CN112028388B - Method for treating wastewater containing DMF, pyridine and pyridine derivatives - Google Patents
Method for treating wastewater containing DMF, pyridine and pyridine derivatives Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 26
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000003222 pyridines Chemical class 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000000701 coagulant Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 239000000645 desinfectant Substances 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 abstract description 8
- 230000001112 coagulating effect Effects 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000005842 biochemical reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- KAQJMEHRXVENSF-UHFFFAOYSA-N 2-(trichloromethyl)pyridine Chemical compound ClC(Cl)(Cl)C1=CC=CC=N1 KAQJMEHRXVENSF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/24—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2303/16—Regeneration of sorbents, filters
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a treatment method of wastewater containing DMF, pyridine and pyridine derivatives, which comprises the steps of adjusting the pH of the wastewater, evaporating the wastewater by a three-effect evaporator, collecting evaporation condensate, adding liquid alkali for alkaline hydrolysis, performing stripping, oil separation, coagulating sedimentation, fenton oxidation sedimentation, obtaining supernatant, filtering, performing resin adsorption treatment, and entering a biochemical treatment system to finally obtain wastewater meeting the discharge requirement. The invention has low energy consumption in the treatment process, can remove toxic and harmful organic matters before the biochemical treatment system, effectively avoids poisoning of a biochemical reaction tank, saves energy sources, is green and pollution-free, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating wastewater containing DMF, pyridine and pyridine derivatives.
Background
The two series of products of the trichloromethyl pyridine, the trifluoromethyl pyridine and the derivatives are organic intermediates with very high application value, and are widely applied to the fields of pesticides, medicines, fine chemical engineering and the like, and a large amount of wastewater containing DMF, pyridine and pyridine derivatives can be generated in the production process of the trichloromethyl pyridine, the trifluoromethyl pyridine and the derivatives.
The Chinese name of DMF is N, N-dimethylformamide, which is an organic solvent with stable chemical property, high boiling point and excellent performance, and can cause the increase of BOD and nitrogen content in water, so that the water quality is rapidly deteriorated, the DMF is difficult to biodegrade, and the DMF can poison microorganisms and cause great impact on biological treatment. Pyridine and pyridine derivatives have strong consistency or toxicity to biological bacteria in biochemical processes, so that biochemistry cannot be performed, namely pyridine substances in wastewater cannot be biochemically treated, and sludge death and biochemical paralysis are easy to cause.
In the prior art, DMF and pyridine in wastewater are separated in a high-temperature distillation mode, but the separation effect is poor, the boiling point is high, the distillation energy consumption is high, and the energy conservation and the environmental protection are not facilitated.
There is therefore a need for a process for the efficient treatment of such waste water.
Disclosure of Invention
In view of this, the present invention proposes a treatment method capable of effectively treating wastewater containing DMF, pyridine and pyridine derivatives.
The technical scheme of the invention is realized as follows: the invention provides a treatment method of wastewater containing DMF, pyridine and pyridine derivatives, which comprises the following steps:
step one, adding a pH regulator into wastewater containing DMF, pyridine and pyridine derivatives to regulate the pH, so as to obtain regulated wastewater;
step two, adding the wastewater obtained in the step one into a triple-effect evaporator for evaporation to obtain evaporation condensate for removing part of organic matters;
step three, carrying out stripping treatment on the evaporation condensate obtained in the step two to obtain stripped wastewater;
step four, adding the blown-off wastewater obtained in the step three into an oil removal regulating tank for oil removal treatment, and collecting a water layer to obtain oil-removed wastewater;
step five, adding the wastewater obtained after oil removal in the step four into a cavitation air floatation device to remove suspended matters, and collecting clear liquid;
sequentially adding a coagulant, 30% hydrogen peroxide and ferrous sulfate into the clear liquid obtained in the step five, carrying out solid-liquid separation after coagulation and flocculation precipitation reaction, and collecting filtrate;
step seven, adsorbing and purifying the filtrate obtained in the step six by using adsorption resin, and collecting the liquid after adsorption and purification;
step eight, adding the liquid obtained after adsorption purification in the step seven into a biochemical reaction tank for biochemical treatment to obtain biochemical treatment wastewater;
and step nine, performing solid-liquid separation on the biochemical treatment wastewater obtained in the step eight by using an MBR system, taking filtrate, adding disinfectant into the filtrate for disinfection, and discharging after reaching the standard through detection.
On the basis of the technical scheme, preferably, in the first step, the pH regulator comprises sodium hydroxide and hydrochloric acid, and the pH value of the regulated wastewater is 6.5-7.5.
On the basis of the above technical solution, preferably, the third step further includes: adding sodium hydroxide into the wastewater obtained in the step two, removing part of organic matters, adjusting the pH value to 11-12, and then transferring the wastewater into a stripping tower for stripping treatment, wherein the stripping treatment temperature is 0-90 ℃, the stripping time is 2-5h, and the stripping gas-liquid ratio is (1000-3000): 1 (v: v).
On the basis of the technical scheme, preferably, the blowing-off temperature is 25 ℃, the blowing-off time is 5h, and the blowing-off gas-liquid ratio is 3000:1 (v: v).
Still more preferably, in the sixth step, the coagulant is one of polymeric ferric sulfate, PAC and PAM, and the coagulant is added in an amount of 0.5-1.5g coagulant per 1L of the supernatant obtained in the fifth step.
Based on the technical scheme, in the sixth step, preferably, 0.5-1.5ml of 30% hydrogen peroxide is added into each 1L of clear liquid obtained in the fifth step, and 1-2g of ferrous sulfate is added into each 1L of clear liquid obtained in the fifth step.
Based on the above technical solution, preferably, in the seventh step, the method of adsorption purification treatment includes: and D, enabling the filtrate obtained in the step six to pass through a single resin adsorption column positively at a flow rate of 1BV/h, and regenerating every 5 hours of adsorption of the resin adsorption column.
On the basis of the above technical solution, preferably, in step seven, the method for regenerating includes: and (3) introducing 1-5kg of steam into the resin adsorption column from top to bottom for resin regeneration for 0.8-3h, extruding the evaporated condensate water in the resin adsorption column by using 0.1-0.15kg of compressed air after the regeneration is finished, and flushing the liquid obtained in the step (seven) after adsorption purification from bottom to top after the extrusion is finished, wherein the upper end water outlet is used as the filtrate obtained in the step (six).
On the basis of the technical scheme, preferably, the filler used for the resin adsorption column is ultra-high crosslinked polystyrene macroporous adsorption resin.
On the basis of the above technical solution, preferably, in step eight, the biochemical treatment method includes: and D, adding the wastewater obtained after the adsorption purification in the step seven into a hydrolytic acidification tank for hydrolysis treatment, adding the wastewater obtained after the hydrolysis treatment into an A2O biochemical tank for denitrification and dephosphorization treatment, and filtering the wastewater subjected to denitrification and dephosphorization treatment through an MBR membrane bioreactor to obtain biochemical treatment wastewater.
Based on the above technical solution, preferably, in step nine, the disinfectant is one of sodium hypochlorite and sodium citrate.
Compared with the prior art, the treatment method of the wastewater containing DMF, pyridine and pyridine derivatives has the following beneficial effects:
(1) The invention provides a wastewater treatment method capable of effectively removing DMF, pyridine and pyridine derivatives in wastewater, wherein the content of ammonia nitrogen, DMF, pyridine and pyridine derivatives is greatly reduced by adopting a blowing-off treatment mode in the process of the front-stage treatment, and simultaneously, residual harmful substances are adsorbed by utilizing a resin adsorption mode in the process of the rear-stage treatment, so that the content of ammonia nitrogen, DMF, pyridine and pyridine derivatives entering the biochemical treatment is greatly reduced, the poisoning of a biochemical treatment system is avoided, and meanwhile, most toxic and harmful organic matters and sediments are removed in the whole flow, and ammonia nitrogen and COD are deeply removed by the biochemical treatment system, so that the wastewater reaches the emission standard;
(2) The whole treatment method can also collect and intensively treat the generated waste gas, and the treatment process consumes less energy, has lower operation cost, is low-carbon and environment-friendly, and is green and free from secondary pollution.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Waste water generated in the production process of trichloromethyl pyridine is divided into three groups and treated as raw materials of examples 1, 2 and 3 respectively.
Example 1
Adding hydrochloric acid and caustic soda flakes into raw material wastewater to adjust the pH value to 6.5, transferring the adjusted wastewater into a triple-effect evaporator to perform evaporation treatment, wherein the evaporation temperature is 60 ℃, the vapor pressure is 0.5MPa, when no obvious liquid flows out, transferring evaporation condensate into a stripping tower, adding caustic soda flakes to adjust the pH value to 11, adjusting the stripping gas temperature to 0 ℃, the stripping time to 5 hours, enabling the stripping gas-liquid ratio to be 1000:1, conducting oil removal treatment on a liquid layer after the stripping, taking a middle liquid layer, removing an upper layer oil layer and a lower layer slag layer, adding the middle water layer into a cavitation air floatation device to further remove suspended matters, collecting clear liquid, adding 0.5gPAC into each 1L clear liquid to perform coagulating sedimentation, adding 1.0ml of 30% hydrogen peroxide and 1.5g ferrous sulfate into each 1L of clear liquid after sedimentation separation, stirring, reacting, precipitating, standing, separating, collecting supernatant, filtering, purifying filtrate by a resin adsorption column, wherein filler in the resin adsorption column is ultra-high crosslinked polystyrene macroporous adsorption resin, treating at a treatment rate of 1 bed volume per hour, carrying out primary regeneration treatment on the resin adsorption column after treating filtrate with 5 bed volumes, adding filtrate after column adsorption into a hydrolytic acidification tank for hydrolysis treatment, transferring wastewater after hydrolysis treatment into an A2O biochemical tank for denitrification and dephosphorization treatment, filtering wastewater after denitrification and dephosphorization treatment by an MBR membrane bioreactor to obtain treated filtrate, and adding sodium hypochlorite into the filtrate for disinfection to obtain waste liquid meeting requirements.
Example 2
Adding hydrochloric acid and caustic soda flakes into raw material wastewater to adjust the pH value to 7.0, transferring the adjusted wastewater into a triple-effect evaporator to perform evaporation treatment, wherein the evaporation temperature is 60 ℃, the vapor pressure is 0.5MPa, when no obvious liquid flows out, transferring evaporation condensate into a stripping tower, adding caustic soda flakes to adjust the pH value to 11.5, adjusting the stripping gas temperature to 25 ℃, the stripping time to 3 hours, carrying out oil removal treatment on a liquid layer through an oil removal adjusting tank after the stripping is completed, taking a liquid layer in the middle, removing an upper layer oil layer and a slag layer at the lower layer, adding an intermediate water layer into a cavitation air floatation device to further remove suspended matters, collecting clear liquid, adding 1g of polymerized ferric sulfate into each 1L of clear liquid to perform coagulating sedimentation, adding 0.5ml of 30% hydrogen peroxide and 1g of ferrous sulfate into each L of clear liquid after the sedimentation separation, stirring, reacting, precipitating, standing, separating, collecting supernatant, filtering, purifying filtrate by a resin adsorption column, wherein filler in the resin adsorption column is ultra-high crosslinked polystyrene macroporous adsorption resin, treating at a treatment rate of 1 bed volume per hour, carrying out primary regeneration treatment on the resin adsorption column after treating filtrate with 5 bed volumes, adding filtrate after column adsorption into a hydrolytic acidification tank for hydrolysis treatment, transferring wastewater after hydrolysis treatment into an A2O biochemical tank for denitrification and dephosphorization treatment, filtering wastewater after denitrification and dephosphorization treatment by an MBR membrane bioreactor to obtain treated filtrate, and adding sodium citrate into the filtrate for disinfection to obtain waste liquid meeting requirements.
Example 3
Adding hydrochloric acid and caustic soda flakes into raw material wastewater to adjust the pH value to 7.5, transferring the adjusted wastewater into a triple-effect evaporator to perform evaporation treatment, wherein the evaporation temperature is 60 ℃, the vapor pressure is 0.5MPa, when no obvious liquid flows out, transferring evaporation condensate into a stripping tower, adding caustic soda flakes to adjust the pH value to 12, adjusting the stripping gas temperature to 90 ℃, the stripping time to 2 hours, carrying out oil removal treatment on a liquid layer through an oil removal adjusting tank after the stripping is completed, taking a middle liquid layer, removing an upper layer oil layer and a lower layer slag layer, adding the middle water layer into a cavitation air floatation device to further remove suspended matters, collecting clear liquid, adding 1.5g PAM into each 1L clear liquid to perform coagulating sedimentation, adding 1.5ml30% hydrogen peroxide and 2g ferrous sulfate into each 1L filtrate after sedimentation separation, stirring, reacting, precipitating, standing, separating, collecting supernatant, purifying filtrate by a resin adsorption column, wherein filler in the resin adsorption column is ultra-high crosslinked polystyrene macroporous adsorption resin, treating at a treatment rate of 1 bed volume per hour, carrying out primary regeneration treatment on the resin adsorption column after treating filtrate with 5 bed volumes, adding filtrate after column adsorption into a hydrolytic acidification tank for hydrolysis treatment, transferring the wastewater after hydrolysis treatment into an A2O biochemical tank for denitrification and dephosphorization treatment, filtering the wastewater after denitrification and dephosphorization treatment by an MBR membrane bioreactor, obtaining treated filtrate, and adding sodium hypochlorite into the filtrate for disinfection, thereby obtaining waste liquid meeting requirements.
And detecting DMF, pyridine derivatives, COD, TOC, total nitrogen and ammonia nitrogen of the wastewater before treatment and filtrate filtered by the MBR membrane bioreactor respectively, wherein the detection results are as follows:
| detecting items | Waste water before treatment | Example 1 | Example 2 | Example 3 |
| DMF/ppm | 2357 | 67 | 54 | 55 |
| Pyridine/ppm | 1405 | 7 | 8 | 7 |
| Pyridine derivatives/ppm | 821 | 4 | 3 | 3 |
| COD/ppm | 15126 | 102 | 100 | 98 |
| TOC/ppm | 7552 | 170 | 153 | 149 |
| Total nitrogen/ppm | 229.4 | 13.54 | 11.74 | 17.70 |
| Ammonia nitrogen/ppm | 25.63 | 4.23 | 4.55 | 4.14 |
Meanwhile, the microbial contents in the sludge before and after wastewater treatment in the hydrolytic acidification tank and the A2O biochemical tank in the examples 1-3 are detected, and the detection results are as follows:
the data show that the treatment method of the invention can not influence the biological activity of the biochemical pool, effectively avoid the microbial poisoning in the biochemical pool, reduce the cost input, and is more green and pollution-free.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method for treating wastewater containing DMF, pyridine and pyridine derivatives is characterized by comprising the following steps:
step one, adding a pH regulator into wastewater containing DMF, pyridine and pyridine derivatives to regulate the pH, so as to obtain regulated wastewater;
step two, adding the wastewater obtained in the step one into a triple-effect evaporator for evaporation to obtain evaporation condensate for removing part of organic matters;
step three, carrying out stripping treatment on the evaporation condensate obtained in the step two to obtain stripped wastewater;
step four, adding the blown-off wastewater obtained in the step three into an oil removal regulating tank for oil removal treatment, and collecting a water layer to obtain oil-removed wastewater;
step five, adding the wastewater obtained after oil removal in the step four into a cavitation air floatation device to remove suspended matters, and collecting clear liquid;
sequentially adding a coagulant, 30% hydrogen peroxide and ferrous sulfate into the clear liquid obtained in the step five, carrying out solid-liquid separation after coagulation and flocculation precipitation reaction, collecting the supernatant and filtering to obtain filtrate;
step seven, adsorbing and purifying the filtrate obtained in the step six by using adsorption resin, and collecting the liquid after adsorption and purification;
step eight, adding the liquid obtained after adsorption purification in the step seven into a biochemical treatment system for biochemical treatment to obtain biochemical treatment wastewater;
step nine, performing solid-liquid separation on the biochemical treatment wastewater obtained in the step eight by using an MBR system, taking filtrate, adding disinfectant into the filtrate for disinfection, and discharging after reaching the standard through detection;
in the sixth step, the dosage of the 30% hydrogen peroxide is that 0.5-1.5ml of 30% hydrogen peroxide is added into each 1L of clear liquid obtained in the fifth step, and the dosage of the ferrous sulfate is that 1-2g of ferrous sulfate is added into each 1L of clear liquid obtained in the fifth step;
forward passing the filtrate obtained in the step six through a single resin adsorption column at a flow rate of 1BV/h, and regenerating the resin adsorption column once every 5 hours of adsorption;
in step seven, the method for regenerating includes: and (3) introducing 1-5kg of steam into the resin adsorption column from top to bottom for resin regeneration, wherein the regeneration time is 0.8-3h, extruding evaporating condensed water in the resin adsorption column by using 0.1-0.15kg of compressed air after the regeneration is finished, and flushing the liquid obtained in the step (seven) after adsorption purification from bottom to top after the extrusion is finished, wherein the upper end water outlet is used as the filtrate obtained in the step (six).
2. The method for treating wastewater containing DMF, pyridine and pyridine derivatives according to claim 1, wherein in the first step, the pH regulator comprises sodium hydroxide and hydrochloric acid, and the pH value of the wastewater after the regulation is 6.5-7.5.
3. The method for treating wastewater containing DMF, pyridine and pyridine derivatives according to claim 1, wherein the third step further comprises: adding sodium hydroxide into the wastewater obtained in the step two, removing part of organic matters, adjusting the pH value to 11-12, and then carrying out stripping treatment, wherein the stripping treatment temperature is 0-90 ℃, the stripping time is 2-5h, and the stripping gas-liquid ratio is (1000-3000): 1.
4. the method for treating wastewater containing DMF, pyridine and pyridine derivatives according to claim 1, wherein in the sixth step, the coagulant is one of polymeric ferric sulfate, PAC and PAM, and the coagulant is added in an amount of 0.5-1.5g per 1L of the clear solution obtained in the fifth step.
5. The method for treating wastewater containing DMF, pyridine and pyridine derivatives according to claim 1, wherein the filler used in the resin adsorption column is ultra-high crosslinked polystyrene macroporous adsorption resin.
6. The method for treating wastewater containing DMF, pyridine and pyridine derivatives according to claim 1, wherein in the eighth step, the biochemical treatment method comprises: and D, adding the wastewater obtained after the adsorption purification in the step seven into a hydrolytic acidification tank for hydrolysis treatment, adding the wastewater obtained after the hydrolysis treatment into an A2O biochemical tank for denitrification and dephosphorization treatment, and filtering the wastewater subjected to denitrification and dephosphorization treatment through an MBR membrane bioreactor to obtain biochemical treatment wastewater.
7. The method for treating wastewater containing DMF, pyridine and pyridine derivatives of claim 1, wherein in step nine, the disinfectant is one of sodium hypochlorite and sodium citrate.
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| CN107673571A (en) * | 2017-12-04 | 2018-02-09 | 湖南大辰环保科技有限公司 | DMF comprehensive treatment method for wastewater and system in a kind of film production |
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| CN107673571A (en) * | 2017-12-04 | 2018-02-09 | 湖南大辰环保科技有限公司 | DMF comprehensive treatment method for wastewater and system in a kind of film production |
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