to obtain clear liquid; adsorbing the clear liquid by resin, and separating liquid; decyanation treatment is carried out on the separating liquid under the conditions that the temperature is 60-80 ℃ and the pH value is 0.5-1.0, so as to obtain low-cyanide brine; deamination is carried out on the low-cyanide brine at the temperature of 30-100 ℃ and the pH value of 10-12, so as to obtain low-cyanide low-ammonia brine; carrying out staged oxidation on the low-cyanide low-ammonia brine to obtain oxidized brine; and (3) adding a reducing agent into the oxidized brine for reduction, and then adding a decoloring agent for decoloring to obtain refined brine. The method provided by the invention is safe and controllable, short in steps, small in investment and low in treatment cost, and can effectively recover high-concentration ammonia nitrogen, cyanide and refractory organic matters in the wastewater.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating byproduct high-salt wastewater.
Background
The problem of decomposition of cyanide is unavoidable in the production process of the cyano derivative product, and the peculiar malodor smell of the benzene ring cyano derivative product causes that the byproduct high-salt wastewater containing high-concentration cyanide, ammonia nitrogen and refractory organic matters is difficult to treat.
At present, an oxidation method is mainly adopted to treat high-salt wastewater rich in high-concentration cyanide, ammonia nitrogen, refractory organic matters, such as electrocatalytic oxidation, photocatalytic oxidation, ultraviolet irradiation, strong oxidants and the like, so that the investment cost is high, particularly the use condition of ultraviolet irradiation is severe, and the components such as the cyanide, the ammonia nitrogen and the like in the treatment process cannot be effectively recycled, so that a great amount of cyanide and ammonia nitrogen elements are wasted. In addition, for the wastewater with high-concentration ammonia nitrogen components, when the chlorine-related oxidant is used for oxidation, the enrichment of nitrogen trichloride is unavoidable, and the safety problem is very easy to be brought. Therefore, with the increasing severity of environmental protection, providing a viable and resource-based treatment method is becoming a major issue in such wastewater treatment research.
Disclosure of Invention
Aiming at the problems of high cost, harsh conditions, difficult recovery of cyanide, ammonia nitrogen and the like of the existing treatment method, the invention provides a treatment method for byproduct high-salt wastewater.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
a method for treating byproduct high-salt wastewater, comprising the following steps:
step one, adding a flocculating agent into the byproduct high-salt wastewater, and filtering to obtain clear liquid;
step two, carrying out resin adsorption on the clear liquid at the temperature of 10-35 ℃ to obtain a separation liquid;
step three, decyanating the separating liquid at the temperature of 60-80 ℃ and the pH value of 0.5-1.0 to obtain low-cyanide brine;
step four, deaminizing the low-cyanide brine at the temperature of 30-100 ℃ and the pH value of 10-12 to obtain low-cyanide low-ammonia brine;
step five, carrying out fractional oxidation on the low-cyanide low-ammonia brine to obtain oxidized brine;
and step six, adding a reducing agent into the oxidized brine for reduction, and then adding a decoloring agent for decoloring to obtain refined brine.
Compared with the prior art, the treatment method for the byproduct high-salt wastewater has the following advantages:
the flocculant is added to remove suspended matters in the high-salt wastewater, and macromolecule refractory organic matters carried in the clear liquid are removed at a limited temperature, so that the concentration of total organic carbon in the clear liquid is reduced, cyanide polymerization easily caused by overhigh temperature of the wastewater clear liquid is avoided, and the subsequent decyanation and deamination are ensured to be carried out smoothly; the decyanation treatment is carried out under the conditions that the temperature is 60-80 ℃ and the pH value is 0.5-1.0, cyanide ions in the separating liquid can be thoroughly converted into hydrogen cyanide, the residual quantity of cyanide in low-cyanide salt water is greatly reduced, the decomposition rate of cyanide is reduced, the maximum recovery rate of cyanide is ensured, and the consumption of energy is obviously reduced; because the byproduct high-salt wastewater contains a large amount of cyano derivatives, the existence of cyano inevitably causes the existence of ammonia nitrogen or ammonium ions with higher concentration in low-cyanide brine, and the ammonia nitrogen or ammonium ions in the separating liquid can be effectively separated from the low-cyanide brine by adopting a stripping method under the conditions that the temperature is 30-100 ℃ and the pH is 10-12, so that the ammonia nitrogen or ammonium ions in the separating liquid can be effectively separated from the low-cyanide brine, the ammonia water with higher concentration can be recovered on the basis that the low-cyanide brine is further purified, and huge additional value is additionally created; and oxidizing the organic matters remained in the wastewater by fractional oxidation, and adding a reducing agent into the excessive oxidant to perform reduction and decoloration treatment to obtain refined brine.
The treatment method provided by the invention is safe and controllable, has short steps, small investment and low treatment cost, can effectively recover high-concentration ammonia nitrogen, cyanide and refractory organic matters in the wastewater, and avoids the problem that the oxidation process is difficult to safely control because the wastewater is rich in the high-concentration ammonia nitrogen, so that the byproduct high-salt wastewater reaches the use standard of chlor-alkali industry, and the byproduct sodium chloride resource is effectively recovered and reused.
After the high-salt wastewater rich in high-concentration cyanide, ammonia nitrogen and refractory organic matters is treated by adopting the treatment method, the total organic carbon concentration in the refined brine can be stably controlled within 1ppm, and the use requirement of chlor-alkali industry is completely met.
Optionally, the specific process of the staged oxidation is as follows: adding a primary oxidant into the low-cyanide low-ammonia brine for primary oxidation to obtain primary oxidized brine; adding a secondary oxidant into the primary oxidized brine to perform secondary oxidation to obtain oxidized brine, wherein the reaction conditions of the primary oxidation are as follows: the pH is 1-3, the temperature is 50-60 ℃ and the time is 0.5-1.5 h; the reaction conditions of the secondary oxidation are as follows: the pH value is 3-8, the temperature is 80-100 ℃, and the time is 0.5-1.5 h.
The application adopts two-stage oxidation, and the primary oxidation process thoroughly oxidizes and decomposes the micromolecular organic matter into water and carbon dioxide, and simultaneously can also fracture and decompose most of the macromolecular organic matter into micromolecular organic matter, and the secondary oxidation process further oxidizes and decomposes the incomplete macromolecular organic matter of primary oxidation into micromolecular organic matter, and then converts the micromolecular organic matter which is cooperated with the incomplete micromolecular organic matter of primary oxidation reaction into carbon dioxide and water, thereby realizing the thorough oxidation of the low-cyanide and low-ammonia brine.
Optionally, the addition amount of the primary oxidant is 1 to 1.5 times of the pure amount of TOC in the low-cyanide low-ammonia brine. When the TOC concentration in the low-cyanide and low-ammonia brine is A and the volume of the byproduct high-salt wastewater is V, the pure TOC amount is A multiplied by V.
Optionally, the adding amount of the secondary oxidant is 5-10 times of the pure amount of TOC in the primary oxidized brine. When the TOC concentration in the primary oxidized brine is B and the volume of the byproduct high-salt wastewater is V, the TOC purity is B multiplied by V.
The addition of the primary oxidant and the secondary oxidant can ensure the oxidation effect of the low-cyanide low-ammonia brine and avoid the waste of the excessive oxidant.
Optionally, the primary oxidant is at least one of sodium chlorate, sodium hypochlorite or chlorine gas.
The preferred primary oxidant utilizes the strong oxidizing property of chlorine in the oxidation process to degrade and decompose small molecular organic matters in the brine into water and carbon dioxide, so that specific conditions are selected: the pH value is 1-3, the temperature is 50-60 ℃, and the excessive temperature is avoided, so that the solubility of chlorine in water is greatly reduced, and the utilization rate of the oxidant is reduced.
Optionally, the secondary oxidant is sodium ferrate or sodium persulfate.
The oxidation performance of the preferred secondary oxidant is higher than that of the primary oxidant, the secondary oxidation is carried out at the pH value of 3-8 and the temperature of 80-100 ℃, and the small molecular organic matters which are not thoroughly oxidized at the first stage and the macromolecular organic matters which remain in the brine can be thoroughly degraded, so that the concentration of organic carbon in the oxidized brine is reduced to the minimum level, the oxidation effect of the low-cyanide and low-ammonia brine is ensured, and the oxidation rate of the brine is obviously improved.
Optionally, the flocculant is at least one of activated carbon, diatomite or sawdust.
Suspended matters in the byproduct high-salt wastewater lose stability under the action of a specific flocculant, colloidal particle matters in the wastewater can mutually agglomerate and form floccules, suspended matters in the wastewater are thoroughly removed through filtration, and then the high-salt wastewater is purified, so that basic conditions are created for subsequent treatment, and the high-salt wastewater is prevented from blocking a production system due to more suspended matters in the subsequent treatment process.
Optionally, the addition amount of the flocculant is 0.1-0.5% based on 100% of the byproduct high-salt wastewater.
The preferable addition amount of the flocculant can thoroughly remove suspended matters in the wastewater to obtain wastewater clear liquid, and the treatment effect of the wastewater clear liquid is ensured.
Further alternatively, the flocculant is activated carbon, and the addition amount of the flocculant is 0.1-0.2% based on 100% of the by-product high-salt wastewater.
The refractory organic matters in the byproduct high-salt wastewater are difficult to degrade due to the complex molecular structure. The activated carbon has larger surface adsorption pore diameter, and can effectively adsorb macromolecular organic matters dissolved in the high-salt wastewater while flocculating and separating suspended matters in the high-salt wastewater, so that the concentration of the macromolecular organic matters in the wastewater is greatly reduced, and the processing load of a subsequent refractory organic matter separation step system is reduced; meanwhile, the filter-aid device can also play a certain role in the filtering and separating process.
And in the flocculation process of the high-salt wastewater by adopting the chemical activated carbon, 0.1-0.2% of the weight of the high-salt wastewater is added, so that suspended matters in the wastewater can be thoroughly removed to obtain wastewater clear liquid, and the treatment effect of the wastewater clear liquid is ensured.
Optionally, the resin is styrene macroporous adsorption resin.
Further optionally, the macroporous resin is of the model HYA-108.
Optionally, the pore diameter of the macroporous resin is 30 m-40 mm, and the pore diameter is 7-8 times of the adsorption target diameter in the byproduct high-salt wastewater.
Optionally, the adsorption volume of the resin is 45 BV-50 BV.
When the adsorption volume of the macroporous resin reaches 45 BV-50 BV, namely after adsorption saturation, methanol is adopted as an analysis solvent to analyze the resin system, and the obtained analysis liquid is purified by a rectification separation method and can also be recovered to obtain a large amount of effective organic matters.
The separation temperature can be limited, so that precipitation of impurities in the clear wastewater liquid can be prevented, cyanide polymerization caused by overhigh temperature of the clear wastewater liquid can be avoided, a resin adsorption system is blocked, the adsorption effect of the resin system is influenced, and the quality of the separation liquid is further guaranteed.
Optionally, the reducing agent is anhydrous sodium sulfite.
Optionally, the mass ratio of the addition amount of the reducing agent to the total amount of the oxidizing substances in the oxidized brine is 1:1-1.7. The concentration of the oxidizing substances in the oxidized brine is C, the volume of the byproduct high-salt wastewater is V, and the total amount of the oxidizing substances in the oxidized brine is C multiplied by V.
Optionally, the decoloring agent is activated carbon.
Optionally, the adding amount of the decoloring agent is 0.04-0.05% based on 100% of the mass of the oxidized brine.
Optionally, the conditions of the reduction are: the temperature is 45-55 ℃ and the time is 0.5-1.5 h.
Residual oxidizing substances exist in the oxidized brine, the oxidizing substances in the wastewater are removed by adding a reducing agent for oxidation-reduction reaction, purified brine is obtained, and the purified brine is obtained by decoloring with activated carbon.
Optionally, the concentration of total nitrogen in the low-cyanide low-ammonia brine is less than or equal to 20ppm.
Further optionally, the concentration of total nitrogen in the low-cyanide low-ammonia brine is less than or equal to 10ppm.
The preferred deamination treatment process can ensure that the total nitrogen concentration in the low-cyanide low-ammonia brine is less than or equal to 10ppm, thoroughly purify the high-salt wastewater in the aspect of ammonia nitrogen control, and lay a foundation condition for the subsequent oxidation treatment of chlorine-related oxidant so as to avoid explosion caused by a large amount of nitrogen trichloride generated due to the overhigh total nitrogen concentration in the low-cyanide low-ammonia brine in the subsequent staged oxidation treatment process and cause unnecessary personal injury.
Optionally, the concentration of total organic carbon in the low cyanide brine is less than 1300ppm.
The total organic carbon concentration in the low-cyanide brine is controlled, so that the maximum recovery rate of cyanide can be ensured, and the addition amount of the oxidant in the subsequent oxidation process can be effectively controlled, so that the waste of the oxidant is avoided.
The treatment method of the byproduct high-salt wastewater can be used for treating wastewater with the sodium chloride content less than or equal to 26wt%, the COD concentration less than or equal to 30000mg/g, the TOC concentration less than or equal to 15000ppm, the total cyanide less than or equal to 20000ppm and the ammonia nitrogen concentration less than or equal to 6000ppm.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a method for treating byproduct high-salt wastewater, wherein 6000g of byproduct high-salt wastewater contains 25.2wt% of sodium chloride, 30000mg/g of COD concentration, 15000ppm of TOC concentration, 20000ppm of total cyanide and 6000ppm of ammonia nitrogen.
The processing method comprises the following steps:
step one, adding 6g of activated carbon into the byproduct high-salt wastewater, stirring for 30min, and filtering to obtain clear liquid;
step two, carrying out styrene macroporous adsorption resin adsorption on the clear liquid at 35 ℃, when the volume of the clear liquid of the resin adsorption wastewater reaches 45BV, carrying out analysis on the resin system by adopting methanol, and rectifying and purifying the analysis liquid to obtain 72g of effective macromolecular organic substances;
adding hydrochloric acid into the separation liquid to adjust the pH value to 1.0, and performing decyanation treatment for 1.5 hours at the temperature of 60 ℃ to obtain low-cyanide brine, wherein the residual cyanide concentration in the low-cyanide brine is 15ppm, and the TOC concentration is 1280ppm;
adding sodium hydroxide into the low-cyanide brine to adjust the pH value to 11, and deaminizing at 30 ℃ for 12 hours to obtain low-cyanide low-ammonia brine, wherein the ammonia nitrogen concentration in the low-cyanide low-ammonia brine is 8ppm, and the TOC concentration is 1280ppm;
step five, heating the low-cyanide low-ammonia brine to 50 ℃, regulating the pH to 1 by using hydrochloric acid, adding 11.52g of sodium hypochlorite, simultaneously controlling the pH of a system to be 1-2 by using hydrochloric acid, and performing primary oxidation for 1h to obtain primary oxidized brine, wherein the TOC content in the primary oxidized brine is 19ppm;
adding 0.57g of sodium persulfate into the primary oxidized brine, heating to 80 ℃, controlling the pH of a system to be 7-8 by adopting hydrochloric acid, and carrying out secondary oxidation for 1h to obtain oxidized brine, wherein TOC in the oxidized brine is 0.8ppm;
step six, detecting that the concentration of the oxidizing substances in the oxidized brine is 0.030%, heating the oxidized brine to 50 ℃, then adding 1.8g of anhydrous sodium sulfite, and stirring for 1h to obtain purified brine; adding 3g of activated carbon into the purified brine, decoloring for 20min, and filtering to obtain refined brine.
The TOC content in the refined brine is 0.4ppm, the residual cyanide concentration is 0ppm, and the ammonia nitrogen concentration is 3ppm.
Example 2
The embodiment of the invention provides a method for treating byproduct high-salt wastewater, wherein 6000g of byproduct high-salt wastewater contains 25wt% of sodium chloride, 20000mg/g of COD (chemical oxygen demand) concentration, 10000ppm of TOC (total carbon) concentration, 8000ppm of total cyanide and 5050ppm of ammonia nitrogen.
The processing method comprises the following steps:
step one, adding 12g of activated carbon into the byproduct high-salt wastewater, stirring for 30min, and filtering to obtain clear liquid;
step two, carrying out styrene macroporous adsorption resin adsorption on the clear liquid at the temperature of 10 ℃, when the volume of the clear liquid of the resin adsorption wastewater reaches 50BV, carrying out analysis on the resin system by adopting methanol, and rectifying and purifying the analysis liquid to obtain 81g of effective macromolecular organic substances;
adding hydrochloric acid into the separation liquid to adjust the pH value to 0.5, and performing decyanation treatment for 1.5 hours at 70 ℃ to obtain low-cyanide brine, wherein the concentration of residual cyanide in the low-cyanide brine is 12ppm and the TOC concentration is 1250ppm;
adding sodium hydroxide into the low-cyanide brine to adjust the pH value to 10, and deaminizing at 65 ℃ for 3.5 hours to obtain low-cyanide low-ammonia brine, wherein the ammonia nitrogen concentration in the low-cyanide low-ammonia brine is 6ppm and the TOC concentration is 1250ppm;
step five, heating the low-cyanide low-ammonia brine to 60 ℃, regulating the pH to 3 by using hydrochloric acid, adding 9g of sodium hypochlorite, controlling the pH of a system to be 2-3 by using hydrochloric acid, and performing primary oxidation for 1h to obtain primary oxidized brine, wherein the TOC content in the primary oxidized brine is 16ppm;
adding 0.96g of sodium persulfate into the primary oxidized brine, heating to 90 ℃, controlling the pH of a system to be 3-4 by adopting hydrochloric acid, and carrying out secondary oxidation for 1h to obtain oxidized brine, wherein TOC in the oxidized brine is 0.6ppm;
step six, detecting that the concentration of the oxidizing substances in the oxidized brine is 0.025%, heating the oxidized brine to 45 ℃, then adding 2.25g of anhydrous sodium sulfite, and stirring for 1.5h to obtain purified brine; adding 2.4g of activated carbon into the purified brine, decoloring for 30min, and filtering to obtain refined brine.
The TOC content in the refined brine is 0.28ppm, the residual cyanide concentration is 0ppm, and the ammonia nitrogen concentration is 2ppm.
Example 3
The embodiment of the invention provides a method for treating byproduct high-salt wastewater, wherein 6000g of byproduct high-salt wastewater contains 24wt% of sodium chloride, 18000mg/g of COD (chemical oxygen demand) concentration, 10000ppm of TOC (total carbon) concentration, 15000ppm of total cyanide and 5000ppm of ammonia nitrogen.
The processing method comprises the following steps:
adding 30g of diatomite into the byproduct high-salt wastewater, stirring for 30min, and filtering to obtain clear liquid;
step two, carrying out styrene macroporous adsorption resin adsorption on the clear liquid at the temperature of 23 ℃, when the volume of the clear liquid of the resin adsorption wastewater reaches 48BV, carrying out analysis on the resin system by adopting methanol, and rectifying and purifying the analysis liquid to obtain 80g of effective macromolecular organic substances;
adding hydrochloric acid into the separation liquid to adjust the pH value to 0.75, and performing decyanation treatment for 1.5 hours at 80 ℃ to obtain low-cyanide brine, wherein the residual cyanide concentration in the low-cyanide brine is 10ppm, and the TOC concentration is 1200ppm;
adding sodium hydroxide into the low-cyanide brine to adjust the pH value to 12, and deaminizing at 100 ℃ for 1.5 hours to obtain low-cyanide low-ammonia brine, wherein the ammonia nitrogen concentration in the low-cyanide low-ammonia brine is 5ppm and the TOC concentration is 1200ppm;
step five, heating the low-cyanide low-ammonia brine to 55 ℃, regulating the pH to 2 by using hydrochloric acid, adding 7.2g of sodium chlorate, controlling the pH of a system to be 2-3 by using hydrochloric acid, and performing primary oxidation for 1.5h to obtain primary oxidized brine, wherein the TOC content in the primary oxidized brine is 14ppm;
adding 0.672g of sodium ferrate into the primary oxidized brine, heating to 100 ℃, controlling the pH value of a system to be 4-6 by adopting hydrochloric acid, and carrying out secondary oxidation for 0.5h to obtain oxidized brine, wherein TOC in the oxidized brine is 0.48ppm;
step six, detecting that the concentration of the oxidizing substances in the oxidized brine is 0.030%, heating the oxidized brine to 55 ℃, then adding 3.06g of anhydrous sodium sulfite, and stirring for 0.5h to obtain purified brine; adding 2.4g of activated carbon into the purified brine, decoloring for 30min, and filtering to obtain refined brine.
The TOC content in the refined brine is 0.35ppm, the residual cyanide concentration is 0ppm, and the ammonia nitrogen concentration is 2ppm.
In order to better illustrate the technical solutions of the present invention, the following is further compared with examples of the present invention.
Comparative example 1
The comparative example provides a method for treating byproduct high-salt wastewater, wherein 6000g of byproduct high-salt wastewater contains 25.2wt% of sodium chloride, 30000mg/g of COD concentration, 15000ppm of TOC concentration, 20000ppm of total cyanide and 6000ppm of ammonia nitrogen.
And replacing the third step in the treatment method with adding hydrochloric acid into the separation liquid to adjust the pH value to 3.0, and performing decyanation treatment for 1.5 hours at 50 ℃ to obtain low-cyanide brine, wherein the residual cyanide concentration in the low-cyanide brine is 1204ppm and the TOC concentration is 2600ppm, and the rest steps are consistent with those in the embodiment 1 and are not repeated.
The TOC content in the refined brine is 1300ppm, the residual cyanide concentration is 0ppm, and the ammonia nitrogen concentration is 5ppm.
It is known from this that the treatment method provided in this comparative example does not completely recover effective cyanide in the wastewater, and that in the subsequent step of staged oxidation, the oxidizing agent oxidizes cyanide first, so that the TOC content in the wastewater is too high.
Comparative example 2
The comparative example provides a method for treating byproduct high-salt wastewater, wherein 6000g of byproduct high-salt wastewater contains 25.2wt% of sodium chloride, 30000mg/g of COD concentration, 15000ppm of TOC concentration, 20000ppm of total cyanide and 6000ppm of ammonia nitrogen.
And replacing the fourth step in the treatment method with adding sodium hydroxide into the low-cyanide brine to adjust the pH value to 9, and deaminizing at 20 ℃ for 12 hours to obtain the low-cyanide low-ammonia brine, wherein the ammonia nitrogen concentration in the low-cyanide low-ammonia brine is 1080ppm and the TOC concentration is 1280ppm, and the rest steps are consistent with the embodiment 1 and are not repeated.
The TOC content in the refined brine is 0.6ppm, the residual cyanide concentration is 0ppm, the ammonia nitrogen concentration is 50ppm, and the nitrogen trichloride concentration is 0.68%.
Therefore, the treatment method provided by the comparative example is adopted, so that ammonia nitrogen in the wastewater is not completely recovered, and the enrichment of nitrogen trichloride is caused in the subsequent step of staged oxidation, so that the safety problem exists.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A method for treating byproduct high-salt wastewater is characterized by comprising the following steps: the processing method comprises the following steps:
step one, adding a flocculating agent into the byproduct high-salt wastewater, and filtering to obtain clear liquid; the byproduct high-salt wastewater contains: the sodium chloride content is less than or equal to 26wt%, the COD concentration is less than or equal to 30000mg/g, the TOC concentration is less than or equal to 15000ppm, the total cyanide content is less than or equal to 20000ppm, and the ammonia nitrogen concentration is less than or equal to 6000ppm;
step two, carrying out resin adsorption on the clear liquid at the temperature of 10-35 ℃ to obtain a separation liquid;
step three, decyanating the separating liquid at the temperature of 60-80 ℃ and the pH value of 0.5-1.0 to obtain low-cyanide brine;
step four, deaminizing the low-cyanide brine at the temperature of 30-100 ℃ and the pH value of 10-12 to obtain low-cyanide low-ammonia brine;
step five, carrying out fractional oxidation on the low-cyanide low-ammonia brine to obtain oxidized brine;
the specific process of the staged oxidation is as follows:
adding a primary oxidant into the low-cyanide low-ammonia brine for primary oxidation to obtain primary oxidized brine; the reaction conditions of the primary oxidation are as follows: the pH is 1-3, the temperature is 50-60 ℃ and the time is 0.5-1.5 h; the primary oxidant is at least one of sodium chlorate, sodium hypochlorite or chlorine gas;
adding a secondary oxidant into the primary oxidized brine for secondary oxidation to obtain oxidized brine; the reaction conditions of the secondary oxidation are as follows: the pH is 3-8, the temperature is 80-100 ℃ and the time is 0.5-1.5 h; the secondary oxidant is sodium ferrate or sodium persulfate; the addition amount of the secondary oxidant is 5-10 times of the pure TOC in the primary oxidized brine;
and step six, adding a reducing agent into the oxidized brine for reduction, and then adding a decoloring agent for decoloring to obtain refined brine.
2. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the addition amount of the primary oxidant is 1 to 1.5 times of the pure amount of TOC in the low-cyanide low-ammonia brine.
3. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the flocculant is at least one of activated carbon, diatomite or sawdust; and/or
The addition amount of the flocculant is 0.1-0.5% based on 100% of the byproduct high-salt wastewater.
4. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the resin is styrene macroporous adsorption resin; and/or
The aperture of the resin is 30 mm-40 mm; and/or
The adsorption volume of the resin is 45 BV-50 BV.
5. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the reducing agent is anhydrous sodium sulfite; and/or
The mass ratio of the addition amount of the reducing agent to the total amount of the oxidizing substances in the oxidized brine is 1:1-1.7; and/or
The conditions of the reduction are as follows: the temperature is 45-55 ℃ and the time is 0.5-1.5 h.
6. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the decoloring agent is activated carbon; and/or
The adding amount of the decoloring agent is 0.04-0.05 percent based on 100 percent of the mass of the byproduct high-salt wastewater.
7. The method for treating by-product high-salinity wastewater according to claim 1, wherein: the concentration of total nitrogen in the low-cyanide low-ammonia brine is less than or equal to 20ppm; and/or
The concentration of total organic carbon in the low-cyanide brine is less than 1300ppm.
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