CN114230106A - Oil refining wastewater treatment method - Google Patents
Oil refining wastewater treatment method Download PDFInfo
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- CN114230106A CN114230106A CN202111621971.4A CN202111621971A CN114230106A CN 114230106 A CN114230106 A CN 114230106A CN 202111621971 A CN202111621971 A CN 202111621971A CN 114230106 A CN114230106 A CN 114230106A
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- 238000007670 refining Methods 0.000 title claims abstract description 78
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 192
- 238000011282 treatment Methods 0.000 claims abstract description 87
- 239000008213 purified water Substances 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002351 wastewater Substances 0.000 claims abstract description 37
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 35
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 17
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims abstract description 17
- 235000019796 monopotassium phosphate Nutrition 0.000 claims abstract description 17
- 239000013505 freshwater Substances 0.000 claims abstract description 16
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims abstract description 11
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000008394 flocculating agent Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000013327 media filtration Methods 0.000 claims 1
- 238000001471 micro-filtration Methods 0.000 claims 1
- 238000009287 sand filtration Methods 0.000 claims 1
- 239000005416 organic matter Substances 0.000 abstract description 13
- 239000010865 sewage Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000004071 biological effect Effects 0.000 abstract 1
- 239000003610 charcoal Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 66
- 230000000052 comparative effect Effects 0.000 description 18
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- 239000002245 particle Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 238000005188 flotation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000005789 organism growth Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004457 water analysis 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
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- 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
- C02F2103/365—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 from petrochemical industry (e.g. refineries)
-
- 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
- C02F3/30—Aerobic and anaerobic processes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Water Treatments (AREA)
Abstract
The application relates to the technical field of sewage treatment, and particularly discloses an oil refining wastewater treatment method, which comprises the following steps: s1, cooling, adding a flocculating agent into the cooled oil refining purified water, performing air floatation treatment, and filtering to obtain primarily treated oil refining purified water; s2, adjusting the pH value; s3, reverse osmosis treatment to obtain concentrated water and fresh water which can be directly recycled; s4, adding monopotassium phosphate and magnesium chloride into the concentrated water, settling and filtering; and S5, introducing the filtered concentrated water into a biological reaction container filled with activated carbon, and introducing air into the biological reaction container to enable organic matters in the concentrated water to have aerobic reaction and anaerobic reaction. This application is mainly through carrying out preliminary treatment, reverse osmosis treatment to oil refining waste water, but the fresh water of production direct retrieval and utilization, and concentrated water is handled through removing ammonia nitrogen and biological activity charcoal again, reaches the organic matter content that reduces the aquatic to reach the purpose that reduces COD emission.
Description
Technical Field
The application relates to the technical field of sewage treatment, in particular to a method for treating oil refining wastewater.
Background
In the process of petroleum refining, certain acidic waste water is generated, and the waste water is mainly derived from the deep processing process of oil products, such as catalytic cracking, hydrocracking, delayed coking and the like. The wastewater mainly contains organic matters such as ammonia nitrogen, hydrogen sulfide, phenols and the like, the wastewater is subjected to extraction of the ammonia nitrogen and the hydrogen sulfide by an acidic water stripping device of an oil refinery, sulfur, ammonia water and the like are produced, the content of the ammonia nitrogen in the extracted discharged water is less than 50mg/L, the content of the hydrogen sulfide is less than 25mg/L, the extracted discharged water is called purified water, however, the purified water still contains a certain amount of hydrocarbons, metal ions and the like, and some substances are harmful to the environmental health, such as phenols, heavy metals and the like contained in the purified water, and the discharge is limited according to the related national sewage discharge standard.
The industrial purified water treatment of the acidic water stripping device is partially directly used for crude oil electric desalting water injection or normal pressure water injection, water quality is utilized, most of purified water is merged into oily sewage to form oil refining wastewater, and organic matter degradation reaches certain discharge requirements through aeration, anaerobic oxidation and aerobic oxidation. The related art also adopts other treatment modes to treat the oil refining wastewater, such as aerobic + sedimentation + anaerobic + MBR treatment mode of oil refining wastewater, and such as biochemical treatment, pretreatment and post-treatment modes, wherein the pretreatment mode comprises primary filtration, ozone oxidation and the like, the post-treatment mode comprises secondary filtration, nanofiltration and the like, and the treatment mode comprises ultrafiltration + reverse osmosis + ozone catalytic oxidation.
The methods provided by the above are generally used for treating the mixed water quality of different units in the oil refining process, and because the water quality of each device has large difference, the water quality fluctuates when the production of a certain device is changed. After different unit water qualities are mixed, the components of the mixed water quality become complex, and the problems can bring difficulty to post-treatment, cause a series of problems of long water treatment period, large occupied area of a treatment device and the like. If membrane treatment is adopted, when the COD content in the wastewater is high and various ions exist, the filter membrane is easy to block, the filter membrane needs to be cleaned frequently, and the treatment cost is high.
Disclosure of Invention
Aiming at the defects in the related technology, the application provides the method for treating the oil refining wastewater, the method mainly comprises the steps of carrying out pretreatment and reverse osmosis treatment on the oil refining wastewater, directly recycling the produced fresh water, and treating the concentrated water by ammonia nitrogen removal and biological activated carbon to reduce the content of organic matters in the water, so that the aim of reducing the COD discharge amount is fulfilled.
In order to achieve the purpose, the application provides a method for treating oil refining wastewater, and adopts the following technical scheme: a method for treating oil refining wastewater comprises the following steps:
s1, cooling the oil refining purified water, adding a flocculating agent into the cooled oil refining purified water, performing air floatation treatment, and filtering to obtain primarily treated oil refining purified water;
s2, adding an alkaline substance to the primarily treated purified water from oil refining obtained in S1 to adjust the pH;
and S3, performing reverse osmosis treatment on the refined purified water after the pH value is adjusted in the S2 to obtain fresh water and concentrated water.
The oil refining purified water is acidic wastewater generated in the oil refining process, and water flow generated after ammonia nitrogen and hydrogen sulfide are removed through an acidic water stripping device. Organic compounds containing elements such as nitrogen, oxygen, sulfur and the like exist in natural crude oil, the compounds are converted into ammonia, hydrogen sulfide or water-soluble nitrogen, oxygen and sulfur compounds through processes such as cracking, hydrogenation reduction and the like in a petroleum refining process, and the ammonia, the hydrogen sulfide or the water-soluble nitrogen, oxygen and sulfur compounds are removed through water washing in an oil refining process, so that acidic water containing ammonia nitrogen, hydrogen sulfide and the like is generated. In order to recover the ammonia and the sulfur in the water and reduce the emission of harmful substances, the water is sent to an acid water stripping device, and the ammonia and the sulfur are recovered through stripping. The stripped water can not meet the discharge requirement although the harmful substances are reduced, and is generally merged into the oily sewage to be sent to a sewage treatment plant for unified treatment. The utilization rate of equipment can be improved through centralized treatment, but the components of the mixed water flow become complex, so that the separation and the reuse become difficult.
This application is handled oil refining purified water through cooling, flocculation, air supporting, filtration and pH regulation, and oil refining purified water is through the cooling back, through air supporting, filtration, can detach aquatic insoluble organic matter and solid particle, reduces the turbidity of oil refining purified water, can reduce the jam of oil refining purified water aquatic impurity to the membrane.
Preferably, the concentrated water further comprises the following treatment steps:
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling and filtering;
and S5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon, and introducing air into the biological reaction container, so that organic matters in the concentrated water undergo aerobic reaction and anaerobic reaction to reduce the COD content of the organic matters in the concentrated water.
By adopting the technical scheme, potassium dihydrogen phosphate and magnesium chloride are added into concentrated water to generate magnesium ammonium phosphate precipitate, and ammonia nitrogen is separated from the water through the steps of sedimentation and filtration, so that nutrition is provided for the growth of organisms in subsequent biochemical degradation, and the activity of the organisms is increased. The concentrated water after ammonia nitrogen removal enters a biological reaction container filled with activated carbon, and organic matters in the concentrated water can be further biodegraded, so that COD (chemical oxygen demand) of the concentrated water is further reduced by about 50%. The biological reaction container filled with the activated carbon used in the application refers to that the activated carbon is used as a carrier, a certain amount of biological films are formed on the surface of the activated carbon through training culture, and organic matters can be degraded by organisms after concentrated water containing the organic matters passes through the biological films.
Preferably, in S1, the filtering is performed by one or a combination of sand filtering, multi-media filtering, fiber bundle filtering, micro-filtering and ultra-filtering.
Preferably, the flocculating agent is a mixture consisting of one or more of ferrous sulfate, polyaluminum chloride, polyaluminum ferric chloride, polyaluminum sulfate, polyaluminum silicate, polyacrylamide, anionic polyacrylamide, cationic polyacrylamide and polyquaternary ammonium salt.
Preferably, the alkaline substance is a mixture of one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
Preferably, in S2, the pH of the purified water from oil refining in the primary treatment is adjusted to 6 to 10.
Through adopting above-mentioned technical scheme, the oil refining purified water accessible high-pressure pump after adjusting pH beats the high-pressure side of reverse osmosis membrane, can produce pure fresh water like this at the low pressure side of membrane, produces the dense water of reverse osmosis at the high-pressure side.
Preferably, the reverse osmosis treatment adopts flat membrane reverse osmosis, roll type reverse osmosis or butterfly tube reverse osmosis, and the membrane is a composite membrane consisting of one or more of a cellulose acetate membrane, a polyvinyl chloride membrane, a polyamide membrane, a polysulfone membrane and a polycarbonate membrane.
By adopting the technical scheme, most of ions and organic hydrocarbon in the fresh water produced by the reverse osmosis membrane are removed, the fresh water can be directly used for supplementing circulating cooling water or boiler water, ions and organic matters in the concentrated water are concentrated and enter the biological activated carbon device for biochemical degradation.
Preferably, the molar ratio of the potassium dihydrogen phosphate to the magnesium chloride to the ammonia nitrogen in the concentrated water obtained from S3 is 1 (0.1-10).
Preferably, in S5, the filtered concentrated water is introduced into the bioreactor in a continuous operation mode.
Through adopting above-mentioned technical scheme, the active carbon is filled in the biological reaction container, and after the ammonia nitrogen was removed to reverse osmosis play water, send into the biological reaction container who is equipped with the active carbon in succession through the pump, let in the air simultaneously bottom the container, water is in active carbon layer and air contact, and wherein the organic matter is absorbed by the organism of being attached to the active carbon surface, produces aerobic reaction on the surface, and inside the active carbon hole, the organic matter takes place anaerobic reaction after diffusing into, goes out water organic matter COD volume and reduces.
Preferably, in the S5, the concentrated water COD entering the biological reaction vesselcrAt 500-2000mg/L, the speed of air in the biological reaction container is 0.5-3L/h, and the treatment load of the biological reaction container is 1-15kgCOD/m3D, a single tower or a combination of multiple towers can be adopted in the operation process.
After the concentrated water generated after reverse osmosis enters the biological reaction container, organic matters in the concentrated water are degraded through biological activated carbon treatment, so that the COD of the discharged water is reduced, and through the parameter control, the COD of the sewage can be reduced by about 50 percent compared with that before degradation.
In summary, the present application has the following beneficial effects:
(1) the oil refining purified water enters the reverse osmosis membrane for treatment after being shunted out from the oil refining wastewater, the hardness of the oil refining purified water is lower, inorganic salt and organic matter are not easy to deposit on the surface of the membrane during the reverse osmosis treatment, the pollution degree of the membrane is slowed down, and the service life of the reverse osmosis membrane can be greatly prolonged;
(2) before the oil refining purified water enters the reverse osmosis membrane treatment, flocculation, air flotation, filtration and pH adjustment operations are carried out, insoluble organic matters and solid particles in the water can be removed, the turbidity of the purified water is reduced, the blockage of impurities to the membrane is reduced, and the service life of the reverse osmosis membrane is greatly prolonged;
(3) before the biological activated carbon treatment, potassium dihydrogen phosphate and magnesium chloride are added into concentrated water obtained by reverse osmosis treatment to remove ammonia nitrogen in the water and provide nutrition for organism growth, so that purified water which is not easy to degrade in natural environment is easy to degrade, and after the biological activated carbon treatment, COD can be reduced by about 50% compared with COD before the treatment.
Drawings
FIG. 1 is a schematic diagram of a self-made bioreactor according to the present application;
FIG. 2 is a schematic flow chart of the oil refining purified water treatment method.
Reference numerals: 1. an activated carbon column; 2. an oxygenation pump.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
The wastewater adopted by the application is selected from hydrocracking acid water and delayed coking acid water produced by China petrochemical Shanghai Gaoqiao division.
The model of the ammonia nitrogen detector is Amtax NA 8000.
The acidic water stripping device is a single-tower stripping device designed by Inpaier chemical engineering Co., Ltd, Qingdao, and the treatment capacity is 50 t/h.
The structure of the bioreactor is shown in figure 1, and comprises an activated carbon column 1, wherein water enters from the bottom of the activated carbon column, water is stored at the top of the activated carbon column, and the bottom of the activated carbon column is communicated with an oxygenation pump 2.
Examples
Example 1
The specific operation method of the oil refining wastewater treatment method can refer to a flow chart in figure 1, the wastewater is hydrocracking acidic water, and the specific treatment steps are as follows:
s1, carrying out steam stripping by using an acidic water steam stripping device to obtain 1 ton of oil refining purified water, naturally cooling to 25 ℃, adding 50g of polyaluminium chloride to enable suspended particles in the liquid to be aggregated, carrying out air floatation treatment, and then carrying out ultrafiltration on the oil refining purified water subjected to air floatation to remove insoluble organic matters and solid particles in the oil refining purified water to obtain primary treated oil refining purified water;
s2, adjusting the pH value of the oil refining purified water obtained in the step S1 to 7.5 by adopting sodium hydroxide;
s3, performing flat membrane reverse osmosis treatment on the oil refining purified water with the pH value adjusted in the S2 by adopting a polysulfone membrane to obtain concentrated water and fresh water which can be directly recycled, wherein the operating pressure in the reverse osmosis treatment is 2Mpa, and the operating temperature is 25 ℃;
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling for 2 hours, filtering generated precipitates to remove ammonia nitrogen in the concentrated water, wherein the molar ratio of the monopotassium phosphate to the magnesium chloride to the ammonia nitrogen in the concentrated water obtained in the step S3 is 1:0.1, and the molar content of the ammonia nitrogen in the concentrated water is directly measured by an ammonia nitrogen detector;
s5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon in a continuous operation mode, and introducing air from the bottom of the biological reaction container to enable organic matters in the concentrated water to have aerobic reaction and anaerobic reaction so as to reduce the COD (chemical oxygen demand) amount of the organic matters in the concentrated water, wherein the air introduction speed is 0.5L/h, and the treatment load of the biological reaction container is 1 kgCOD/d.m3The run time was 30 days.
Example 2
A treatment method of oil refining wastewater is disclosed, wherein the wastewater is hydrocracking acidic water, and the treatment method comprises the following specific treatment steps:
s1, carrying out steam stripping by using an acidic water steam stripping device to obtain 1 ton of oil refining purified water, naturally cooling to 25 ℃, adding 50g of polyacrylamide to enable suspended particles in the liquid to be aggregated, carrying out air floatation treatment, and then carrying out ultrafiltration on the oil refining purified water subjected to air floatation to remove insoluble organic matters and solid particles in the oil refining purified water to obtain primary treated oil refining purified water;
s2, adjusting the pH value of the oil refining purified water obtained in the step S1 to 8.5 by adopting sodium hydroxide;
s3, carrying out plate membrane reverse osmosis treatment on the refined oil purified water with the pH value adjusted in the step S2 by adopting a polyvinyl chloride membrane to obtain concentrated water and fresh water which can be directly recycled, wherein the operating pressure in the reverse osmosis treatment is 2Mpa, and the operating temperature is 25 ℃;
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling for 2 hours, filtering generated precipitates to remove ammonia nitrogen in the concentrated water, wherein the molar ratio of the monopotassium phosphate to the magnesium chloride to the ammonia nitrogen in the concentrated water obtained in the step S3 is 1:5, and the molar content of the ammonia nitrogen in the concentrated water is directly measured by an ammonia nitrogen detector;
s5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon in a continuous operation mode, and introducing air from the bottom of the biological reaction container to enable organic matters in the concentrated water to have aerobic reaction and anaerobic reaction so as to reduce the COD (chemical oxygen demand) amount of the organic matters in the concentrated water, wherein the air introduction speed is 1.5L/h, and the treatment load of the biological reaction container is 8 kgCOD/d.m3The run time was 30 days.
Example 3
A treatment method of oil refining wastewater is disclosed, wherein the wastewater is hydrocracking acidic water, and the treatment method comprises the following specific treatment steps:
s1, carrying out steam stripping by using an acidic water steam stripping device to obtain 1 ton of oil refining purified water, naturally cooling to 25 ℃, adding 50g of polyaluminium chloride to enable suspended particles in the liquid to be aggregated, carrying out air floatation treatment, and then carrying out ultrafiltration on the oil refining purified water subjected to air floatation to remove insoluble organic matters and solid particles in the oil refining purified water to obtain primary treated oil refining purified water;
s2, adjusting the pH value of the oil refining purified water obtained in the step S1 to 9.5 by adopting sodium hydroxide;
s3, performing butterfly tube reverse osmosis treatment on the oil refining purified water with the pH value adjusted in the S2 by adopting a polyamide membrane to obtain concentrated water and fresh water which can be directly recycled, wherein the operating pressure in the reverse osmosis treatment is 2Mpa, and the operating temperature is 25 ℃;
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling for 2 hours, filtering generated precipitates to remove ammonia nitrogen in the concentrated water, wherein the molar ratio of the monopotassium phosphate to the magnesium chloride to the ammonia nitrogen in the concentrated water obtained in the step S3 is 1:10, and the molar content of the ammonia nitrogen in the concentrated water is directly measured by an ammonia nitrogen detector;
s5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon in a continuous operation mode, and introducing air from the bottom of the biological reaction container to enable organic matters in the concentrated water to have aerobic reaction and anaerobic reaction so as to reduce the COD (chemical oxygen demand) amount of the organic matters in the concentrated water, wherein the air introduction speed is 3L/h, and the treatment load of the biological reaction container is 10 kgCOD/d.m3The run time was 30 days.
Example 4
A treatment method of oil refining wastewater is disclosed, wherein the wastewater is delayed coking acidic water, and the specific treatment steps are as follows:
s1, carrying out steam stripping by using an acidic water steam stripping device to obtain 1 ton of oil refining purified water, naturally cooling to 25 ℃, adding 50g of polyaluminium chloride to enable suspended particles in the liquid to be aggregated, carrying out air floatation treatment, and then carrying out ultrafiltration on the oil refining purified water subjected to air floatation to remove insoluble organic matters and solid particles in the oil refining purified water to obtain primary treated oil refining purified water;
s2, adjusting the pH value of the oil refining purified water obtained in the step S1 to 7.5 by adopting sodium hydroxide;
s3, performing flat membrane reverse osmosis treatment on the oil refining purified water with the pH value adjusted in the S2 by adopting a polysulfone membrane to obtain concentrated water and fresh water which can be directly recycled, wherein the operating pressure in the reverse osmosis treatment is 2Mpa, and the operating temperature is 25 ℃;
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling for 2 hours, filtering generated precipitates to remove ammonia nitrogen in the concentrated water, wherein the molar ratio of the monopotassium phosphate to the magnesium chloride to the ammonia nitrogen in the concentrated water obtained in the step S3 is 1:0.1, and the molar content of the ammonia nitrogen in the concentrated water is directly measured by an ammonia nitrogen detector;
s5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon in a continuous operation mode, and introducing air from the bottom of the biological reaction container to enable organic matters in the concentrated water to have aerobic reaction and anaerobic reaction so as to reduce the COD (chemical oxygen demand) amount of the organic matters in the concentrated water, wherein the air introduction speed is 0.5L/h, and the treatment load of the biological reaction container is 1 kgCOD/d.m3The run time was 30 days.
Comparative example
Comparative example 1
A method for treating refinery waste water, which lacks the operation of adding polyaluminium chloride to aggregate suspended particles in step S1, and the other steps are the same as those in example 1.
Comparative example 2
A method for treating refinery waste water, which lacks the operation of adding polyaluminium chloride to perform the aggregation of suspended particles and the air flotation treatment in step S1, and the other steps are the same as those in example 1.
Comparative example 3
A method for treating refinery waste water is different from example 1 in that steps S4 and S5 comprise the following steps: the concentrated water obtained in S3 was allowed to stand at 25. + -. 5 ℃ for 30 days and then cultured in an incubator at 30 ℃ for 7 days.
Comparative example 4
A method for treating refinery waste water is different from example 1 in that the specific operation steps of step S5 are as follows: and (3) placing the concentrated water filtered by the S4 in a natural environment at 25 +/-5 ℃ for 10 days.
Comparative example 5
A method for treating refinery wastewater, which does not include step S4, and the other steps are the same as those of example 1.
Comparative example 6
The oil refining waste water is hydrocracking acid water, oil refining purified water is obtained after the hydrocracking acid water is treated by an acid water stripping device, and after the oil refining purified water is mixed with biological sewage, the water quality COD is 280mg/L, and the conductivity is 1230 us/cm. After the effluent is treated by a regulating reservoir, contact oxidation, aeration, precipitation, oxygen deficiency, aerobiotic and MBR, the COD of the effluent is 53.2mg/L, and the conductivity is 1250us/cm, namely the COD of the treated water is reduced by 81 percent, and the conductivity is not changed.
Performance test
The membrane fluxes of the water and the reverse osmosis membrane treated by the methods for treating refinery wastewater of examples 1 to 4 and comparative examples 1 to 5 were measured, respectively, and the results are shown in the following table.
The conductivity test is based on the determination of the conductivity of the water and cooling water analysis method for the GB/T6908-2018 boiler; the test instrument is a thunder magnetic DDS11A conductivity meter.
CODcrThe test is based on a dichromate method for determining the chemical oxygen demand of water quality in GB/T11914-1989; the testing instrument is a Lianhua COD tester.
The formula for calculating the membrane flux (J) is: j ═ V/(T × a);
in the formula: j- -Membrane flux (L/m)2H); v- -sample volume (L); t- -sampling time (h); a- -effective area of the membrane (m)2)。
Results of membrane flux test of reverse osmosis membrane
Comparing the test results of examples 1 to 4, it can be seen that the membrane flux reduction rates are substantially the same, which indicates that the treatment of the refinery wastewater by the treatment method of the present application can reduce the blockage of the reverse osmosis membrane by impurities, and the treatment method is more stable.
Comparing the test results of the example 1 and the comparative examples 1 and 2, it can be seen that the membrane flux reduction rate of the example 1 is 3%, and the membrane flux reduction rates of the comparative examples 1 and 2 are 11% and 15%, respectively, which indicates that the oil refining purified water is subjected to flocculation treatment and air floatation treatment before reverse osmosis treatment, so that the impurities in the oil refining purified water can be greatly reduced, the pollution of the oil refining purified water to the reverse osmosis membrane is greatly reduced, the membrane flux reduction range is small, and the reverse osmosis membrane can be repeatedly used for multiple times, so that the cleaning times are reduced, and the treatment cost is reduced.
Results of testing changes of organic matters before and after oil refining water purification treatment
From the test results of examples 1 to 4, it can be seen that the fresh water obtained by subjecting the oil refining purified water to flocculation treatment, air flotation and filtration treatment and reverse osmosis treatment has an organic content of 93.5% or more compared with that of the fresh water obtained before treatment, and the removal rate of the organic content in the fresh water obtained by using the delayed coking acidic water in example 4 is the highest and can reach 97%. And the concentrated water obtained by the reverse osmosis treatment of the refined purified water in the embodiments 1 to 4 is subjected to ammonia nitrogen removal and biodegradation, so that the removal rate of the organic matter content can reach about 75%, and the biodegradation method provided by the application is relatively stable and has relatively high repeatability.
Comparing the results of the two tests, it can be seen that in comparative examples 1-2, compared to example 1, the continuous flocculation and air flotation treatment steps have less influence on the change of the organic matter content of the fresh water and the concentrated water obtained by reverse osmosis, but have a greater influence on the reduction rate of the membrane flux.
The test results of examples and comparative examples 3 to 5 were compared:
the concentrated water obtained by the reverse osmosis treatment in comparative example 3 did not undergo any treatment, and the organic content thereof did not change depending on the ambient temperature and the standing time.
The concentrated water obtained by the reverse osmosis treatment in the comparative example 4 only has the removal rate of the organic matter content of about 50% after ammonia nitrogen is removed. In the embodiment 1, the removal rate of the organic matter content of the concentrated water obtained by reverse osmosis treatment can reach about 75% after ammonia nitrogen removal and biodegradation. The method shows that after the concentrated water is settled by adopting the potassium dihydrogen phosphate and the magnesium chloride, the content of organic matters in the concentrated water can be reduced by about 50 percent, and the content of the organic matters can be further reduced by about 50 percent through biodegradation.
The concentrated water obtained by the reverse osmosis treatment in the comparative example 5 is directly subjected to biodegradation treatment without ammonia nitrogen removal, the organic matter content is reduced by about 50% according to the conclusion, and the actual test result shows that the organic matter content is only reduced by 15%. The reason is that the concentrated water is treated by adopting the potassium dihydrogen phosphate and the magnesium chloride, so that ammonia nitrogen can be removed, growth nutrition can be provided for organisms in the subsequent biodegradation process, and the degradation effect of the organisms can be improved.
Comparative example 6 provides a conventional refinery wastewater treatment method, and comparing example 1 with comparative example 6, it can be seen that purified water having lower conductivity can be obtained by the present application, compared to comparative example 6, in which refinery purified water is combined with other sewage and then subjected to an aerobic-anaerobic-MBR treatment process.
The above description is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above embodiments, and all technical solutions belonging to the idea of the present application belong to the protection scope of the present application. It should be noted that several improvements and modifications to the present application without departing from the principles of the present application will occur to those skilled in the art, and such improvements and modifications should also be considered within the scope of the present application.
Claims (9)
1. The method for treating the oil refining wastewater is characterized by comprising the following steps of:
s1, cooling the oil refining purified water, adding a flocculating agent into the cooled oil refining purified water, performing air floatation treatment, and filtering to obtain primarily treated oil refining purified water;
s2, adding an alkaline substance to the primarily treated purified water from oil refining obtained in S1 to adjust the pH;
s3, performing reverse osmosis treatment on the purified oil refining water with the pH value adjusted in the step S2 to obtain concentrated water and fresh water which can be directly recycled;
s4, adding monopotassium phosphate and magnesium chloride into the concentrated water obtained in the step S3, settling and filtering;
and S5, introducing the concentrated water filtered in the step S4 into a biological reaction container filled with activated carbon, and introducing air into the biological reaction container, so that organic matters in the concentrated water undergo aerobic reaction and anaerobic reaction.
2. The method for treating refinery waste water according to claim 1, wherein in the step S1, the filtration is one or a combination of sand filtration, multi-media filtration, fiber bundle filtration, microfiltration and ultrafiltration.
3. The refining wastewater treatment method according to claim 1, wherein the flocculating agent is a mixture of one or more of ferrous sulfate, polyaluminum chloride, polyaluminum ferric chloride, polyaluminum sulfate, polyaluminum silicate, polyacrylamide, anionic polyacrylamide, cationic polyacrylamide and polyquaternary ammonium salt.
4. The refining wastewater treatment method according to claim 1, wherein the alkaline substance is a mixture of one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
5. The refining wastewater treatment method according to claim 1, wherein the pH of the primary treated refined purified water in S2 is adjusted to 6-10.
6. The oil refining wastewater treatment method according to claim 1, wherein the reverse osmosis treatment is a flat membrane reverse osmosis, a roll type reverse osmosis or a butterfly tube reverse osmosis, and the membrane is a composite membrane composed of one or more of a cellulose acetate membrane, a polyvinyl chloride membrane, a polyamide membrane, a polysulfone membrane and a polycarbonate membrane.
7. The method for treating refinery waste water according to claim 1, wherein the molar ratio of potassium dihydrogen phosphate to magnesium chloride to ammonia nitrogen in the concentrated water obtained from S3 is 1 (0.1-10).
8. The method for treating refinery waste water according to claim 1, wherein in S5, the filtered concentrated water is introduced into the bioreactor in a continuous operation mode.
9. The method for treating refinery waste water according to claim 1, wherein the rate of introduction of air into the biological reaction vessel in S5 is 0.5 to 3L/h.
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| CN118026462A (en) * | 2024-03-20 | 2024-05-14 | 上海淼清水处理有限公司 | Treatment process of oil refining wastewater |
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