CN115594322B - Ethylene waste alkali liquid treatment method - Google Patents
Ethylene waste alkali liquid treatment method Download PDFInfo
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- CN115594322B CN115594322B CN202110719354.1A CN202110719354A CN115594322B CN 115594322 B CN115594322 B CN 115594322B CN 202110719354 A CN202110719354 A CN 202110719354A CN 115594322 B CN115594322 B CN 115594322B
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000005977 Ethylene Substances 0.000 title claims abstract description 35
- 239000003513 alkali Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 84
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 241000894006 Bacteria Species 0.000 claims abstract description 29
- 238000001728 nano-filtration Methods 0.000 claims abstract description 26
- 239000010802 sludge Substances 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000010865 sewage Substances 0.000 claims description 14
- 239000002912 waste gas Substances 0.000 claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000003568 thioethers Chemical class 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 241000638738 Halomonas nigrificans Species 0.000 claims description 3
- 238000009629 microbiological culture Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- -1 chlorine ions Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000002341 toxic gas Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 20
- 231100000419 toxicity Toxicity 0.000 abstract description 9
- 230000001988 toxicity Effects 0.000 abstract description 9
- 231100000614 poison Toxicity 0.000 abstract description 4
- 239000003440 toxic substance Substances 0.000 abstract description 4
- 235000002639 sodium chloride Nutrition 0.000 description 75
- 230000001580 bacterial effect Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 230000015784 hyperosmotic salinity response Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 238000009279 wet oxidation reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001640 fractional crystallisation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 239000012137 tryptone Substances 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
- C02F11/04—Anaerobic treatment; Production of methane by such processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The treatment method of the ethylene waste alkali liquid comprises a pretreatment section, an advanced treatment section, a salt treatment section and a sludge treatment section; the pretreatment section sequentially comprises an air separation system, a pure oxygen reactor, a neutralization reaction tank and a stripping reactor; the advanced treatment section sequentially comprises a primary biochemical section, a high-grade oxidation section, a secondary biochemical section and a tail gas treatment section, wherein the primary biochemical section and the secondary biochemical section adopt high-salt-tolerance bacteria GXNYJ-DL-1; the salt treatment section comprises a two-stage nanofiltration section, an MVR concentration section and a crystallization section; the sludge treatment section is used for recycling redundant sludge generated by primary biochemistry and secondary biochemistry, converting biological sludge into methane through sludge anaerobic oxidation and recycling the methane. The salt-resistant strain used by the invention has strong capability of tolerating sulfide toxicity, strong vitality and high stability; the method effectively solves the problem that malodor and toxic substances affect a biochemical system, and the content of the effluent salt reaches the standard, thereby realizing recycling.
Description
Technical Field
The invention relates to a method for treating ethylene waste alkali liquid, in particular to a process method for strengthening treatment of ethylene waste alkali liquid by utilizing a strain of high-salt-tolerance bacteria, belonging to the technical field of microorganism and wastewater treatment. .
Background
The ethylene waste alkali liquor is waste water generated by alkali washing of pyrolysis gas in the ethylene production process, the pollutant components are complex, the contents of organic matters, sulfides and salts are high, meanwhile, the ethylene waste alkali liquor also contains malodorous gases such as mercaptan, thioether and the like, and the treatment difficulty is high. Along with the expansion of the scale of ethylene units, the discharge amount of waste lye is continuously increased, and the harmless treatment and comprehensive utilization of the waste lye become important points.
The most mainstream method of ethylene waste alkali liquor is a wet oxidation method, which is operated under the conditions of high temperature (120-320 ℃) and high pressure (0.5-20 MPa), so that a large amount of high-temperature steam is required to be consumed, the operation cost is higher, the requirement on equipment materials is high, the disposable investment is also high, the wet oxidation can only be used for pretreatment, and the effluent has higher COD.
In recent years, the field of bioengineering has been rapidly developed, dominant bacteria suitable for high-salt environment are domesticated by a scientific method, alkali residue wastewater can be intensively treated, for example, a high-concentration wastewater biological treatment process (QBR) is developed by Korean SK group, and Xu Chuanhai is used for pilot-scale research on ethylene alkali residue wastewater by utilizing specific microorganism bacteria contained in the technology, and in the "pilot-scale research on treating ethylene alkali residue wastewater by biological intensification process", the QBR process is clearly pointed out that the inflow TDS is less than 20g/L, and raw water is greatly diluted. The Showcfrom peak in experimental study of biological strengthening technology for treating ethylene caustic sludge indicates that TDS should be controlled below 25g/L to keep the biological strengthening pool device running stably.
CN98121081.3 discloses a treatment method of refined waste lye of petroleum refining industrial oil, which combines wet oxidation and SBR technology to treat waste lye, in order to ensure the treatment effect of SBR biological reaction tank, wet oxidation effluent needs to be diluted, so that the salt content is controlled below 30g/L, preferably below 25 g/L, most preferably below 18 g/L. CN201110309325.4 discloses a treatment and reuse system and a treatment and reuse method for sewage from ethylene plants, wherein alkaline residue waste water is mixed with circulating cooling water sewage after wet oxidation treatment, and enters a lower-stage aeration biological filter after the salt content is reduced.
CN201610901997.7 discloses a method for treating alkaline residue waste water, which adopts sulfureted bacteria flora and salt-tolerant microbial flora in a biochemical treatment device, wherein the concentration of TDS tolerant to salt-tolerant microbes is 25-30 g/L, belonging to weak halophilic bacteria, and the alkaline residue waste water needs to be diluted by more than 5 times when being treated. CN201810167970.9 discloses a method for treating waste liquid of liquefied gas alkaline residue, which adopts a micro-electrolysis reactor and a high-efficiency bioreactor, wherein the micro-electrolysis effluent is diluted with nutrient salt to a salt content of 20g/L and then enters the high-efficiency bioreactor for biochemical treatment by salt-tolerant bacteria.
The invention discloses a method for treating alkaline residue wastewater by utilizing halophilic microorganisms, which comprises the steps of adsorbing by polyurethane sponge adsorption particles, treating by a halophilic microorganism reactor, sequentially passing through a hydrolytic acidification tank, a contact oxidation tank, an ozone generator, a double membrane and the like, and finally realizing reclaimed water recycling, wherein the two halophilic bacteria used by the method have the TDS (total dissolved solids) tolerance concentration of up to 30-150 g/L, the sulfide tolerance concentration of up to 10-50 g/L and the volatile phenol concentration of up to 5-10 g/L, and the sulfide and the volatile phenol have very strong biotoxicity.
To sum up, aiming at the problems of large investment, high operation cost and low COD removal rate of the existing wet oxidation treatment of the ethylene waste alkali liquid, the problems of large dilution of low-salt water and difficult treatment of malodorous and toxic substances such as sulfides exist in the biological treatment.
Disclosure of Invention
Aiming at the defects, the invention provides a method for treating ethylene waste lye in the prior art, which utilizes a strain with high salt tolerance to treat the ethylene waste lye, realizes the efficient removal of organic matters and malodor of the waste lye through the procedures of pure oxygen aeration, biological strengthening, nanofiltration desalination and the like, meets the control requirement of salt content in special areas and realizes the recycling of resources.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
The treatment method of the ethylene waste alkali liquid comprises a pretreatment section, an advanced treatment section, a salt treatment section and a sludge treatment section;
the pretreatment section sequentially comprises an air separation system, a pure oxygen reactor, a neutralization reaction tank and a stripping reactor;
The air separation system separates high-purity oxygen and nitrogen through air; the pure oxygen reactor adopts pure oxygen to oxidize and remove sulfides and partial organic matters in the waste alkali liquid, and waste gas is intermittently discharged through a pressure reducing valve; regulating the pH value of the effluent of the pure oxygen reactor to 6-8 in the neutralization reaction tank; the stripping reactor is used for stripping the malodorous gases such as hydrogen sulfide, mercaptan, thioether, volatile phenol and the like in the wastewater through air, so that the influence of malodorous toxic gases on subsequent biochemistry is reduced, and the stripping gas is discharged to a waste gas pipe network;
The advanced treatment section sequentially comprises a primary biochemical section, a high-grade oxidation section, a secondary biochemical section and a tail gas treatment section; the primary biochemical section adopts high salt tolerant bacteria GXNYJ-DL-1 to treat wastewater, and most organic matters are removed through aeration biochemistry; the high-grade oxidation section changes the organic matters difficult to degrade of the macromolecules into small molecular organic matters and removes malodorous gases; the secondary biochemical section adopts high salt tolerant bacteria GXNYJ-DL-1 to treat the effluent of the advanced oxidation section, so that organic matters in the wastewater are further removed; the tail gas treatment section is used for treating the residual waste gas of the advanced oxidation section and discharging the treated waste gas;
The high salt tolerant bacteria GXNYJ-DL-1 (Halomonas nigrificans) is preserved in China general microbiological culture Collection center (CGMCC) with the preservation number of CGMCC No. 20350 in the year 2020, 7 and 13;
The salt treatment section comprises a two-stage nanofiltration section, an MVR concentration section and a crystallization section; the two-stage nanofiltration filters sulfate ions, calcium magnesium ions and other divalent and trivalent ions to ensure that the sulfate ions, the calcium magnesium ions and the other divalent and trivalent ions are on the concentrated water side, and the main chlorine ions and sodium ions are on the water production side; the water produced by the two-stage nanofiltration is regulated and controlled, and then is discharged according to the quality of the water to reach the standard or discharged into a second-stage sewage treatment field; concentrated water produced by the two-stage nanofiltration enters an MVR reactor, the concentrated water enters a crystallizer after being further concentrated by MVR, sodium sulfate with purity more than 98% is obtained by high-temperature section crystallization, mixed salt is obtained by low-temperature crystallization, and the residual mother liquor returns to the water inlet end of the MVR reactor;
the sludge treatment section is used for recycling redundant sludge generated by primary biochemistry and secondary biochemistry, converting biological sludge into methane through sludge anaerobic oxidation and recycling the methane.
Further, the salt concentration in the wastewater entering the primary biochemical section is controlled below 250g/L, preferably 50-130 g/L. The salt tolerant bacteria GXNYJ-DL-1 can still keep vitality and higher organic matter removal efficiency under the salt concentration of 250g/L, and the growth condition of the salt tolerant bacteria is integrated and the organic matter removal efficiency is optimized to be 50-130 g/L; the salt tolerant bacteria GXNYJ-DL-1 also has higher sulfide toxicity tolerance.
Furthermore, the pure oxygen reactor can remove 90-98% of sulfide to change the sulfide into high-valence salt; when the oxygen or the insoluble gas is excessive, the air pressure of the reactor is too high, so that a pressure reducing valve is triggered to exhaust, and the pressure of the pressure reducing valve is controlled to be 0.15-0.3 MPa; further, the waste gas intermittently discharged by the pressure reducing valve is discharged to the advanced oxidation section for treatment by the waste gas pipe network.
It should be understood by those skilled in the art that the pure oxygen reactor adopts pure oxygen instead of air, so that the diffusion capability of oxygen in the wastewater can be greatly improved, and the oxygen utilization rate is 7-15 times that of air aeration, so that sulfides and other substances easily oxidized by oxygen in the wastewater are removed as much as possible; on the other hand, if the reactor uses an air source, nitrogen in the air source is used as insoluble gas, the pressure reducing valve is frequently triggered to exhaust, so that the reaction pressure is always in a lower value, oxygen is easy to escape, and finally the reaction efficiency is seriously affected.
Further, the pH value in the neutralization reaction tank is adjusted by adding sulfuric acid. The sulfuric acid is used instead of the hydrochloric acid, and the reason is that the salt brought by the sulfuric acid can be removed in the nanofiltration section, the chloride ions of the hydrochloric acid can not be removed by nanofiltration, the salt content of the effluent regulating tank is finally too high, and the chloride ions are easy to cause equipment corrosion.
Furthermore, the stripping reactor adopts a microporous aeration disc, and hydrogen sulfide and partial light components such as mercaptan, thioether, volatile phenol and the like in the wastewater generated by acid addition regulation of the upper neutralization reaction tank are discharged to a high-grade oxidation section for treatment by an exhaust pipe network after air stripping, so that the influence of malodor and toxic substances on a biochemical system is greatly reduced.
Furthermore, the primary biochemical section is selected from one of the processes of biological contact oxidation, MBBR and other high volume load, the volume load is 2kg (COD 5）/m3.d or more, the dissolved oxygen is controlled to be 2mg/L or more, and the wastewater residence time is 24-168 h.
Furthermore, the secondary biochemical section is selected from one of BAF or MBR technology, has moderate volume load, not only can remove COD, but also has a filtering function, the dissolved oxygen is controlled to be more than 2mg/L, and the residence time of wastewater is 12-72 h.
Furthermore, the advanced oxidation section can improve the biodegradability of wastewater on the one hand and can remove odor exhausted by an exhaust pipe network on the other hand. The advanced oxidation section is a coupling process of ozone and hydrogen peroxide, and the ozone can be taken out or prepared by using empty segmented surplus oxygen; the ozone adding amount is 50 mg/L-300 mg/L, and the hydrogen peroxide adding amount is 10 mg/L-400 mg/L; the section can achieve the treatment effect without complex advanced oxidation technology by coupling ozone and hydrogen peroxide, and meanwhile, the salt in the water can not be increased, so that the total salt in the water reaches the standard.
It should be understood by those skilled in the art that the two-stage biochemical stage can decompose most of organic matters in the wastewater through the high salt tolerant bacteria GXNYJ-DL-1, partially convert the organic matters into inorganic carbon (carbon dioxide), and partially transfer the inorganic carbon into activated sludge for removal by sludge discharge; the high salt tolerant bacteria GXNYJ-DL-1 solves the problem that common strains cannot survive under the condition of high salt content, and the sulfide toxicity tolerance of the high salt tolerant bacteria also solves the problem that common salt tolerant bacteria have higher sulfide concentration or even cannot survive due to uneven aeration or local anaerobic oxidation of flora under the existence of a large amount of sulfate.
Furthermore, the tail gas treatment section adopts a physical adsorption method (such as activated carbon adsorption) or other physical and chemical methods, and a biological deodorization method can not be adopted, so that the problem that the excessive ozone is forced to damage biological deodorization microorganisms is avoided.
Further, the water yield of the first-stage nanofiltration is 70% -90%, and the water yield of the second-stage nanofiltration is 60% -80%; the nanofiltration can remove most of salt and part of organic matters.
Further, the vapor generated by the MVR reactor is condensed and then recycled, and the liquid phase enters a crystallizer for crystallization and salt separation, wherein the salt separation technical basis is as follows: in the range of 50-120 ℃, the solubility of most salts increases with the temperature, the solubility of Na 2SO4 decreases with the temperature, under the high temperature condition, na 2SO4 is firstly separated out due to supersaturation with the concentration of salts, high-purity Na 2SO4 is obtained, when the temperature is reduced, other salts are separated out due to supersaturation with the continuous concentration, and the mixed salts comprise sodium chloride, sodium carbonate and the like, and possibly contain a small amount of organic matters.
Compared with the prior art, the invention has the following advantages:
(1) The salt-tolerant strain GXNYJ-DL-1 used in the method has excellent salt tolerance, stronger sulfide toxicity tolerance, strong vitality and high stability, and plays an irreplaceable role in the treatment of the ethylene waste alkali solution.
(2) The method effectively solves the influence of malodor and toxic substances on a biochemical system, and solves the problem of process tail gas, and is specifically characterized in that: the pure oxygen reactor effectively removes most of sulfides, so that the hydrogen sulfide production (acid addition regulation production) of the neutralization pond is greatly reduced, the influence of sulfide toxicity on subsequent biochemistry is greatly reduced, meanwhile, sulfide is oxidized into high-valence salts, and the salt cannot influence salt tolerance bacteria; the stripping reactor further removes sulfides, mercaptans, sulfides and volatile phenols in the wastewater; the waste gas generated by the pure oxygen reactor and the stripping reactor is collected and then sent to the advanced oxidation section for treatment, no special waste gas treatment facilities are needed, and only a small amount of tail gas of the advanced oxidation section is needed to be treated.
(3) The method effectively solves the problem of salt in the wastewater, and is specifically characterized in that: the salt-tolerant strain GXNYJ-DL-1 and advanced oxidation combination remove most of organic matters in the wastewater, so that the wastewater can be desalted by using a membrane technology in the follow-up process; the neutralization of sulfuric acid and two-stage nanofiltration can be realized, so that the salt content of the effluent reaches the standard; sodium sulfate can be separated by MVR reactor and fractional crystallization.
(4) The method of the invention realizes recycling and reusing while removing COD greatly, namely realizes methane recycling through sludge anaerobic oxidation and sodium sulfate recycling through nanofiltration and MVR reactor. Meanwhile, the process method provided by the invention almost does not need dilution water.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 growth curves of the strains of example 1 at different salt contents;
FIG. 2 shows the COD removal rate of the strain of example 1 at different salt contents;
FIG. 3 growth curves of the strain of example 2 at S 2- concentration;
FIG. 4 is a flow chart showing the treatment of ethylene lye in example 3.
Description of biological Material preservation
The high salt-tolerant strain (Halomonas nigrificans) GXNYJ-DL-1 provided by the invention is preserved in the China general microbiological culture Collection center (China Committee); address: the institute of microorganisms at national academy of sciences of China, national academy of sciences, no. 1, north Star West way, no. 3, chat.Chao, beijing, city; preservation number: CGMCC No. 20350; preservation date: 7 months and 13 days 2020.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
Example 1
Salt tolerance measurement of high salt tolerance bacterium GXNYJ-DL-1
Preparing simulated wastewater (g/L): phenol 0.4,NaCl 3,FeSO4 0.02,CaCl2 0.03,MgSO4 1,Na2SO43,KH2PO4 0.034 ,NH4Cl 0.3, yeast extract 0.1, tryptone 0.05g, pH 7, salt content about 10g/L. Na 2SO4 is added on the basis of the simulated wastewater with the salt content of 10g/L to prepare wastewater with the salt content of 50g/L, 90g/L, 130 g/L, 170 g/L, 210 g/L and 250 g/L respectively.
Adding GXNYJ-DL-1 bacterial liquid into a conical flask according to the volume ratio of the bacterial liquid to the simulated wastewater of 1:20, controlling the temperature to be 35 ℃ by adopting a shaking table oscillation method, controlling the rotating speed to be 150 rpm, sampling at fixed time, measuring the bacterial density (OD 600) by using a spectrophotometer, and drawing a bacterial strain growth curve, wherein the bacterial strain growth curve under different salt concentrations is shown in figure 1; and the COD value of the final reaction solution was measured to determine the removal rate of COD by the strain, and the removal rate of COD of the strain at different salt concentrations after 76 hours is shown in FIG. 2.
According to the results shown in the figures 1 and 2, the growth of the strain is relatively slowed down along with the increase of the salt concentration, but the strain can be rapidly grown after a certain adaptation period, the strain grows faster under the salt concentration of 10-130 g/L, and the COD removal rate (initial phenol COD is about 1247 mg/L) is higher than 65%; at a salt concentration of 250 g/L, the strain adaptation period is relatively long, about 50 hours, then the strain starts to enter the growth period, the OD 600 value is obviously increased, and the corresponding COD removal rate can still reach 53%.
As shown in the embodiment, the strain GXNYJ-DL-1 has stronger salt tolerance, and can still lead the COD removal rate to reach 53% under the condition of the salt concentration of 250 g/L, but the optimal salt concentration is 50-130 g/L.
Example 2
S 2- toxicity resistance assay for high salt tolerant bacteria GXNYJ-DL-1
Preparing simulated wastewater (g/L): phenol 0.4,NaCl 3,FeSO4 0.02,CaCl2 0.03,MgSO4 1,Na2SO443,KH2PO4 0.034 ,NH4Cl 0.3, yeast extract 0.1, tryptone 0.05g, pH 7, salt content about 50g/L. Na 2 S is additionally added on the basis of simulating the wastewater to prepare wastewater with the mass concentration of S 2- of 0mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L and 300 mg/L.
Adding GXNYJ-DL-1 bacterial liquid into a conical flask according to the volume ratio of the bacterial liquid to the simulated wastewater of 1:20, standing for 24 hours, oscillating by a shaking table, controlling the temperature at 35 ℃, rotating at 150rpm, sampling at fixed time, measuring the bacterial density (OD 600) by a spectrophotometer, and drawing a bacterial strain growth curve, wherein the bacterial strain growth curve is shown in figure 3.
As can be seen from FIG. 3, the growth of the strain during the standing period is very slow, on the one hand, the strain is limited by the dissolved oxygen and on the other hand, the strain is limited by the toxicity of S 2-, and the shaking table shaking reaction starts after the 24-hour standing period, at the moment, the concentration of the strain starts to be obviously increased, but compared with the example 1, the strain growth is relatively slow; over two days of growth, the overall OD 600 value was increased from 0.25 to 0.45, indicating that the strain did not lose viability due to the toxicity of the earlier stage S 2-, and began to gradually revive after a relatively long adaptation period, especially with the 300mg/L S 2- sample, the strain concentration was still steadily increasing.
As shown in the example, the strain GXNYJ-DL-1 has strong S 2- toxicity resistance, and can tolerate the concentration of S 2- to 300mg/L.
Example 3
The process method of the invention is adopted to treat the ethylene waste alkali liquor
The process flow chart for treating the ethylene waste lye is shown in figure 4: the ethylene waste alkali liquid sequentially passes through a pure oxygen reactor, a neutralization reaction tank, a stripping reactor, a primary biochemical treatment, a high-grade oxidation, a secondary biochemical treatment and a two-stage nanofiltration, and then enters a water outlet regulating tank. The pure oxygen reactor is characterized in that oxygen is sourced from an air separation system, and the reaction gas is discharged through a pressure reducing valve after reaching a certain pressure; the stripping reactor adopts an air source, and the stripping waste gas is communicated with a pressure reducing valve to discharge waste gas and is sent to advanced oxidation treatment; the advanced oxidation is carried out by combining ozone with hydrogen peroxide, and the tail gas treatment adopts activated carbon adsorption; the sludge produced by two-stage biochemistry is changed into methane after being subjected to sludge anaerobic oxidation and is recycled to a storage tank; concentrated water generated by two-stage nanofiltration is subjected to MVR reactor and fractional crystallization to obtain sodium sulfate and mixed salt, and the residual mother liquor is returned to the water inlet end of the MVR reactor.
Ethylene waste lye, its quality of water is as follows: COD 25930mg/L, chloride 785mg/L, sulfate 38405mg/L, total salt content 75000mg/L, sulfide 12138mg/L, pH 12.6 and wastewater flow 20t/h.
The specific operating conditions for treating the waste lye are as follows: the sulfide is reduced to 364mg/L, COD is reduced to 11560mg/L after the wastewater is treated by a pure oxygen reactor, the pseudo COD of the sulfide is mainly removed, sulfate ions are increased to 59120mg/L, the pressure of the pure oxygen reactor is controlled to be 0.15 MPa-0.3 MPa by a pressure reducing valve, and effluent enters a neutralization reaction tank; adding concentrated sulfuric acid into a neutralization reaction tank until the pH value is 6.5, increasing sulfate ions to 61134mg/L, and increasing the total salt content to 77230mg/L; the effluent is blown off by air of a stripping reactor, sulfide is further reduced to 35mg/L, COD is reduced to 8693mg/L, and salt is basically unchanged; the subsequent primary biochemistry adopts a biological contact oxidation pond process, the strain is high-efficiency salt-tolerant bacteria GXNYJ-DL-1, the dissolved oxygen is controlled to be more than 2mg/L, the retention time of wastewater is 80 hours, the COD of the final effluent is 650mg/L, the ozone addition amount is 100mg/L after the treatment of ozone and hydrogen peroxide, the hydrogen peroxide addition amount is 200mg/L, the COD after the treatment is reduced to 320mg/L, the secondary biochemistry adopts a BAF process, the same high-efficiency salt-tolerant bacteria GXNYJ-DL-1 is adopted, the retention time of wastewater is 24 hours, the COD is reduced to 71mg/L, and the salinity of the effluent is unchanged; after the secondary biochemical effluent enters the two-stage nanofiltration, the water yield of the primary nanofiltration is 86%, the water yield of the secondary nanofiltration is 78%, and the final yield of the secondary nanofiltration is about 13.3t/h, and the effluent flows into the effluent regulating and controlling tank, so that the COD is reduced to 56mg/L, the chloride ion concentration is 893mg/L, the salt content is 2830mg/L, and the effluent can reach the standard. The MVR reactor and the fractional crystallization obtain sodium sulfate products and mixed salt, and the purity of the sodium sulfate is 98.5 percent. The biochemical sludge is subjected to sludge anaerobic oxidation to obtain methane with the purity of 93.5%.
The embodiment of the invention can effectively treat the ethylene waste alkali liquid, can realize the standard discharge of total salt and COD, and simultaneously realizes the recycling of resources.
Example 4
Treatment of certain ethylene lye by the process shown in FIG. 4
Ethylene waste lye, its quality of water is as follows: COD 45930mg/L, chloride ions 1156mg/L, sulfate ions 53000mg/L, total salt content 119000mg/L, sulfide 21490mg/L, pH 13.1 and wastewater flow rate 19.1t/h.
The specific operating conditions for treating the waste lye are as follows: the sulfide is reduced to 1053mg/L, the COD is reduced to 22340mg/L after the wastewater is treated by the pure oxygen reactor, the pseudo COD of the sulfide is mainly removed, sulfate ions are increased to 87045mg/L, the pressure of the pure oxygen reactor is controlled to be 0.15 MPa-0.3 MPa by a pressure reducing valve, and the effluent enters a neutralization reaction tank; adding concentrated sulfuric acid into a neutralization reaction tank until the pH value is 6.6, rising sulfate ions to 89076mg/L, and rising the total salt content to 121230mg/L; the effluent is blown off by air of a blowing-off reactor, sulfide is further reduced to 236mg/L, COD is reduced to 18756mg/L, and salt is basically unchanged; the subsequent primary biochemistry adopts a biological contact oxidation pond process, the strain is high-efficiency salt-tolerant bacteria GXNYJ-DL-1, the dissolved oxygen is controlled to be more than 2mg/L, the retention time of wastewater is 156 hours, the COD of the final effluent is 1340mg/L, the wastewater is treated by ozone and hydrogen peroxide, the ozone addition amount is 150mg/L, the hydrogen peroxide addition amount is 300mg/L, the COD after treatment is reduced to 730mg/L, the secondary biochemistry adopts a BAF process, the same high-efficiency salt-tolerant bacteria GXNYJ-DL-1 is adopted, the retention time of wastewater is 36 hours, the COD is reduced to 305mg/L, and the salinity of the effluent is unchanged; after the secondary biochemical effluent enters the two-stage nanofiltration, the water yield of the primary nanofiltration is 83%, the water yield of the secondary nanofiltration is 71%, and finally about 11.1t/h of the effluent flows into the effluent regulating and controlling tank, at the moment, COD is reduced to 215mg/L, the chloride ion concentration is 1345mg/L, the salt content is 3514mg/L, the water quality requirement of the secondary sewage treatment field is met, the municipal sewage pipe network requirement of the municipal sewage in part of the area is met, the COD of the municipal sewage required to be discharged is lower than 500mg/L, and the salt content is lower than 5000mg/L. The MVR reactor and the fractional crystallization obtain sodium sulfate products and mixed salt, and the purity of the sodium sulfate is 98.8 percent. The biochemical sludge is subjected to sludge anaerobic oxidation to obtain methane with the purity of 94.1%.
The embodiment of the invention can effectively treat high-concentration ethylene waste alkali liquor, the total salt and COD are removed greatly, the effluent meets the requirement of entering a secondary sewage treatment field or municipal sewage pipe network, and the resource recycling is realized.
Example 5
Treatment of certain ethylene lye by the process shown in FIG. 4
Ethylene waste lye, its quality of water is as follows: COD 62000mg/L, chloride ion 1450mg/L, sulfate ion 75000mg/L, total salt content 169470mg/L, sulfide 31490mg/L and pH 13.2.
The total salt content of the ethylene waste alkali liquor is 169470mg/L, which exceeds the optimal salt tolerance interval (10-130 g/L) of the salt tolerant bacteria GXNYJ-DL-1, and in order to obtain better treatment effect, the ethylene waste alkali liquor is diluted by a small amount by using the effluent regulating pool water, the volume ratio of the ethylene waste alkali liquor to the diluted water is 1:0.5, and the total salt content of the mixed water is about 113000mg/L after dilution.
The specific operation conditions of the waste alkali liquid treatment are similar to those of the embodiment 4, and the COD and the total salt content of the waste alkali liquid can meet the water quality requirement of the secondary sewage treatment field and also meet the requirement of the municipal sewage pipe network.
According to the embodiment, the ultra-high concentration ethylene waste alkali liquid can be effectively treated by only a small amount of dilution water, so that the total salt and COD (chemical oxygen demand) are greatly removed, the effluent meets the requirement of entering a secondary sewage treatment plant or municipal sewage pipe network, and the resource recycling is realized.
Claims (13)
1. The treatment method of the ethylene waste alkali liquid comprises a pretreatment section, an advanced treatment section, a salt treatment section and a sludge treatment section;
the pretreatment section sequentially comprises an air separation system, a pure oxygen reactor, a neutralization reaction tank and a stripping reactor;
The air separation system separates high-purity oxygen and nitrogen through air; the pure oxygen reactor adopts pure oxygen to oxidize and remove sulfides and partial organic matters in the waste alkali liquid, and waste gas is intermittently discharged through a pressure reducing valve; regulating the pH value of the effluent of the pure oxygen reactor to 6-8 in the neutralization reaction tank; the stripping reactor is used for stripping the hydrogen sulfide, mercaptan, thioether and volatile phenol malodorous gas in the wastewater through air, so that the influence of malodorous toxic gas on subsequent biochemistry is reduced, and the stripped gas is discharged to a waste gas pipe network;
The advanced treatment section sequentially comprises a primary biochemical section, a high-grade oxidation section, a secondary biochemical section and a tail gas treatment section; the primary biochemical section adopts high salt tolerant bacteria GXNYJ-DL-1 to treat wastewater, and most organic matters are removed through aeration biochemistry; the high-grade oxidation section changes the organic matters difficult to degrade of the macromolecules into small molecular organic matters and removes malodorous gases; the secondary biochemical section adopts high salt tolerant bacteria GXNYJ-DL-1 to treat the effluent of the advanced oxidation section, so that organic matters in the wastewater are further removed; the tail gas treatment section is used for treating the residual waste gas of the advanced oxidation section and discharging the treated waste gas;
The high salt tolerant bacteria GXNYJ-DL-1 (Halomonas nigrificans) is preserved in China general microbiological culture Collection center (CGMCC) with the preservation number of CGMCC No. 20350 in the year 2020, 7 and 13;
The salt treatment section comprises a two-stage nanofiltration section, an MVR concentration section and a crystallization section; the two-stage nanofiltration filters sulfate ions, calcium magnesium ions and other divalent and trivalent ions to ensure that the sulfate ions, the calcium magnesium ions and the other divalent and trivalent ions are on the concentrated water side, and the main chlorine ions and sodium ions are on the water production side; the water produced by the two-stage nanofiltration is regulated and controlled, and then is discharged according to the quality of the water to reach the standard or discharged into a second-stage sewage treatment field; concentrated water produced by the two-stage nanofiltration enters an MVR reactor, the concentrated water enters a crystallizer after being further concentrated by MVR, sodium sulfate with purity more than 98% is obtained by high-temperature section crystallization, mixed salt is obtained by low-temperature crystallization, and the residual mother liquor returns to the water inlet end of the MVR reactor;
the sludge treatment section is used for recycling redundant sludge generated by primary biochemistry and secondary biochemistry, converting biological sludge into methane through sludge anaerobic oxidation and recycling the methane.
2. The method according to claim 1, wherein the salt concentration in the wastewater entering the primary biochemical stage is controlled to be 250g/L or less.
3. The method according to claim 2, wherein the salt concentration in the wastewater entering the primary biochemical stage is controlled to be 50-130 g/L.
4. The treatment method according to claim 1, wherein the exhaust gas intermittently discharged by the pressure reducing valve is discharged from the exhaust gas pipe network to the advanced oxidation stage for treatment, and the pressure of the pressure reducing valve is controlled to be 0.15-0.3 MPa.
5. The process of claim 1 wherein the pH is adjusted in the neutralization reaction tank by adding sulfuric acid.
6. The process of claim 1 wherein said stripping reactor employs a micro-porous aeration disc.
7. The process of claim 1, wherein the primary biochemical stage is selected from one of a biological contact oxidation and MBBR process.
8. The treatment method according to claim 1, wherein the dissolved oxygen in the primary biochemical stage is controlled to be more than 2mg/L, and the retention time of the wastewater is 24-168 hours.
9. The process of claim 1, wherein the secondary biochemical stage is selected from one of BAF or MBR processes.
10. The treatment method according to claim 1, wherein the dissolved oxygen in the secondary biochemical stage is controlled to be more than 2mg/L, and the retention time of the wastewater is 12-72 h.
11. The treatment method according to claim 1, wherein the ozone addition amount of the advanced oxidation stage is 50mg/L to 300mg/L, and the hydrogen peroxide addition amount is 10mg/L to 400mg/L.
12. The process of claim 1 wherein the tail gas treatment stage employs a physical adsorption process.
13. The process of claim 1 wherein the vapor produced in the MVR reactor is condensed and recycled and the liquid phase is fed to a crystallizer for crystallization to separate salts.
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