CN114804456A - Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method - Google Patents
Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method Download PDFInfo
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- CN114804456A CN114804456A CN202210372839.2A CN202210372839A CN114804456A CN 114804456 A CN114804456 A CN 114804456A CN 202210372839 A CN202210372839 A CN 202210372839A CN 114804456 A CN114804456 A CN 114804456A
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002351 wastewater Substances 0.000 title claims abstract description 48
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005406 washing Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 239000012267 brine Substances 0.000 claims abstract description 83
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 83
- 239000002699 waste material Substances 0.000 claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 238000005189 flocculation Methods 0.000 claims abstract description 18
- 230000016615 flocculation Effects 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011033 desalting Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000010612 desalination reaction Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000010979 pH adjustment Methods 0.000 claims description 8
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- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000029219 regulation of pH Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 abstract description 2
- 230000033228 biological regulation Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000012528 membrane Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 239000005416 organic matter Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 241001671213 Staphylea Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular 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
- C02F1/72—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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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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- Hydrology & Water Resources (AREA)
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- Water Treatment By Electricity Or Magnetism (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a recovery system and a recovery method of alkaline washing wastewater generated in chloroethylene production by an oxychlorination method, which relate to the field of chemical sewage treatment and comprise a flocculation precipitation kettle, an air stripping tower, an adsorption tower, a condenser, a PH regulation kettle, a catalytic oxidation reactor, a filter and an electro-adsorption desalting unit; add the flocculation and precipitation cauldron with the alkali wash waste water raw water, the supernatant among the flocculation and precipitation cauldron gets into the air stripping tower, the waste brine after the air stripping gets into the pH regulation cauldron, add hydrochloric acid and carry out the pH value regulation, then get into the catalytic oxidation reactor, waste brine and oxidant react under the catalyst effect, further reduce waste brine COD and total organic carbon content, waste brine through catalytic oxidation treatment gets into the electro-adsorption desalination unit through the filter and carries out desalination formation strong brine, reach salt water retrieval and utilization standard, get into the salt dissolving system, replace partial original salt and obtain recycling.
Description
Technical Field
The invention relates to the field of chemical sewage treatment, in particular to a system and a method for recovering alkaline washing wastewater generated in chloroethylene production by an oxychlorination method.
Background
Vinyl Chloride (VCM), also known as vinyl chloride, is colorless and easily liquefied. VCM is an important monomer in high molecular chemical industry and is also the most main raw material for producing polyvinyl chloride (PVC). At present, two routes are mainly used for producing VCM in China, namely a calcium carbide acetylene method based on coal chemical industry and an ethylene method based on petrochemical industry. In the ethylene-based VCM production process, ethylene is first chlorinated or oxychlorinated to synthesize 1, 2-dichloroethane (EDC), and then cracked by EDC to produce VCM monomer. The method is called as an oxychlorination method, generated vinyl chloride monomer enters a finished product storage tank after alkali washing, acid washing, rectification and other procedures, a large amount of salt-containing sewage is generated in the refining process, the sewage contains organic matters with certain concentration, the salt content is high, and the treatment difficulty is high. At present, most domestic manufacturers generally introduce other wastewater to dilute the wastewater and then carry out biochemical treatment, but the effluent C0D still has 100mg/L, particularly contains salt up to 2000mg/L, cannot reach the discharge standard, and only can enter a secondary treatment system to be mixed with other sewage for dilution treatment.
High salt waste water treatment of chemical production enterprise is difficult point, and most enterprises adopt MVR evaporation technique to carry out evaporation treatment to high salt waste water that contains, but because the existence of corroding seriously and organic matter makes evaporation plant often can not normal operating, the solid salt purity that obtains can not reach the industrial product requirement, can only regard as the useless processing of danger, and the treatment cost is very high, in addition the evaporation energy consumption is very big for contain salt sewage treatment cost is high. When the reverse osmosis membrane method is adopted for concentration, the organic carbon in the strong brine is increased along with the concentration ratio, and the organic matter removal difficulty of the high-salinity brine is very high, so that the organic carbon in the strong brine does not reach the standard. Therefore, the saline sewage treatment is the biggest problem for enterprises. The high-salt-content sewage of an oxychlorination method chloroethylene production enterprise has large flow, contains organic matters such as dichloroethane and polychlorinated alkane, is difficult to carry out COD (chemical oxygen demand) advanced treatment, and particularly has more difficulty in meeting the requirement that the total organic carbon content of the ionic membrane production caustic soda is less than 10mg/L, so that a large amount of waste salt cannot be recycled to an ionic membrane caustic soda factory with the largest salt consumption, and huge environmental pollution and resource waste are caused. At present, no economic and efficient treatment system is formed, so that the waste brine is discharged up to the standard or is recycled to produce the ionic membrane caustic soda.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a system and a method for recovering alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method, so that the production requirements of caustic soda by an ion membrane method are met.
The purpose of the invention can be realized by the following technical scheme:
in a first aspect, the invention provides a recovery system of alkaline washing wastewater generated in chloroethylene production by an oxychlorination method, which comprises a flocculation precipitation kettle 1, an air stripping tower 3, an adsorption tower 4, a condenser 5, a pH adjusting kettle 6, a catalytic oxidation reactor 7, a filter 8 and an electro-adsorption desalting unit; the liquid outlet of the flocculation precipitation kettle 1 is connected with the feed inlet of an air stripping tower 3, the discharge outlet of the air stripping tower 3 is respectively connected with the feed inlet of an adsorption tower 4 and the feed inlet of a PH adjusting kettle 6, and the discharge outlet of the adsorption tower 4 is respectively connected with a condenser 5 and the feed inlet of the air stripping tower 3; and a discharge port of the pH adjusting kettle 6 is connected with a catalytic oxidation reactor 7, a filter 8 and an electro-adsorption desalting unit in sequence.
Further, an air circulating pump 2 is arranged between the air stripping tower 3 and the adsorption tower 4.
Further, the electro-adsorption desalination unit at least comprises three electro-adsorbers which are connected in sequence.
On the other hand, the invention provides a method for recovering alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method, which specifically comprises the following steps:
step (a): coagulating sedimentation:
collecting alkaline washing wastewater generated in chloroethylene production by an oxychlorination method to be treated, sending the alkaline washing wastewater into a flocculation precipitation kettle, adding a precipitator, and precipitating solid impurities in the wastewater to obtain clarified waste brine; the precipitated solid impurities are sent into a sludge unit through an outlet at the bottom of the flocculation precipitation kettle;
step (b): air stripping:
sending the clarified waste brine obtained in the step (a) into an air stripping tower, enabling air pressurized by an air circulating pump to be in countercurrent contact with the waste brine in the air stripping tower, enabling most organic matters in the waste brine, such as dichloroethane, tetrachloroethylene and the like, to be in full contact with the air under the action of a filler in the air stripping tower, enabling the organic matters in full contact with the air to enter an adsorption tower along with the air, enabling adsorption resin in the adsorption tower to absorb the organic matters in the air, then enabling the air to be recycled, continuing to enter the air stripping tower to strip the organic matters in the waste brine, obtaining waste brine with COD (chemical oxygen demand) less than 100mg/L in the air stripping tower, performing steam regeneration on the adsorption resin after the organic matters are saturated, and recovering the organic matters after condensation by a condenser;
step (c): adjusting the pH value:
feeding the waste brine blown off by air in the step (b) into a pH adjusting kettle for pH adjustment, and adding hydrochloric acid or sulfuric acid to adjust the pH to 3-6;
step (d): catalytic oxidation reaction:
continuously feeding the waste brine subjected to pH regulation in the step (c) into a catalytic oxidation reactor, and fully reacting organic matters in the waste brine with an oxidant in the catalytic oxidation reactor under the action of a catalyst to convert the organic matters into CO 2 And H 2 O, the COD of the obtained waste saline is less than 30mg/L, and the total organic carbon is less than 10 mg/L;
a step (e): electro-adsorption desalination:
enabling the wastewater subjected to catalytic oxidation in the step (d) to enter a filter, enabling filtered waste brine to enter an electro-adsorption desalting unit, and continuously desalting the waste brine by using a multi-stage electro-adsorber to obtain effluent with salt content of light brine less than 500mg/L and COD less than 30mg/L, wherein the effluent can be discharged after reaching the standard; the NaCl concentration of the concentrated brine obtained after the treatment of the electric absorber is more than 190g/L, the total organic carbon is less than 10mg/L, the concentrated brine reaches the brine recycling standard, and the concentrated brine enters a salt dissolving system to replace part of original salt to be recycled.
Further, the precipitant in step (a) is polyaluminium chloride or polyacrylamide, and is added in an amount of 8 ppm.
Further, the packing of the air stripping tower in the step (b) is ceramic or plastic, and the gas-liquid ratio in the air stripping tower is 50-1000: 1.
further, the packing of the air stripping tower in the step (b) is polypropylene pore plate corrugated packing.
Further, in the step (d), the catalyst is an iron-based catalytic oxidant, and the catalytic oxidation reactor is a fixed bed reactor.
Further, the oxidant in the catalytic oxidation reactor in the step (d) is one or more of hydrogen peroxide, ozone, sodium ferrate or sodium hypochlorite, and the adding concentration of the oxidant is 0.1-10 g/L.
Furthermore, the electrode material in the multi-stage electric absorber in the step (e) is made of carbon fiber, and the direct current voltage between the electrodes is 0.5-10 volts.
Compared with the prior art, the invention has the beneficial effects that:
(1) the organic matters in the wastewater are blown off by air and are adsorbed and recovered by resin, so that organic matters such as dichloroethane, tetrachloroethylene and the like which are difficult to biodegrade in the wastewater can be efficiently and quickly separated, the COD value of the wastewater is reduced, useful chemical raw materials are obtained after recovery, and the method has good economic benefit;
(2) the catalytic oxidation treatment technology is more efficient than the traditional biochemical treatment, the composite oxidant is specially used for carrying out advanced treatment on chlorinated organic matters, the total organic carbon can reach less than 10mg/L, which is a specific index of preparing caustic soda brine by an ionic membrane, and other treatment processes cannot reach the index;
(3) the brine is concentrated by adopting electric adsorption, the total organic carbon and COD content of the concentrated brine is not increased, and the requirement of preparing the caustic soda brine by using an ionic membrane is met;
(4) the process is simple, easy to implement and low in treatment cost, realizes an ionic membrane caustic soda system for recycling waste salt, eliminates the pollution of the waste salt as hazardous waste to the environment, and provides a direction for recycling the waste salt in chemical industry and other industries.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic diagram of a system for recovering alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method according to the present invention;
in the figure: 1-a flocculation precipitation kettle, 2-an air circulating pump, 3-a stripping tower, 4-a tail gas adsorption tower, 5-a condenser, 6-a pH value adjusting kettle, 7-a catalytic oxidation reactor, 8-a filter, 9-a first-stage electro-adsorber, 10-a second-stage electro-adsorber and 11-a third-stage electro-adsorber.
Detailed Description
The technical scheme of the invention is described in detail in the following with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the embodiment provides a recovery system of alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method, comprising a flocculation precipitation kettle 1, a stripping tower 3, an adsorption tower 4, a condenser 5, a PH adjusting kettle 6, a catalytic oxidation reactor 7, a filter 8 and an electro-adsorption desalination unit; the electro-adsorption desalting unit consists of a first-stage electro-adsorber 9, a second-stage electro-adsorber 10 and a third-stage electro-adsorber 11; the liquid outlet of the flocculation precipitation kettle 1 is connected with the feed inlet of the stripping tower 3, the discharge outlet of the stripping tower 3 is respectively connected with the feed inlet of the adsorption tower 4 and the feed inlet of the PH adjusting kettle 6, and the discharge outlet of the adsorption tower 4 is respectively connected with the feed inlets of the condenser 5 and the stripping tower 3; an air circulating pump 2 is also arranged between the stripping tower 3 and the adsorption tower 4; and a discharge port of the pH adjusting kettle 6 is connected with a catalytic oxidation reactor 7, a filter 8, a first-stage electric adsorber 9, a second-stage electric adsorber 10 and a third-stage electric adsorber 11 in sequence.
The recovery principle of the recovery system of the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method is as follows:
adding alkaline washing wastewater raw water into a flocculation precipitation kettle 1, adding a flocculating agent polyaluminium chloride through stirring, flocculating and precipitating to obtain solid impurities, discharging the solid impurities from an outlet at the bottom of the flocculation precipitation kettle 1 to be transported outside as sludge, feeding supernatant in the flocculation precipitation kettle 1 into a stripping tower 3, fully contacting the counter current with air, contacting organic matters in the waste brine with the air, feeding the air containing the organic matters into an adsorption tower 4, absorbing the organic matters by an absorbing material in the adsorption tower 4, and pressurizing the air by an air circulating pump 2 for recycling; performing steam desorption after the resin in the tail gas adsorption tower 4 is saturated with adsorbed organic matters, and recovering the organic matters from the desorbed organic matters through a condenser 5; waste brine subjected to air stripping enters a pH adjusting kettle 6, hydrochloric acid is added to adjust the pH value to 3-6, then the waste brine enters a catalytic oxidation reactor 7, the waste brine reacts with an oxidant under the action of a catalyst to further reduce the COD (chemical oxygen demand) and the ammonium content of the waste brine, the waste brine subjected to catalytic oxidation enters a first-stage electric adsorber 9 through a filter 8 to be desalted, and light brine is discharged; the concentrated waste brine enters a second-stage electric adsorber 10 for desalination treatment, and the light brine is discharged, and the concentrated waste brine enters a third-stage electric adsorber 11 for desalination treatment, and the light brine is discharged; the waste brine is desalted by a three-stage electric adsorber to form strong brine, and the salt system is hydrolyzed by the deionized membrane electrolytic salt.
Example 2
The recycling system of the alkaline washing wastewater generated in the production of vinyl chloride by oxychlorination described in example 1 is used for recycling the alkaline washing wastewater of chloroethylene by oxychlorination of Tianjin Staphylea chemical industry Co., Ltd, and the specific steps are as follows:
step (a): coagulating sedimentation:
collecting alkaline washing wastewater generated in chloroethylene production by an oxychlorination method to be treated, sending the alkaline washing wastewater into a flocculation precipitation kettle, adding precipitator polyaluminium chloride with the addition of 8ppm, and precipitating solid impurities in the wastewater to obtain clarified waste brine; sending the precipitated solid impurities into a sludge unit;
a step (b): air stripping:
continuously feeding the clarified waste brine obtained in the step (a) into an air stripping tower, and carrying out countercurrent contact on air pressurized by an air circulating pump and the waste brine, wherein the gas-liquid ratio is 600: 1, under the action of a filler in an air stripping tower, most organic matters in the waste brine, such as dichloroethane, tetrachloroethylene and the like, are fully contacted with air and are taken out by the air to be absorbed by a tail gas adsorption tower, waste brine with COD (chemical oxygen demand) of 87mg/L is obtained in the air stripping tower, the air can be recycled by an air circulating pump, the adsorption tower is saturated with the organic matters to carry out steam regeneration, and the regenerated organic matters are condensed and recovered by a condenser;
step (c): adjusting the pH value:
adding the waste brine blown off by air in the step (b) into a pH value adjusting kettle for pH adjustment, and adding hydrochloric acid for pH adjustment to ensure that the pH value is 4.5;
step (d): catalytic oxidation reaction:
continuously feeding the waste saline water subjected to pH adjustment in the step (c) into a catalytic oxidation reactor, and simultaneously adding hydrogen peroxide and sodium ferrate with the waste saline water amount of 1g/L, wherein the weight ratio of the hydrogen peroxide to the sodium ferrate is 5: 1, carrying out catalytic oxidation reaction, and controlling the retention time for 1 hour to obtain waste brine COD of 26mg/L and total organic carbon of less than 9.2 mg/L;
a step (e): electro-adsorption desalination:
enabling the wastewater subjected to catalytic oxidation in the step (d) to enter a filter, enabling filtered waste brine to enter a first-stage electric adsorber 9, a second-stage electric adsorber 10 and a third-stage electric adsorber 11, connecting reactors of the third-stage electric desalter in series, and enabling electrode voltages to be 8 volts, 6 volts and 4 volts respectively; the electrodes are made of carbon fiber materials; and continuously desalting the waste brine by using a three-stage electro-adsorber to obtain effluent with the salt content of 560mg/L, COD of 27mg/L of the light brine, and discharging the effluent after reaching the standard. The concentration of NaCl in the concentrated brine obtained after the electro-adsorption treatment is 206g/L, and the total organic carbon is 9.3mg/L, thereby reaching the brine recycling standard.
Example 3
The recycling system of the alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method described in example 1 is used for recycling alkaline washing wastewater of vinyl chloride branch plants of the oxychlorination method of a certain company in Jiangsu, and the specific steps are as follows:
step (a): coagulating sedimentation:
collecting alkaline washing wastewater generated in chloroethylene production by an oxychlorination method to be treated, sending the alkaline washing wastewater into a coagulating sedimentation kettle 1, adding a precipitator polyaluminium chloride with the addition of 8ppm, precipitating solid impurities in the wastewater to obtain clarified waste brine, and sending the precipitated solid impurities into a sludge unit through an outlet at the bottom of the coagulating sedimentation kettle;
step (b): air stripping:
continuously feeding the clarified waste brine obtained in the step (a) into an air stripping tower 3, and carrying out countercurrent contact on air pressurized by an air circulating pump 2 and the waste brine, wherein the gas-liquid ratio is 800: 1, under the action of a filler in an air stripping tower, most organic matters in the waste brine, such as dichloroethane and tetrachloroethylene, are in full contact with air and are carried out by the air, the organic matters and the air enter an adsorption tower together, the air is recycled after the organic matters in the air are absorbed by adsorption resin in the adsorption tower, the air continues to enter the air stripping tower to strip the organic matters in the waste brine, waste brine with COD of 77mg/L is obtained in the air stripping tower, steam regeneration is carried out after the adsorbed organic matters are saturated, and the regenerated organic matters are condensed and recovered by a condenser 5;
step (c): adjusting the pH value:
and (c) adding the waste brine subjected to air stripping in the step (b) into a pH adjusting kettle 6 for pH adjustment, and adding hydrochloric acid for pH adjustment to make the pH value be 4.0.
Step (d): catalytic oxidation reaction:
continuously feeding the waste saline water subjected to pH adjustment in the step (c) into a catalytic oxidation reactor 7, and simultaneously adding hydrogen peroxide and sodium ferrate with the waste saline water amount of 0.8g/L, wherein the weight ratio of the hydrogen peroxide to the sodium ferrate is 6: 1, carrying out catalytic oxidation reaction, and controlling the retention time to be 1.5 hours to obtain waste brine COD of 24mg/L and total organic carbon of 8.9 mg/L.
A step (e): electro-adsorption desalination:
enabling the wastewater subjected to catalytic oxidation in the step (d) to enter a filter 8, sequentially enabling filtered waste brine to enter a first-stage electric adsorber 9, a second-stage electric adsorber 10 and a third-stage electric adsorber 11, connecting the three-stage electric desalting reactors in series, and enabling electrode voltages to be 8 volts, 6 volts and 4 volts respectively; the electrodes are made of carbon fiber materials; continuously passing the waste brine through a three-stage electro-adsorption desalter to obtain effluent with the salt content of the light brine of 420mg/L, COD being 25mg/L, and discharging the effluent after reaching the standard; the concentration of NaCl in the concentrated brine obtained after electro-adsorption treatment is 197g/L, and the total organic carbon is 8.8mg/L, which all reach the brine recycling standard.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A recovery system of alkaline washing wastewater generated in chloroethylene production by an oxychlorination method is characterized by comprising a flocculation precipitation kettle (1), an air stripping tower (3), an adsorption tower (4), a condenser (5), a PH adjusting kettle (6), a catalytic oxidation reactor (7), a filter (8) and an electro-adsorption desalting unit; the liquid outlet of the flocculation precipitation kettle (1) is connected with the feed inlet of the air stripping tower (3), the discharge outlet of the air stripping tower (3) is respectively connected with the feed inlet of the adsorption tower (4) and the feed inlet of the PH adjusting kettle (6), and the discharge outlet of the adsorption tower (4) is respectively connected with the feed inlets of the condenser (5) and the air stripping tower (3); and a discharge port of the pH adjusting kettle (6) is connected with a catalytic oxidation reactor (7), a filter (8) and an electro-adsorption desalting unit in sequence.
2. The recovery system of the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method according to claim 1, wherein an air circulating pump (2) is arranged between the air stripping tower (3) and the adsorption tower (4).
3. The system for recovering the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method according to claim 1, wherein the electro-adsorption desalination unit comprises at least three electro-adsorbers which are connected in sequence.
4. The recycling method of the recycling system of the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method according to claim 1, which is characterized by comprising the following steps:
step (a): coagulating sedimentation:
collecting alkaline washing wastewater generated in chloroethylene production by an oxychlorination method to be treated, sending the alkaline washing wastewater into a flocculation precipitation kettle, adding a precipitator, and precipitating solid impurities in the wastewater to obtain clarified waste brine; the precipitated solid impurities are sent into a sludge unit through an outlet at the bottom of the flocculation precipitation kettle;
step (b): air stripping:
sending the clarified waste brine obtained in the step (a) into an air stripping tower, enabling air pressurized by an air circulating pump to be in countercurrent contact with the waste brine in the air stripping tower, enabling most organic matters in the waste brine such as dichloroethane and tetrachloroethylene to be in full contact with the air under the action of a filler in the air stripping tower, enabling the organic matters in full contact with the air to enter an adsorption tower along with the air, enabling adsorption resin in the adsorption tower to absorb the organic matters in the air, recycling the air, continuously entering the air stripping tower to strip the organic matters in the waste brine, obtaining waste brine with COD (chemical oxygen demand) less than 100mg/L in the air stripping tower, performing steam regeneration on the adsorption resin after the adsorption of the organic matters are saturated, and recovering the organic matters after condensation by a condenser;
step (c): adjusting the pH value:
feeding the waste brine blown off by air in the step (b) into a pH adjusting kettle for pH adjustment, and adding hydrochloric acid or sulfuric acid to adjust the pH to 3-6;
step (d): catalytic oxidation reaction:
adjusting the pH of the solution obtained in step (c)The waste brine is continuously fed into a catalytic oxidation reactor, organic matters in the waste brine fully react with an oxidant in the catalytic oxidation reactor under the action of a catalyst, and the organic matters are changed into CO 2 And H 2 O, the COD of the obtained waste saline is less than 30mg/L, and the total organic carbon is less than 10 mg/L;
a step (e): electro-adsorption desalination:
enabling the wastewater subjected to catalytic oxidation in the step (d) to enter a filter, enabling filtered waste brine to enter an electro-adsorption desalting unit, and continuously desalting the waste brine by using a multi-stage electro-adsorber to obtain effluent with salt content of light brine less than 500mg/L and COD less than 30mg/L, wherein the effluent can be discharged after reaching the standard; the NaCl concentration of the concentrated brine obtained after the treatment of the electric absorber is more than 190g/L, the total organic carbon is less than 10mg/L, the concentrated brine reaches the brine recycling standard, and the concentrated brine enters a salt dissolving system to replace part of original salt to be recycled.
5. The method for recovering alkaline waste water generated in the production of vinyl chloride by oxychlorination according to claim 4, wherein the precipitant in step (a) is polyaluminium chloride or polyacrylamide and is added in an amount of 8 ppm.
6. The method for recovering alkaline washing wastewater generated in the production of vinyl chloride by an oxychlorination method according to claim 4, wherein the filler of the air stripping tower in the step (b) is ceramic or plastic, and the gas-liquid ratio in the air stripping tower is 50-1000: 1.
7. the method for recovering alkaline waste water generated in the production of vinyl chloride by oxychlorination process according to claim 4, wherein the filler of the air stripping tower in the step (b) is polypropylene pore plate corrugated filler.
8. The method for recovering the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method according to claim 4, wherein the catalyst in the step (d) is an iron-based catalytic oxidant, and the catalytic oxidation reactor is a fixed bed reactor.
9. The method for recovering the alkaline washing wastewater generated in the production of vinyl chloride by the oxychlorination method according to claim 4, wherein the oxidant in the catalytic oxidation reactor in the step (d) is one or more of hydrogen peroxide, ozone, sodium ferrate or sodium hypochlorite, and the adding concentration of the oxidant is 0.1-10 g/L.
10. The method for recovering alkaline washing wastewater generated in the production of vinyl chloride by using an oxychlorination method according to claim 4, wherein the electrode material in the multistage adsorber in the step (e) is made of carbon fiber, and the direct current voltage between the electrodes is 0.5-10 volts.
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