CN113371879A - Pretreatment method of wastewater containing vinyl chloride - Google Patents
Pretreatment method of wastewater containing vinyl chloride Download PDFInfo
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- CN113371879A CN113371879A CN202110668337.XA CN202110668337A CN113371879A CN 113371879 A CN113371879 A CN 113371879A CN 202110668337 A CN202110668337 A CN 202110668337A CN 113371879 A CN113371879 A CN 113371879A
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- vinyl chloride
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- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002203 pretreatment Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 30
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 22
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000805 Pig iron Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 23
- 239000010865 sewage Substances 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 42
- 238000007254 oxidation reaction Methods 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 18
- 238000004062 sedimentation Methods 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 8
- 230000016615 flocculation Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000005997 Calcium carbide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009967 tasteless effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 206010002091 Anaesthesia Diseases 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000007674 genetic toxicity Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 sulfate radical Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood 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
- C02F1/52—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
- C02F1/72—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
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a pretreatment method of wastewater containing vinyl chloride, which is characterized by comprising the following steps: mixing the waste water containing vinyl chloride with iron or ferrumMixing gold and oxidizing salt for reaction, adjusting the pH value after the reaction is finished, and carrying out solid-liquid separation. The pretreatment method has simple process flow, and can reduce the content of vinyl chloride, chroma, COD, ammonia nitrogen and S in the wastewater containing the vinyl chloride2‑And the sewage treatment effect is good, and good prerequisites can be provided for subsequent sewage treatment.
Description
Technical Field
The invention belongs to the field of chemical production, and particularly relates to a pretreatment method of wastewater containing vinyl chloride.
Background
The chloroethylene in China is mainly produced by a calcium carbide acetylene method, calcium carbide is prepared by taking quick lime and coke as raw materials, the calcium carbide reacts with water to generate acetylene, and the acetylene and hydrogen chloride undergo an addition reaction to obtain a chloroethylene monomer. The waste water discharged in the vinyl chloride production process and the liquid seal of the gas tank for storing vinyl chloride is the waste water containing vinyl chloride. The wastewater containing the vinyl chloride dissolves volatile organic matters such as vinyl chloride, chloroethane, acetylene and the like, ammonia nitrogen, sulfides, ferrous salts and other pollutants, the Chemical Oxygen Demand (COD) is often used as an index for measuring the content of organic substances in water, and the larger the chemical oxygen demand, the more serious the water body is polluted by the organic matters, and the higher the COD concentration in the wastewater containing the vinyl chloride is. In addition, vinyl chloride has genetic toxicity and carcinogenic effect, exists in all aspects of real life, can be detected in plastic finished products, cigarettes, medicines and cosmetics, and is more seriously polluted in water and air of sewage treatment plants, thus being possibly a new pollution source outside occupational contact. The chloralkane also belongs to volatile organic pollutants, has high solubility and stability in water, has density higher than that of water, has accumulation effect in underground water, mainly acts on central nerve and respiratory system, has anesthesia effect, and has harm to heart, liver and kidney. A large amount of pollutants can be discharged along with industrial wastewater every year, and the wastewater containing the pollutants of volatile chloroethylene, chloroethane, acetylene and the like is directly discharged into a water body without being treated, so that the hazards of aquatic organisms, damage to soil structures, reduction of crop yield and the like are caused.
At present, with the aim of paying attention to the environment, COD is also taken as an important index to be strictly controlled in domestic and foreign sewage discharge standards, and the treatment requirements on chlorine-containing wastewater, high-concentration COD wastewater and other difficult wastewater generated in the industrial production process are higher and higher. However, since chloroethylene and chloroalkane are biologically toxic volatile substances, and are treated by the aeration biochemical treatment method, microorganisms are poisoned, and chloroethylene is volatilized in the aeration process to cause secondary pollution, so that the method is harmful to human bodies and the environment, and can explode in the air under certain conditions, and chloroethylene and chloroalkane are short-chain halogenated hydrocarbons, and the substances are difficult to be thoroughly oxidized into inorganic states by the traditional chemical oxidation method.
Therefore, how to effectively reduce the content of the pollutants is an urgent problem to be solved in wastewater treatment.
Disclosure of Invention
The invention aims to provide a pretreatment method of wastewater containing vinyl chloride, which can obviously reduce the biological toxic volatile substances, COD, ammonia nitrogen and S in the wastewater2-High sewage treating effect.
The invention provides a pretreatment method of wastewater containing vinyl chloride, which comprises the following steps: mixing the wastewater containing the chloroethylene with iron or iron alloy and oxidizing salt for reaction, adjusting the pH value after the reaction is finished, and carrying out solid-liquid separation.
The invention adopts iron or iron alloy as Fe2+The donor and the oxidizing salt generate hypochlorous acid and hydroxyl radical (OH) under the weak acid environment, and the hydroxyl radical (OH) can completely oxidize and decompose organic matters in the wastewater into inorganic CO2And reduces COD. Hypochlorous acid can be turned into nitrogen gas with ammonia nitrogen and flee, turns into the sulfate radical with the sulphide, reduces the concentration of ammonia nitrogen and sulphide, and the ferric ion that obtains of oxidation simultaneously takes place the hydrolysis, forms the colloid in the solution to flocculate and subside organic matter, suspended solid etc. in with the waste water, be favorable to reducing turbidity, colourity and the smell of waste water, thereby further improve sewage treatment effect.
Further, the iron is one or two of reduced iron and pig iron.
Further, the iron alloy is one or more of iron-copper alloy, iron-zinc alloy and iron-nickel alloy.
The form of the iron or the iron alloy can be one or more of granules, powder and wood shavings.
Further, the oxidizing salt is selected from one of hypochlorite, chlorate and nitrite, preferably hypochlorite.
Further, the hypochlorite is one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, preferably sodium hypochlorite; more preferably sodium hypochlorite with the mass percentage concentration of 5-15%.
In a specific embodiment of the invention, the pH value of the mixed chlorine-containing ethylene wastewater and iron or iron alloy is 4-7.
In the invention, if the pH value of the mixed wastewater containing the vinyl chloride and the iron or the iron alloy is more than 7 or less than 4, the pH value can be adjusted to be within the range of 4-7 by using a reagent, and the used reagent has no substantial influence on the sewage treatment effect.
In a particular embodiment of the invention, the iron or iron alloy: oxidizing salt: the mass ratio of COD in the wastewater is 0.2-0.8: 10-50: 0.5-2, and the preferable mass ratio is 0.5: 15-30: 1.
in a specific embodiment of the invention, the temperature of the mixing reaction is 15-40 ℃ and the time is 1-2 h.
The content of chloroethylene in the sewage treated by the method is 0.5-1 mg/L, the removal rate of COD is 85-87%, the removal rate of ammonia nitrogen is up to 98%, the removal rate of sulfides is up to 99%, the chroma is reduced by 15-30 times, the turbidity is lower than 0.18, meanwhile, the pungent odor in the sewage is removed, and the effect is obvious.
In a specific embodiment of the invention, the reagent used for adjusting the pH value is selected from one or more of strong base, carbonate and bicarbonate.
The source of the wastewater containing the vinyl chloride is not particularly limited, volatile vinyl chloride, chloroethane, acetylene and the like are dissolved in the wastewater containing the vinyl chloride, wherein the COD concentration is more than or equal to 2000mg/L, and sulfide (S)2-) The concentration is 30-80 mg/L, the ammonia nitrogen concentration is 200-300 mg/L, the pH is 9-11, and the product is orange yellow and has strong pungent smell.
Furthermore, the COD concentration in the wastewater containing the vinyl chloride is 2000-4000 mg/L.
The concentration of COD, ammonia nitrogen and sulfide in the wastewater supernatant after the pretreatment and the concentration of substances with biological toxicity are reduced, and the wastewater supernatant can automatically flow to a biochemical treatment tank of a sewage station for further treatment.
The technical scheme of the invention has the following beneficial effects:
(1) the method can obviously reduce the chloroethylene, the chroma, the COD, the ammonia nitrogen and the S in the sewage2-The content reduces the harm of sewage treatment to human bodies and the environment, and is beneficial to environmental protection.
(2) The invention has simple process flow and low production cost, and can be used for large-scale industrial production.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chlorine-containing wastewater used in the invention is one or more of the chlorine-containing wastewater generated by VCM, PVC synthesis and gas holder liquid seal, and the chlorine-containing wastewater used in the examples and the comparative examples of the invention is the chlorine-containing wastewater generated by gas holder liquid seal.
Example 1
(1) Putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. Adding a certain amount of iron particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to enable the pH value in the wastewater to be 4-7. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio of the added iron particles, the sodium hypochlorite with the concentration of 10% and the COD of the wastewater is m (iron particles): m (10% NaClO)：m(COD)＝0.5：15：1。
(2) And (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH value to 8-9 by using sodium carbonate, staying for 5-8 min in the sedimentation tank, after the flocculation precipitation is finished, enabling the obtained supernatant to be tasteless, reducing the chroma to 30 times, reducing the COD content by 80%, reducing the ammonia nitrogen content by 90%, reducing the sulfide content by 95%, and sending the pretreated supernatant to a sewage station biochemical tank for advanced treatment.
Example 2
(1) Putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. A certain amount of iron/copper alloy particles are added into the wastewater, and the pH value of the wastewater is 5.5-7 by adding dilute sulfuric acid with the mass concentration of 10%. Slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying wastewater in the oxidation pond for 1.5h, wherein the mass ratio m (iron/copper alloy particles) of the added iron/copper alloy particles, the sodium hypochlorite with the concentration of 10% and the wastewater COD is as follows: m (10% NaClO): m (cod) ═ 0.5: 20: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH value to 8-9 by using sodium hydroxide, staying in the sedimentation tank for 5-8 min, after the flocculation precipitation is finished, enabling the obtained supernatant to be tasteless, reducing the chroma to 20 times, reducing the COD content by 85%, reducing the ammonia nitrogen content by 95%, reducing the sulfide content by 97%, and sending the pretreated supernatant to a sewage station biochemical tank for advanced treatment.
Example 3
(1) Putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. Adding a certain amount of iron/zinc alloy particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to enable the pH value in the wastewater to be 4-6. Slowly adding the mixture into an oxidation pond with the concentration of 1Reacting 0% sodium hypochlorite solution, maintaining the temperature of an oxidation tank at 30-40 ℃, and allowing wastewater to stay in the oxidation tank for 1.5-2 h, wherein the mass ratio m of the added iron/zinc alloy particles, 10% sodium hypochlorite and wastewater COD (chemical oxygen demand) is as follows: m (10% NaClO): m (cod) ═ 0.5: 30: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation to a sedimentation tank, adjusting the pH to 8-9 by using calcium hydroxide, staying in the sedimentation tank for 5-8 min, after the flocculation precipitation is finished, enabling the supernatant to be odorless, reducing the chroma to 15 times, reducing the COD content by 87%, reducing the ammonia nitrogen content by 98%, reducing the sulfide content by 99%, and sending the pretreated supernatant to a biochemical tank of a sewage station for advanced treatment.
Comparative example 1
Compared with the embodiment 1, the method does not add iron particles and comprises the following specific steps:
(1) putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. And adding dilute sulfuric acid with the mass concentration of 10% into the wastewater to enable the pH value of the wastewater to be 4-7. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio of the added 10% sodium hypochlorite to the wastewater COD is m (10% NaClO): m (cod) ═ 15: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH to 8-9 by using sodium carbonate, staying in the sedimentation tank for 5-8 min, and after the flocculation precipitation is finished, sending the pretreated supernatant to a biochemical tank of a sewage station for advanced treatment.
Comparative example 2
Compared with the reaction temperature difference of the example 1, the method comprises the following specific steps:
(1) putting 1m into an oxidation pond3The wastewater containing the chloroethylene contains 6400mg/L of chloroethylene, 3500mg/L of COD, 250mg/L of ammonia nitrogen concentration, 40mg/L of sulfide concentration, 10-11 of pH value, 20NTU of turbidity, orange yellow color and colorHas a degree of 500 times and has pungent odor. Adding a certain amount of iron particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to enable the pH value in the wastewater to be 4-7. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 10 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio m (iron particles) of the added iron particles, the sodium hypochlorite with the concentration of 10% and the COD of the wastewater is as follows: m (10% NaClO): m (cod) ═ 0.5: 15: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH to 8-9 by using sodium carbonate, staying in the sedimentation tank for 5-8 min, and after the flocculation precipitation is finished, sending the pretreated supernatant to a biochemical tank of a sewage station for advanced treatment.
Comparative example 3
Compared with the embodiment 1, the pH value of the wastewater after 10% of dilute sulfuric acid is added is different, and the specific steps are as follows:
(1) putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. Adding a certain amount of iron particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to ensure that the pH value in the wastewater is 2. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio of the added iron particles, the sodium hypochlorite with the concentration of 10% and the COD of the wastewater is m (iron particles): m (10% NaClO): m (cod) ═ 0.5: 15: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH to 8-9 by using sodium carbonate, staying in the sedimentation tank for 5-8 min, and after the flocculation precipitation is finished, sending the pretreated supernatant to a biochemical tank of a sewage station for advanced treatment.
Comparative example 4
Compared with the embodiment 1, the pH value of the wastewater after 10% of dilute sulfuric acid is added is different, and the specific steps are as follows:
(1) putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. Adding a certain amount of iron particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to ensure that the pH value in the wastewater is 9. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio of the added iron particles, the sodium hypochlorite with the concentration of 10% and the COD of the wastewater is m (iron particles): m (10% NaClO): m (cod) ═ 0.5: 15: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH to 8-9 by using sodium carbonate, staying in the sedimentation tank for 5-8 min, and after the flocculation precipitation is finished, sending the pretreated supernatant to a biochemical tank of a sewage station for advanced treatment.
Comparative example 5
(1) Putting 1m into an oxidation pond3The method comprises the following steps of preparing vinyl chloride-containing wastewater, wherein the content of vinyl chloride in the wastewater is 6400mg/L, the COD is 3500mg/L, the concentration of ammonia nitrogen is 250mg/L, the concentration of sulfide is 40mg/L, the pH value is 10-11, the turbidity is 20NTU, the color is orange yellow, the chroma is 500 times, and the wastewater has pungent odor. Adding a certain amount of ferrous sulfate particles into the wastewater, and adding dilute sulfuric acid with the mass concentration of 10% to enable the pH value in the wastewater to be 4-7. After the pH value is adjusted, slowly adding a sodium hypochlorite solution with the concentration of 10% into an oxidation pond for reaction, maintaining the temperature of the oxidation pond at 15-40 ℃, and staying the wastewater in the oxidation pond for 1.5h, wherein the mass ratio m (ferrous sulfate) of the added ferrous sulfate, the sodium hypochlorite with the concentration of 10% and the wastewater COD is as follows: m (10% NaClO): m (cod) ═ 0.5: 15: 1.
(2) and (3) automatically flowing the mixed liquid after the oxidation treatment to a sedimentation tank, adjusting the pH value to 8-9 by using sodium carbonate, staying for 5-8 min in the sedimentation tank, after the flocculation precipitation is finished, enabling the obtained supernatant to be tasteless, reducing the chroma to 30 times, reducing the COD content by 80%, reducing the ammonia nitrogen content by 90%, reducing the sulfide content by 95%, and sending the pretreated supernatant to a sewage station biochemical tank for advanced treatment.
The supernatants obtained in examples 1-3 and comparative examples 1-5 were tested and the results are given in the following table:
in the comparative example 1, no iron or iron alloy is added, the reaction temperature after hypochlorite addition in the comparative example 2 is lower than the temperature range of 15-40 ℃, the pH values of the reactions in the comparative examples 3 and 4 are respectively less than or greater than 4-7, and when ferrous sulfate is adopted in the comparative example 5, the content of the obtained chloroethylene is at least 20 times that in the examples 1-3, the COD removal rate is 30-70%, the ammonia nitrogen removal rate is 65-87%, the sulfide removal rate is 75-90%, the chroma dilution multiple is 35-55 times, the turbidity is 0.45-1, and the chloroethylene has pungent odor; in the embodiments 1 to 3, the content of vinyl chloride in the supernatant obtained by a pretreatment method of adding iron or an iron alloy into wastewater, adjusting the pH value to 4 to 7, and reacting the wastewater with an oxidizing salt at a specific temperature is 0.5 to 1mg/L, the COD removal rate is 85 to 87%, the ammonia nitrogen removal rate is 98%, the sulfide removal rate is 99%, the chroma is reduced by 15 to 30 times, the turbidity is lower than 0.18, and the offensive odor in the sewage is removed2-The content and the sewage treatment effect are better.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The method for pretreating the wastewater containing the vinyl chloride is characterized by comprising the following steps of: mixing the wastewater containing the chloroethylene with iron or iron alloy and oxidizing salt for reaction, adjusting the pH value after the reaction is finished, and carrying out solid-liquid separation.
2. The pretreatment method according to claim 1, wherein the iron is one or both of reduced iron and pig iron.
3. The pretreatment method of claim 1, wherein the iron alloy is one or more of an iron-copper alloy, an iron-zinc alloy, and an iron-nickel alloy.
4. The pretreatment method of claim 1, wherein the oxidizing salt is selected from one of hypochlorite, chlorate, nitrite, preferably hypochlorite.
5. The pretreatment method according to claim 4, wherein the hypochlorite is one of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, preferably sodium hypochlorite; more preferably sodium hypochlorite with the mass percentage concentration of 5-15%.
6. The pretreatment method according to claim 1, wherein the pH value of the vinyl chloride-containing wastewater after mixing with iron or an iron alloy is 4 to 7.
7. The pretreatment method of claim 1, wherein the iron or iron alloy: weak acid salt: the mass ratio of COD in the wastewater is 0.2-0.8: 10-50: 0.5-2, and the preferable mass ratio is 0.5: 15-30: 1.
8. the pretreatment method according to claim 1, wherein the temperature of the mixing reaction is 15 to 40 ℃ and the time is 1 to 2 hours.
9. The pretreatment method according to claim 1, wherein the reagent for adjusting the pH is one or more selected from the group consisting of a strong base, a carbonate, and a bicarbonate.
10. The pretreatment method according to any one of claims 1 to 9, wherein the COD concentration in the vinyl chloride-containing wastewater is 2000 to 4000 mg/L.
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