CN114644425A - Treatment method of cellulose ether industrial wastewater with high salt content and high COD value - Google Patents
Treatment method of cellulose ether industrial wastewater with high salt content and high COD value Download PDFInfo
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- CN114644425A CN114644425A CN202011521675.2A CN202011521675A CN114644425A CN 114644425 A CN114644425 A CN 114644425A CN 202011521675 A CN202011521675 A CN 202011521675A CN 114644425 A CN114644425 A CN 114644425A
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- 238000011282 treatment Methods 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims abstract description 99
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- 239000010842 industrial wastewater Substances 0.000 title claims description 9
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- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
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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
- C02F1/02—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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- 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
- C02F2103/38—Polymers
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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
- C02F3/28—Anaerobic digestion processes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A method for treating cellulose ether enterprise process wastewater with high salt content and high COD value comprises (A) diluting by adding water into wastewater in a wastewater adjusting tank and adjusting pH value; (B) hydrolytic acidification of the wastewater; (C) anaerobic treatment of the wastewater; (D) aerobic treatment; (E) chemical advanced treatment; (F) filtering by using a plurality of media; (G) ultrafiltration; (H) reverse osmosis or electrodialysis; (I) and (3) evaporating and crystallizing the obtained concentrated water to obtain sodium chloride salt which reaches or is superior to the national standard of industrial salt, and obtain fresh water which reaches or is superior to the standard of surface three types of water, wherein one part of the fresh water is circulated into the wastewater regulating tank in the step (A), and the rest part of the fresh water can be used as industrial water or civil water for enterprises. Thus, the purpose of recycling the waste water in the industry can be achieved.
Description
Technical Field
The invention relates to a method for treating industrial wastewater with high salt content and high COD value, in particular to a method and a system for treating cellulose ether industrial wastewater with high salt content and high COD value.
Background
Hydroxypropyl methyl cellulose ether is a high-polymerization cellulose ether prepared by taking cellulose, caustic soda, chloromethane and epoxypropane as main raw materials, is called HPMC for short, has a molecular weight of millions, is a macromolecular organic matter, and is widely applied to the industries of buildings, coatings, plastics and the like. A large amount of high-concentration and high-salinity organic chemical wastewater is generated in the production process, and the wastewater contains macromolecular substances such as methyl cellulose, cellulose and hydroxypropyl cellulose and also contains micromolecular substances such as propylene oxide, chloromethane, toluene and inorganic salt. The wastewater has the characteristics of high COD (chemical oxygen demand) content, high salt content, poor biodegradability and great harm to the environment, and if the wastewater is directly discharged without being treated, the wastewater brings serious harm to the ecological environment.
These enterprises producing hydroxypropyl methyl cellulose ether have generally dedicated research, development, production and sale of water-soluble high molecular compounds, and the main products are nonionic cellulose ethers, which have the capability of autonomously developing and producing middle and high-end model building material-grade, pharmaceutical-grade and food-grade nonionic cellulose ethers.
CN203319823U discloses a cellulose ether wastewater treatment device, which comprises: a regulating tank, a micro-electrolysis tank, an oxidation tank, a sedimentation tank, a hydrolysis acidification tank, an up-flow anaerobic sludge bed reactor, a sequential intermittent activated sludge tank and an aeration biological filter.
CN102344225B discloses a method for treating salt-containing wastewater in cellulose ether production, 1. desalination of brine: carrying out triple effect evaporation on the washing wastewater of the salt-containing cellulose ether product, separating crystallized salt and insoluble organic matters, and roasting the separated salt and insoluble organic matters to obtain industrial salt; 2. anaerobic treatment of wastewater: carrying out anaerobic treatment on the separated mother liquor, wherein the anaerobic treatment can be upflow anaerobic sludge blanket anaerobic treatment; 3. aerobic treatment of wastewater: the wastewater is subjected to A/O contact oxidation treatment, Fenton reagent (Fenton reagent) treatment and contact oxidation treatment in sequence.
CN106746198B discloses an integrated treatment method of high-salt high-concentration refractory organic wastewater for producing cellulose ether, 1, pretreating wastewater to be treated by coagulating sedimentation and Fenton reaction in sequence; 2. performing biochemical treatment on the Fenton reaction effluent sequentially through cellulose hydrolysis, anaerobic treatment, primary contact oxidation and secondary contact oxidation; adding cellulase in the hydrolysis process of cellulase to degrade the wastewater, and adding a salt-tolerant microbial inoculum for producing cellulase in the anaerobic treatment, the primary contact oxidation and the secondary contact oxidation processes to strengthen the treatment of the wastewater; 3. performing advanced treatment on the secondary contact oxidation effluent through Fenton reaction, and finally discharging; the biochemical treatment process is carried out in a cellulase hydrolysis tank, an anaerobic tank, a primary contact oxidation tank and a secondary contact oxidation tank in sequence, combined fillers are added into the anaerobic tank, the primary contact oxidation tank and the secondary contact oxidation tank, inoculated activated sludge is a salt-tolerant microbial inoculum for producing cellulase, cellulase is added into the cellulase hydrolysis tank, and DO in the primary contact oxidation tank and the DO in the secondary contact oxidation tank are controlled to be 3-4 mg/L.
CN110451727A discloses a method for treating wastewater in cellulose ether production: 1. pretreatment of wastewater: filtering solid impurities with larger volume in the wastewater by a filter screen, depositing the filtered wastewater on a separation membrane, slowly separating, and allowing the filtered and separated wastewater to flow into the bottom of a pretreatment tank (S1); 2. biological treatment of wastewater by an anaerobic method: pumping the wastewater filtered and separated from the bottom of the pretreatment tank into an anaerobic biological treatment tank, adding anaerobic bacteria liquid into the anaerobic biological treatment tank, sealing the top of the anaerobic biological treatment tank, and pumping out air in a cavity at the top of the wastewater (S2); 3. anaerobic management: starting a stirring mechanism to fully mix the wastewater with the anaerobic bacteria, stirring once every 1-2h for 15-20min, maintaining the anaerobic environment of the anaerobic biological treatment tank, treating for 3-5 days, and then opening a cover for inspection (S3); 4. aerobic biological treatment of wastewater: pumping the wastewater into an aeration tank, adding aerobic bacteria liquid, stirring and aerating to enable aerobic bacteria in the wastewater to fully obtain oxygen for wastewater treatment, wherein the aerobic treatment lasts for 6-8 days (S4); 5. and (3) sterilization and disinfection treatment of wastewater: and (S5) injecting the wastewater after the aerobic treatment into a disinfection tank, and adding a disinfectant for sterilization and disinfection treatment.
However, the prior art treatment method can not achieve ideal purification effect on wastewater with high salt content and high COD value in cellulose ether production, especially wastewater containing fluorine and silicon, and the treatment cost is too high.
Disclosure of Invention
Raw (raw) waste water (W) from cellulose ether production0) Containing both organic compounds and hardly degradable organic polymers, especially waste water (W)0) The content of sodium chloride in the condensate is 5-15 wt%, and the COD content in the condensate is high by evaporation and desalination separation, and the content of organic matters in the crystallized salt is high, so that the post-treatment difficulty is high, the generated salt is dangerous waste, and the treatment cost is higher. If a membrane separation process is adopted, experiments show that the COD removal rate is only 40% and a better separation effect cannot be achieved when a 10nm tubular ultrafiltration membrane is adopted for separation experiments.
Generally, raw waste water (W)0) The content of the main ions in the formula is as follows: na (Na)+The content is 2.5-14.5 wt%, i.e., 25000-145000ppm (mg/L), preferably 2.6-14 wt%, preferably 2.7-13 wt%, preferably 2.8-12 wt%, preferably 2.9-11 wt%, preferably 3-10 wt%, such as 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt% or 9.5 wt%; cl-The content is 2.5-16.5 wt%, i.e. 25000-165000ppm, preferably 2.7-16 wt%, preferably 2.9-15.5 wt%, preferably 3-15 wt%, such as 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt% or 14 wt%.
In addition, raw wastewater (W)0) The medium Chemical Oxygen Demand (COD) and TDS (dissolved total solids, i.e., soluble salts) are each independently 3-17 wt%, i.e., 30000-170000ppm (mg/L). Preferably, raw waste water (W)0) The medium COD value is from 5 to 15 wt%, more preferably from 6 to 14 wt%, more preferably from 7 to 13 wt%, for example 8, 9, 10, 11 or 12 wt%.
In addition, raw wastewater (W)0) Total hardness of medium calcium magnesium (Ca)2++Mg2+) Is 150ppm or more or 180ppm, for example 150ppm to 3000ppm, preferably 300-2500ppm, more preferably 350-2000ppm, such as 500, 800, 1000,1200 or 1500 ppm; f-In an amount of 1ppm or more, for example 1ppm to 150ppm, such as 4 or 6 or 20 or 40 or 100 ppm; in this type of raw wastewater (W)0) SiO 23 2-(+ optional SiO)4 4-) Is generally greater than or equal to 3ppm, for example from 3ppm to 350ppm, such as 5, 12, 20, 50, 150 or 300 ppm.
The waste water from cellulose ether production is raw (raw) waste water (W) with high salt content and high COD value0) Typically contain complex contaminant components and are often collected in catch basins and conditioning distribution basins on the plant area. In the adjusting distribution tank, adjusting water (W) in the adjusting distribution tank is performed by adjusting the pH value of the wastewater and adding dilution water1) Has a COD of less than 3000mg/L and a TDS of less than 30000 mg/L.
In addition, the wastewater (W) to be treated in the distribution reservoir is regulated1) Not only contains Ca2+And Mg2+Also containing heavy metal cations, e.g. Fe3+，Fe2+，Cu2+，Ni2+,Cd2+,Zn2+,Hg+,Hg2+，Cr3+,Pb2+,Mn2+And so on. Furthermore, such waste water (W)1) Often contain organic compounds and refractory organic polymers (COD), and such waste waters may also contain ammonia-nitrogen impurities (e.g. NH)4 +). In addition, such waste water may contain arsenic (arsenate AsO)4 3-Arsenite AsO3 3-) And, such wastewater may also contain TP total phosphorus (e.g., PO)4 3-Or organophosphorus) (total P content)>0.5 ppm). In addition, such waste water may contain F- (in its content)>1ppm)，SO4 2-，S2-(content thereof)>1ppm)，SiO4 4-,SiO3 2-，PO4 3-，CO3 2-，HCO3 -And (3) plasma anions.
In the present application, a 1ppm content or concentration is 1mg/L content or concentration.
In addition, the wastewater (W) to be treated in the distribution reservoir is regulated1) Is independently of each other<30000mg/L, exampleSuch as 8000mg/L to 30000mg/L (i.e. 0.8 to 3 wt%), preferably 10g/L to 29g/L, such as 12, 15, 18, 20, 22, 23, 25, 26 or 28 g/L. In addition, the waste water (W) to be treated1) Total hardness of medium calcium magnesium (Ca)2++Mg2+) Typically 50ppm or more, for example 50 to 1500ppm, preferably 80ppm to 1300ppm, such as 100, 300, 500, 700, 900, 1000 or 1200 ppm; f-At a level of 1ppm or more, for example 1ppm to 70ppm, such as 4, 6, 12, 20, 30, 35, 40 or 50 ppm; in the waste water (W) to be treated1) SiO 23 2-+SiO4 4-Is generally greater than or equal to 3ppm, for example from 3ppm to 200ppm, such as 5, 10, 15, 20, 30, 40, 50, 60, 70, 90, 100, 120, 150 or 180 ppm. In addition, the Total Phosphorus (TP) content is generally ≧ 0ppm, e.g., 0ppm, or 0.1-100 ppm, such as 1, 4, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80 or 90 ppm. In addition, it is possible to treat the waste water (W) to be treated1) Middle Fe3+，Fe2 +，Cu2+，Ni2+,Cd2+,Zn2+,Hg+,Hg2+，Cr3+,Pb2+Or Mn2+The amount of each heavy metal cation in the composition is 1ppm or more, for example 1ppm to 20ppm, such as 2, 5, 8, 10, 12 or 15 ppm. In addition, it is possible that ammonia Nitrogen (NH)3N) in an amount of 0.2ppm or more, for example 0.2 to 100ppm, such as 1, 5, 20, 30, 40, 50, 60 or 70 or 80 ppm. It is possible that S2-The content is ≥ 0ppm or 0.2ppm, for example 0.2-40ppm, such as 2 or 10 or 20 ppm. It is possible that the AsO4 3-+AsO3 3-The content is ≥ 0 or 0.2ppm, for example 0.2-30ppm, such as 2, 7, 15, 20 or 25 ppm. In addition, SO4 2-The content is 40-500ppm, preferably 50-470ppm, such as 70, 90, 120, 150, 180, 200, 250, 300, 350, 400 or 450 ppm. In addition, CO3 2-In an amount of 50-1200ppm, such as 70, 100, 200, 300, 500, 600, 700, 800, 900 or 1000 ppm.
In the multiple treatment steps of the wastewater, the mutual interference effect of more types of the pollution components (impurities) exists, and the separation and purification effects of the wastewater are influenced. For example, organic macromolecular impurities (COD) often coat or complex the aboveHeavy metal ions and anions, and in addition, metal ions also interfere with each other in each step in the purification treatment method of wastewater. Due to the strong hydrogen bonding between the HF molecules and the fact that the concentration of certain cations in the wastewater is not too high, a portion of the HF in the wastewater is often present in the form of aggregates or associations "(HF) n", which do not necessarily have to be associated with the free Ca contained in the wastewater2+Ion formation of CaF2And (4) precipitating. Also, Silicate Ion (SiO)3 2-Or SiO4 4-) Also as aggregates or associated complexes (H)2SiO3) n and (H)4SiO4) n is not necessarily present in combination with free Ca contained in the waste water2+The ions form calcium orthosilicate or calcium metasilicate precipitates. Phosphate radical (PO) like silicate radical4 3-) It is also possible to form aggregates or associations (H)3PO4) n is not necessarily present in combination with free Fe contained in the waste water3+Ion formation of precipitate (Fe)3++PO4 3-→FePO4). In addition, anions, water (or OH) in the wastewater-Or NH3) With certain heavy metal cations (e.g. Cu)2+、Cd2+,Hg2+，Cr3+) It is possible to form complexes, and therefore, these heavy metal cations do not necessarily form precipitates with specific anions. The term "aggregate" or "association" as used herein is also considered to be equivalent to "aggregate". The above-mentioned impurities of fluorine, silicon and phosphorus species easily clog a porous filtration membrane such as an ultrafiltration membrane or a reverse osmosis membrane.
On the one hand, in general, the above-mentioned waste water may contain toxic heavy metals such as cadmium, chromium, mercury and arsenic, etc., and may contain fluorine, silicon and phosphorus elements (for example, F present in the waste water)-Silicate or phosphate tends to clog the pores of the filtration membrane because these anions form hard "fouling" precipitates with cations such as calcium and magnesium ions) and thus, such wastewater is a type of wastewater that is difficult to treat. On the other hand, environmental regulations are applied to the heavy metal content of water discharged to the environment and obtained after wastewater is purified,The fluorine content is also very critical.
In order to treat the wastewater, the invention provides a method for treating the wastewater containing fluorine and silicon impurities (such as F)-The content is more than or equal to 1ppm, even F-The content is more than or equal to 2ppm or more than or equal to 3 ppm; and SiO4 4-+SiO3 2-A content of more than or equal to 2ppm, even more than or equal to 3ppm or more than or equal to 4 ppm). The invention aims to provide a zero-emission wastewater treatment process and a zero-emission wastewater treatment system.
Since the flow rate of wastewater containing fluorine and silicon impurities to be treated is large, the fluorine and silicon impurities in the wastewater are very likely to block the pores of various filtration membranes (such as ultrafiltration membranes, reverse osmosis membranes and electrodialysis membranes), and therefore, the purification treatment of wastewater containing high content of fluorine and silicon impurities is a difficult technical problem to solve.
The inventors of the present application have found that most of fluorine and silicon-based impurities in wastewater can be removed by a combination of a biochemical treatment process and an electrochemical treatment process using a double anode (combined anode or composite anode) containing iron and/or aluminum.
In addition, the inventors have found that the combined use of these two processes also desirably removes most of the heavy metals, but also most of the other deleterious anions (e.g., phosphate, arsenate and S)2-) At the same time, it is also possible to additionally (or incidentally) remove a portion of the other "hardness" cations (e.g. calcium, magnesium ions).
Firstly, in the biochemical treatment process, the wastewater to be treated is subjected to at least two biochemical treatment processes including an anaerobic zone (zone) and an aerobic zone in sequence. Wherein the main function of the anaerobic segment is denitrification by denitrification of microorganisms [ e.g. heterotrophic bacteria ammoniate contaminants such as proteins, fats (N in the organic chain or amino groups in amino acids) to free ammonia (NH)3、NH4 +) While the denitrification of the heterotrophic bacteria produces NO3 -Reduced to molecular nitrogen (N)2)]Simultaneously hydrolyzing macromolecular organic matters; the aerobic section is used for removing organic matters in water and simultaneously removing ammonia nitrogen through the nitrification of microorganisms[ nitrification of autotrophic bacteria to react NH3-N(NH4 +) Oxidation to NO3 -]. Anaerobic treatment and aerobic treatment degrade or decompose most COD (namely organic impurities) contained in the wastewater to expose or keep heavy metal ions or anions in a free state, so that the problem that the heavy metal ions and the anions are wrapped or complexed by the organic impurities in the wastewater purification method in the prior art is solved.
Secondly, (HF) n, (H) in the form of aggregates or associations under the action of an electric field during electrochemical decontamination using a double anode (combined anode or composite anode) comprising iron and/or aluminium4SiO4)n、(H2SiO3) n or (H)3PO4) n is dissociated or ionized, a specific anion (e.g. F)-、SiO3 2-、PO4 3-Or AsO4 3-) Form a precipitate with the corresponding heavy metal cation. The current action between the polar plates can change the molecular aggregation state of silicon dioxide, silicic acid (radical) and fluoride compounds in the waste water to make SiO2Silicic acid radical, F-The plasma is combined with the calcium and magnesium ions to precipitate and coprecipitate, thereby reducing SiO2Silicic acid radical, F-And the indexes of pollutants are equal.
The electrode reactions in the cell are as follows:
anode: fe-2e-→Fe2+
2H2O-4e-→O2+4H+
2Cl-→Cl2+2e
MOX+H2O→MOX(HO·)+H++e-(direct Oxidation reaction)
In the formula MOXRepresents a metal oxide
Cathode: 2H2O+2e-＝H2+2OH-(direct reduction reaction)
The following reactions take place in solution: for example
Ca2++HCO3 -+OH-→CaCO3↓+H2O
Mg2++2OH-→Mg(OH)2↓
Fe3++3OH-→Fe(OH)3↓
Cu2++2OH-→Cu(OH)2↓
Ni2++2OH-→Ni(OH)2↓
Cd2++2OH-→Cd(OH)2↓
Zn2++2OH-→Zn(OH)2↓
Fe3++PO4 3-→FePO4↓
Mn2++2OH-→Mn(OH)2↓
Ca2++2F-→CaF2↓
2Ca2++SiO4 4-→Ca2SiO4↓
Ca2++SiO3 2-→CaSiO3↓
Mg2++SiO3 2-→MgSiO3↓
Cr3++AsO4 3-→CrAsO4↓
Hg2++S2-→HgS↓
Pb2++2OH-→Pb(OH)2↓
Thirdly, using a sacrificial anode and an inert anode as a combined anode or using a ferrotitanium alloy, an aluminum-titanium alloy or a ferroaluminum-titanium alloy as a composite anode in an electrochemical treatment tank, and using iron ions and/or aluminum ions in the wastewater as or to form a flocculating agent or a flocculating substance; on the one hand, the flocculant is beneficial to the agglomeration and flocculation of inorganic salt precipitates and small particles of organic matters (COD), and on the other hand, the flocculant promotes the further agglomeration and sedimentation of particulate matters in wastewater. In addition, Fe produced3+Ions or Al3+The ions also facilitate removal of phosphate by forming a precipitate. Can also form in the electrochemical treatment cell[FeF6]3-And [ AlF6]3-Ions, which settle by flocculation or are adsorbed by activated carbon in a subsequent stage.
Fourth, the inventors of the present application found through experimentation that chlorine-containing oxidants (i.e.: Cl, Cl) were generated in situ (in situ) in the wastewater2And/or hypochlorite) is much higher than the chlorine-containing oxidizing agent (Cl) added in the waste water2Gas or hypochlorite), and thus the high oxidation activity of the former can oxidize COD impurities (e.g., ammonia nitrogen impurities, some inorganic anions or cations that can be oxidized, and organic impurities, etc.) as impurities that are difficult to be (sufficiently) oxidized, decomposed, or degraded in the previous biochemical treatment. In particular, during electrolysis (i.e., electrochemical treatment), highly active free chlorine and hypochlorite are generated in situ (in situ) in the wastewater, with much higher oxidation activity than Cl2(or added Cl)2) Oxidatively decomposable linear, branched or cyclic paraffinic organic compound (i.e., non-aromatic hydrocarbon organic compound) or derivative thereof (e.g., C)1-C7Linear alkylcarboxylic acids), benzene and other aromatic and heteroaromatic compounds, and also ammonia nitrogen to nitrogen.
Therefore, the invention can remove most of fluorine and silicon impurities at low cost and with high efficiency, and the impurities are difficult to remove by the wastewater treatment method in the prior art. Meanwhile, the total hardness (calcium and magnesium) in the wastewater is greatly reduced. Although the prior art wastewater treatment methods employ more treatment steps, it is still difficult to effectively remove fluorine and silicon impurities, and in addition, the removal of ammonia nitrogen impurities, inorganic salts (in the form of precipitates and/or flocs) and COD (i.e., organic impurities) is unsatisfactory.
In the present application, various wastewaters from various segments of cellulose ether production facilities (including domestic washing water of plant areas) are collected in a conditioning tank to form raw wastewaters or raw wastewaters, and these wastewaters or wastewaters to be treated are subjected toReferred to as raw (raw) waste water or raw (raw) waste water (W)0)。
According to a first embodiment of the present invention, there is provided a method for treating cellulose ether industrial wastewater having a high salt content and a high COD value, the method comprising:
(A) process waste water (W) from cellulose ether production enterprises0) Is conveyed into a regulating distribution reservoir (1) and diluted by adjusting the pH value and adding water to obtain wastewater to be treated (W1) with a total dissolved solids content (TDS) of less than 30000mg/L (e.g. 8-30g/L, such as 10, 12, 15, 18, 20, 23, 24, 25, 26 or 27 g/L);
(B) conveying the wastewater (W1) to be treated in the adjusting distribution tank (1) to a hydrolysis acidification tank (2) for preliminary anaerobic fermentation;
(C) the wastewater flowing out of the hydrolytic acidification tank (2) is conveyed into a primary anaerobic fermentation tank (3) for primary anaerobic fermentation;
(D) the wastewater flowing out of the primary anaerobic fermentation tank (3) is conveyed into a secondary anaerobic fermentation tank (4) for secondary anaerobic fermentation;
(E) the wastewater (W2) flowing out of the secondary anaerobic fermentation tank (4) is conveyed into a primary aerobic aeration tank (5) for primary aerobic biochemical treatment;
(F) the wastewater flowing out of the primary aerobic aeration tank (5) is conveyed into a secondary aerobic aeration tank (6) for secondary aerobic biochemical treatment;
(G) the wastewater (W3) flowing out of the secondary aerobic aeration tank (6) is conveyed to a chemical advanced treatment system (7) for chemical advanced treatment;
(H) filtering the wastewater (W4) flowing out of the chemical advanced treatment system (7) through a multi-media filter (8) to obtain primary purified wastewater (W5);
(I) carrying out ultrafiltration on the primary purified wastewater (W5) by an ultrafiltration system (9) to obtain secondary purified wastewater (W6);
(J) concentrating the secondary purified wastewater (W6) by a reverse osmosis membrane or electrodialysis device (10) to obtain fresh water and concentrated water; and
(K) and (D) evaporating and crystallizing the concentrated water obtained in the step (J) by using an evaporation desalting device (11) to respectively obtain industrial salt sodium chloride and evaporation condensed water.
Wherein, the COD value of the fresh water obtained by the reverse osmosis treatment is between 5 and 15mg/L (such as 5 to 10), and the TDS value is less than 500mg/L or less than 200 mg/L. The industrial salt sodium chloride obtained by evaporation and crystallization is a high-quality industrial salt product with the NaCl purity of more than 99 percent.
Preferably, the fresh water from step (J) and, optionally, the evaporated condensate from step (K) are recycled to the conditioning cut-off tank for use as dilution water.
Preferably, a major portion (e.g., greater than 50 wt%, such as 55-95 wt%, preferably 60-90 wt%, more preferably 65-85 wt%) of the sludge collected from the primary anaerobic fermentation tank (3) and the secondary anaerobic fermentation tank (4). In addition, a major portion (e.g., more than 50 wt%, such as 55 to 95 wt%, preferably 60 to 90 wt%, more preferably 65 to 85 wt%) of the sludge collected from the primary aerobic aeration tank (5) and the secondary aerobic aeration tank (6) is sent to the sludge concentration tank (13).
Preferably, a part of the sludge (for example, 5 to 45 wt% or 10 to 40 wt% or 15 to 35 wt% of the sludge) collected from the primary anaerobic fermentation tank (3) and the secondary anaerobic fermentation tank (4) is refluxed to the hydrolysis acidification tank (2), the primary anaerobic fermentation tank (3) and/or the secondary anaerobic fermentation tank (4).
Preferably, a part of the sludge (for example, 5 to 45 wt% or 10 to 40 wt% or 15 to 35 wt% of the sludge) collected from the primary aerobic fermentation tank (5) and the secondary aerobic fermentation tank (6) is returned to the primary aerobic fermentation tank (5) and/or the secondary aerobic fermentation tank (6).
Generally, in step (A), process waste water (W) from cellulose ether production facilities0) Is conveyed into a regulating distribution pool (1) and diluted by regulating the pH value and adding water to obtain the wastewater (W1) with the Total Dissolved Solids (TDS) lower than 30000mg/L and the COD value lower than 30000 mg/L. The TDS and COD values are each independently 8-30g/L, such as 10, 12, 15, 18, 20, 23, 24, 25, 26 or 27 g/L.
Typically, the aerobic bacteria used in the aerobic section include one or more of Escherichia coli, Bacillus subtilis, Pichia pastoris, Aspergillus niger and Penicillium chrysogenum. In addition, the anaerobic bacteria used in the anaerobic zone are bifidobacteria and/or clostridium butyricum.
Preferably, heterotrophic bacteria are also used in both the anaerobic and aerobic sections, the heterotrophic bacteria including rhizopus and/or penicillium. In addition, autotrophic bacteria including facultative autotrophic rhizobia, thiobacillus ferrooxidans, thiobacillus thiooxidans or alcaligenes eutrophus are also used in the anaerobic zone.
In general, the chemical deep treatment in the chemical deep treatment system (7) is one or more of the following processes: ozone oxidation process, electrochemical process, chemical catalytic oxidation process, Fenton process or chemical specific medicament treatment process; preferably, the COD removal rate of the influent water of the chemical advanced treatment process section is 30-40% of the COD of the influent water after the influent water is treated by the chemical advanced treatment process section.
Through the treatment, the obtained purified water can be discharged up to the standard.
Preferably, the chemical depth treatment in the chemical depth treatment system (7) is an electrochemical process comprising electrochemically treating the effluent (W3) from the secondary aerobic aeration tank (6) in the chemical depth treatment system (7) comprising an electrochemical treatment tank by applying a direct current voltage between the combined anode or composite anode and cathode to remove ammonia nitrogen impurities, inorganic salts and COD, thereby obtaining a primary purified effluent (W4).
In general, a sacrificial anode and an inert anode are used as a combined anode in an electrochemical treatment cell or an alloy material containing a sacrificial metal and an inert metal is used as a composite anode, and the content or concentration of alkali metal chlorides (e.g., NaCl and KCl) in wastewater (W3) in the electrochemical treatment cell is sufficient to enable in-situ (in situ) generation of highly active chlorine-containing oxidants in wastewater (W3) under application of a direct current voltage between the above-mentioned anode and cathode [ i.e.: cl, Cl2And/or hypochlorite (or salt thereof)]。
In general, a voltage (V) applied between an inert anode or a composite anode and a cathode as an electrode pair by a DC power supply is used1) Sufficient to enable the generation of highly active chlorine-containing oxidants in situ (in situ) in the wastewater (W3) [ i.e.: cl, Cl2And/or hypochlorite (or salt thereof)]And optionallyOxygen-containing oxidizing agents of (i.e.,. O,. OH and O)2) (when the content or concentration of chloride ions in the wastewater is low, oxygen with lower activity is generated in the electrolysis process), and simultaneously, a voltage (V) is applied between a sacrificial anode or a composite anode as an electrode pair and a cathode by a direct current power supply2) Sufficient to cause the elemental metal of the sacrificial or composite anode (as oxidized) to lose electrons and enter the wastewater (W3) in the form of metal cations that form or act as flocculants in the wastewater contained within the electrochemical treatment cell. Wherein the voltage (V)1) And voltage (V)2) The same or different.
Preferably, the wastewater (W) in the electrochemical treatment cell3) The NaCl + KCl content is between 8g/L and 30g/L, preferably between 10g/L and 29g/L, preferably between 12g/L and 28g/L, for example 13, 15, 18, 20, 22, 23, 24, 25 or 26 g/L. More preferably from 15g/L to 25g/L, still more preferably from 18g/L to 23 g/L.
Generally, in step (G), an inorganic base (e.g., Na) is added to the wastewater (W3)2CO3And/or NaOH) for conditioning waste water (W)3) To a pH of 7.2 to 13.5, preferably in the range of 9 to 13.2, more preferably in the range of 10 to 13, more preferably 10.5 to 12.5, more preferably 11 to 12, to wastewater (W)3) And carrying out electrochemical treatment.
Preferably, the direct voltage (V)1) Or (V)2) Is between 5 and 100V, preferably between 7 and 70V, more preferably between 10 and 36V.
Preferably, the current density between the anode and the cathode is 10mA/cm2To 60mA/cm2Preferably between 12mA/cm2To 55mA/cm2More preferably between 14mA/cm2To 50mA/cm2In the meantime.
Preferably, plate-like anodes and plate-like cathodes are used in the electrochemical treatment cell.
Preferably, in step (G), the wastewater (W) in the electrochemical treatment cell is conditioned3) At the pH of (A) and in the wastewater (W)3) With or without the addition of additionally water-soluble calcium salts and/or water-soluble magnesium salts (preferably magnesium chloride):
maintaining the total hardness of the effluent of the electrochemical treatment tank to be higher than 80 mg/L; and/or
Waste water (W)3) Middle Ca2+And F-Is equal to or greater than 1, preferably equal to or greater than 1.5, preferably equal to or greater than 2, preferably equal to or greater than 2.5; and/or
Waste water (W)3) Medium Mg2+With SiO3 2-Is 1.5 or more, preferably 2 or more, preferably 2.5 or more, preferably 3 or more, preferably 3.5 or more.
Preferably, in the electrochemical treatment tank, the wastewater (W)3) The concentration of the medium electrolyte is between 0.02mol/L and 0.6mol/L, preferably between 0.035mol/L and 0.5mol/L, preferably between 0.05mol/L and 0.4mol/L, more preferably between 0.06mol/L and 0.3mol/L, more preferably between 0.08mol/L and 0.2 mol/L.
Preferably, iron or aluminum or an iron-aluminum alloy is used as the sacrificial anode when a sacrificial anode and an inert anode are used as the combined anode, or an iron-titanium alloy, an aluminum-titanium alloy or an iron-aluminum-titanium alloy is used as the composite anode when an alloy material containing a sacrificial metal and an inert metal is used as the composite anode.
Generally, a plurality of anodes and a plurality of cathodes are alternately arranged or arranged in pairs in the electrochemical treatment cell, or the electrodes are arranged in the electrochemical treatment cell in a set of 2 anodes and 1 cathode.
Preferably, a filler or three-dimensional filler is placed between the anode and the cathode in the electrochemical treatment cell; and/or, waste water (W) to the electrochemical treatment cell3) In which a coagulant aid or flocculant, such as polyacrylamide, is added.
Preferably, the multi-media filter (8) is a multi-media filter comprising a quartz sand filter layer; and/or the ultrafiltration system (9) is a ceramic membrane ultrafiltration device, more preferably a ceramic flat sheet membrane ultrafiltration device.
Generally, the waste water (W) to be treated1) Is 8000mg/L to 30000mg/L, preferably 10g/L to 29g/L, such as 12, 15, 18, 20, 22, 23, 24, 25, 26/27 or 28 g/L. In addition, the waste water (W) to be treated1) Total hardness of medium calcium magnesium (Ca)2++Mg2+) From 50 to 1500ppm, preferably from 80ppm to 1300ppm, such as 100,300. 500, 700, 900, 1000 or 1200 ppm.
Preferably, in the waste water (W) to be treated1) In (F)-The content is 1 ppm-70 ppm, such as 4, 6, 12, 20, 30, 35, 40 or 50 ppm. SiO 23 2-+SiO4 4-Is present in an amount of 3ppm to 200ppm, such as 5, 10, 15, 20, 30, 40, 50, 60, 70, 90, 100, 120, 150 or 180 ppm. The Total Phosphorus (TP) content is 0ppm or 0.1-100 ppm, such as 1, 4, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80 or 90 ppm.
Preferably, in the waste water (W) to be treated1) Medium ammonia Nitrogen (NH)3N) in an amount of 0.2 to 100ppm, such as 1, 5, 20, 30, 40, 50, 60 or 70 or 80 ppm. In addition, SO4 2-The content is 40-500ppm, preferably 50-470ppm, such as 70, 90, 120, 150, 180, 200, 250, 300, 350, 400 or 450 ppm.
In addition, in the waste water (W) to be treated1) Middle Fe3+，Fe2+，Cu2+，Ni2+,Cd2+,Zn2+,Hg+,Hg2+，Cr3+,Pb2+Or Mn2+Wherein each heavy metal cation is present in an amount of 0ppm or 1ppm to 20ppm, such as 2, 5, 8, 10, 12 or 15 ppm. Furthermore, S2-The content is 0ppm or 0.2-40ppm, such as 2, 10 or 20 ppm. Furthermore, AsO4 3-+AsO3 3-The content is 0 or 0.2-30ppm, such as 2, 7, 15, 20 or 25 ppm.
According to a second embodiment of the present invention, there is also provided a wastewater treatment system, i.e., a wastewater treatment system for use in the above wastewater treatment method, comprising the following devices in the following order:
1) adjusting the distribution pool (1);
2) a hydrolysis acidification pool (2);
3) a primary anaerobic fermentation tank (3);
4) a secondary anaerobic fermentation tank (4);
5) a primary aerobic aeration tank (5);
6) a secondary aerobic aeration tank (6);
7) a chemical deep treatment system (7);
8) a multimedia filter (8);
9) an ultrafiltration system (9);
10) a reverse osmosis membrane or electrodialysis apparatus (10); and
11) an evaporation desalination device (11);
wherein the chemical advanced treatment system (7) is or comprises one or more of the following devices: ozone oxidation treatment equipment, an electrochemical treatment pool, chemical catalytic oxidation treatment equipment, Fenton process treatment equipment or chemical specific reagent treatment equipment.
Preferably, in a chemical depth treatment system (7) comprising an electrochemical treatment cell, a sacrificial anode and an inert anode are used as a combined anode or an alloy material comprising a sacrificial metal and an inert metal is used as a composite anode in the electrochemical treatment cell, and a direct current voltage is provided between the combined anode or the composite anode and a cathode by a direct current power supply.
Preferably, the multimedia filter (8) is a multimedia filter comprising a quartz sand filter layer.
Preferably, the ultrafiltration system (9) is a ceramic flat membrane ultrafiltration device.
In general, the COD of the feed water (W3) of the electrochemical treatment cell (7) is 600mg/L or less, for example 250-600mg/L, such as 300, 400 or 500mg/L, and its TDS value is 8000mg/L to 30000mg/L, preferably 10000mg/L to 29000mg/L, such as 12000, 15000, 20000, 22000, 25000 or 28000 mg/L. The effluent (W4) from the electrochemical treatment cell (7) has a COD of <300 mg/L, for example 20-300mg/L, such as 30, 50, 80, 100, 150, 200 or 250mg/L, and a TDS value of 8000mg/L-30000mg/L, preferably 10000mg/L-29000mg/L, such as 12000, 15000, 20000, 22000, 25000 or 28000 mg/L. In addition, the total hardness (Ca/Mg) of the effluent (W4) can reach below 80mg/L, typically between 10-80mg/L, such as 20, 40 or 50 mg/L.
And respectively collecting the sediment at the bottom of the electrochemical treatment tank and the scum on the surface of the wastewater, and conveying the sediment and the scum to a sludge collection tank.
The electrochemical treatment can effectively remove fluorine and silicon impurities. In addition, the hardness (total hardness based on calcium and magnesium ions is less than 80mg/L) is also significantly reduced, and heavy metals are removed. The electrochemical treatment method has the advantages of low cost and good effect.
In this application, "optional" means with or without. In the present application, "electrochemical" has the same meaning as "electrolysis" and is used interchangeably. An "electrochemical treatment cell" may also be referred to as an "electrolysis cell". "hardness" and "(calcium and magnesium) total hardness" are used interchangeably.
The power supply used in the present invention is preferably a direct current pulse power supply, more preferably a pulse adaptive power supply. The power supply parameters can be automatically adjusted according to the work reflection condition. If necessary, a plurality of flow deflectors (or water barriers) are provided in the electrochemical treatment cell to guide the wastewater to meander (zigzag) between all the anodes and cathodes.
The biochemical treatment process comprises the steps of sequentially carrying out anaerobic zone (zone) treatment and aerobic zone treatment on the wastewater. In addition, in the biochemical treatment process, the treatment of the anaerobic zone (zone) and the treatment of the aerobic zone can be performed each independently a plurality of times. For example, the anaerobic treatment and the aerobic treatment are each carried out 2 times or 3 times or 4 times or 5 times or 6 times, that is, each may be divided into 2, 3, 4 or 5 or 6 stages, respectively. In addition, anaerobic treatment and aerobic treatment may be alternately performed.
Anaerobic bacteria generate denitrification to change organic matters (amino acid and protein) and nitrate radicals into ammonia nitrogen. Typically, Nitrate (NO)3 -) Nitrogen (N) in (A) is passed through a series of intermediates (NO)2 -、NO、N2O) reduction to nitrogen (N)2). The aerobic section is used for removing organic matters in the wastewater and removing ammonia nitrogen through nitration.
Anaerobic and aerobic treatment can greatly reduce the COD value in the wastewater. For the selection of anaerobic bacteria or aerobic bacteria, corresponding bacteria sources are selected according to different specific waste water for cultivation. Selecting various bacteria to cultivate in the specific wastewater; then, the number and activity of microorganisms suitable for biochemical treatment are observed under a microscope, and water indexes are detected, so that bacteria which can propagate fast in corresponding wastewater are selected. For example, the aerobic bacteria used in the aerobic zone include one or more of escherichia coli, bacillus subtilis, pichia pastoris, aspergillus niger and penicillium chrysogenum, and the anaerobic bacteria used in the anaerobic zone are bifidobacterium and/or clostridium butyricum. In addition, heterotrophic bacteria can be used in both the anaerobic and aerobic sections, including one or more of rhizopus and/or penicillium. Autotrophic bacteria including facultative autotrophic rhizobia (Rhizobium species F43bT, CN105925516A), Thiobacillus ferrooxidans, Thiobacillus thiooxidans or Alcaligenes eutrophus (Alcaligenes) may be used in the anaerobic zone.
According to the characteristics of the waste water, a biochemical treatment process is designed and proper bacteria are selected, the process has the advantages of low cost, high efficiency, small side effect and less generated secondary pollutants, and particularly, the influence on the subsequent procedures is reduced.
The biochemical treatment can degrade harmful organic impurities (such as impurities at a molecular level, such as soluble cellulose ether, micromolecular alcohols, ethers or other micromolecular organic matters, and biological macromolecules), and greatly reduce indexes of COD, ammonia nitrogen, total phosphorus and the like of the wastewater.
Above V1And V2May be the same or different. The direct voltage (V)1) Or (V)2) Is between 5 and 100V, preferably between 7 and 70V, more preferably between 10 and 36V. Preferably, the voltage V is such that it is necessary to remove different types of impurities1Or V2Is kept constant or is gradually adjusted or is gradually increased, preferably the voltage V1Or V2Are gradually turned up.
Preferably, the sodium chloride content or concentration in the wastewater (W3) in the electrochemical treatment cell is from 1g/L to 30g/L (i.e., between 1000ppm and 30000 ppm), preferably from 3g/L to 28g/L, preferably from 5g/L to 27g/L, more preferably from 7g/L to 26g/L, more preferably from 8g/L to 25g/L, such as 10, 12, 15, 18, 20, or 23 g/L. It has been found experimentally that the above sodium chloride content results in the generation of a sufficient amount of active chlorine in the vicinity of the inert anode of the electrochemical treatment cell.
For a voltage (V) applied between the anode and the cathode1Or V2) By gradually regulating the voltage from low to high until detectionDetection of free Cl or Cl2The "chlorine" smell is generated or smelled until the actual voltage or current density is determined.
In the case of using a sacrificial anode and an inert anode as combined anode in an electrochemical treatment cell, it is preferred to use iron or aluminum or an iron-aluminum alloy as sacrificial anode. In contrast, in the case where an alloy material containing a sacrificial metal (e.g., iron and/or aluminum) and an inert metal (e.g., titanium) is used as the composite anode in the electrochemical treatment cell, it is preferable to use an iron-titanium alloy, an aluminum-titanium alloy, or an iron-aluminum-titanium alloy as the composite anode, in which an iron, aluminum, or iron-aluminum element (referred to as sacrificial metal) contained in the composite anode functions as the sacrificial anode, and titanium (referred to as inert metal) functions as the inert anode.
There is no limitation on the material for forming the cathode, and materials commonly used in the art for forming the cathode may be used in the present application, for example, materials for forming the cathode include graphite, iron, titanium, and the like. The inert anode comprises graphite or titanium metal and, thus, the inert anode plate comprises a graphite plate or a titanium metal plate.
In general, the anode or the cathode is generally shaped as a flat plate (e.g., an iron plate, an aluminum plate, or an iron-aluminum alloy plate), a perforated plate (plate with openings), a grid (grate), a fence (grate), a wire mesh, or the like. These anodes or cathodes generally have one or two major faces (i.e., front or back) with a large area. The main face is in the form of a plane or a curved surface. For example, when the anode or cathode is in the form of a fence, in the fence-shaped anode or cathode, a plurality of anodes in the shape of rods or bars are arranged upright on a plane or on a curved surface, or a plurality of cathodes in the shape of rods or bars are arranged upright on a plane or on a curved surface. Typically, the major face (or front) of the anode faces the cathode or faces the major face (or front) of the cathode. Preferably, an iron, aluminum or iron-aluminum alloy plate is used as the anode, with the major plane (or face) of the anode facing the cathode or facing the major plane (or face) of the cathode. When iron or aluminum or an iron-aluminum alloy (e.g. iron or aluminum or iron-aluminum alloy plate) is used as the sacrificial anode,or when an alloy material containing a sacrificial metal and an inert metal is used as the composite anode, a flocculant (or a substance having a flocculation effect) is formed from iron ions, aluminum ions, or iron ions + aluminum ions in the wastewater contained in the electrochemical treatment cell. Such flocculants include, but are not limited to, Fe2+(e.g., [ Fe (H))2O)6]2+)、Fe3+(e.g., [ Fe (H))2O)6]3+)、Al3+(e.g., [ Al (H) ]2O)6]3+) And corresponding inorganic high molecular polymers (such as polymeric ferric chloride, polymeric ferric sulfate, polymeric aluminum chloride) or composite inorganic high molecular polymers (such as polymeric aluminum ferric chloride, polymeric aluminum ferric sulfate, polymeric sulfuric acid (chloride) silicon aluminum ferric), etc.
In general, multiple pairs of anodes and cathodes may be used in an electrochemical treatment cell, for example 2 to 150 pairs, preferably 3 to 120 pairs, more preferably 4 to 100 pairs, more preferably 5 to 90 pairs, more preferably 6 to 85 pairs, such as 8, 9, 10, 12, 14, 16, 18, 20, 22, 25, 28, 30, 32, 35, 40, 60, 70 or 80 pairs. For example, when one cathode plate (or anode plate) with a larger surface area is paired with two anode plates (or cathode plates) with a smaller surface area, then 2 pairs of anode and cathode are considered to be present; when one cathode plate (or anode plate) with a larger surface area is paired with three anode plates (or cathode plates) with a smaller surface area, then there are 3 pairs of anodes and cathodes. The number of pairs is calculated as an average.
The plurality of anodes and cathodes may be alternately arranged in the electrochemical treatment cell (or electrolytic cell) or may be arranged in pairs or in a set of 2 anodes and 1 cathode. Preferably, a plurality of anodes and cathodes (e.g., 8 anodes and 7 cathodes) are alternately arranged, as shown in fig. 3. In addition, two or more anodes may be adjacent to or electrically connected to each other. Also, two or more cathodes may be adjacent to or electrically connected to each other.
Generally, to generate highly active oxidizing agents, Cl and Cl, in situ (in situ) in waste water2And/or hypochlorite, the magnitude of the direct voltage applied between the inert anode and the cathode as an electrode pair andthe distance (d) between the anode and the cathode is related. The distance between the anode and the cathode (distance d) is typically between 2 and 40cm, preferably between 3 and 35cm, more preferably between 4 and 30cm, more preferably between 5 and 28cm, such as 6, 7, 8, 9, 10, 11, 12, 13, 15, 16, 17, 20, 22 or 25 cm. The larger the pitch, the higher the applied dc voltage (V1 or V2). For a spacing (d) of between 2 and 25cm, the voltage is generally between 1.7V and 30V. In electrochemical processes (otherwise known as electrolysis processes), the DC voltage is generally adjusted from low to high until active chlorine (e.g., free Cl or Cl) is detected2) Producing or smelling a "chlorine" smell.
During the electrochemical treatment, the current density between the anode (plate) and the cathode (plate) was 10mA/cm2To 60mA/cm2Preferably between 12mA/cm2To 55mA/cm2More preferably between 14mA/cm2To 50mA/cm2E.g. 13, 15, 17, 20, 30, 40 or 45mA/cm2。
Generally, the adjustment of the alkali chloride content or concentration of the wastewater in the electrochemical treatment cell also depends on the content of reducing impurities (e.g., aromatic organic compounds, organic polymers, and ammonia nitrogen impurities) in the wastewater. That is, the higher the alkali chloride content or concentration of the wastewater in the electrochemical treatment cell, the more chlorine-containing oxidants (i.e.: Cl, Cl) are generated by the electrochemical treatment2And/or hypochlorite) to more rapidly fully oxidize the reducing impurities.
During (G) the electrochemical treatment, the formed precipitate is scraped off and collected in a sludge collection tank.
Preferably, a filler or three-dimensional filler (filler diameter of, for example, 4 to 8 mm) is placed between the anode and the cathode in the electrochemical treatment cell; for example, a ceramic filler (for example alumina ceramic, silicon carbide ceramic or silicon nitride ceramic), or a wire mesh filler (mesh size of for example 4-8 mm). The filler exerts an adsorption effect and provides a reaction interface and a crystallization point at the same time.
Preferably, a coagulant aid (or flocculant or sedimentation agent), such as polyacrylamide, may be added to the wastewater (W3) during the electrochemical treatment. Organic scum such as oily matter or floating matter floats on the surface of the wastewater due to bubbling caused by hydrogen generated by electrolysis in the wastewater and air (aeration) introduced into the wastewater, so that the organic scum is further aggregated or precipitated by means of a coagulant aid (or a flocculant or a settling agent), and the scum is conveniently fished or the precipitate is conveniently collected.
Preferably, during the electrochemical treatment in step (G), an inorganic base (e.g., Na) is added to the wastewater (W3), preferably at the front or inlet end of the electrochemical treatment cell2CO3And/or NaOH) to adjust the pH of the wastewater (W3) to 7.2-13.5, preferably in the range of 9-13.2, more preferably in the range of 10-13, more preferably in the range of 10.5-12.5, preferably in the range of 11-12, the wastewater (W3) being electrochemically treated.
The inventors of the present application have unexpectedly found that, in the electrochemical treatment step (G), although the sacrificial anode generates a flocculant containing iron or aluminum under the action of an electric field and a coagulant aid such as polyacrylamide is further added to the wastewater (W3) in the electrochemical treatment tank (e.g., at the front end or the water inlet end of the electrochemical treatment tank), which facilitates the removal of fluorine and silicon in the wastewater and the reduction of the total hardness of the wastewater, if the total hardness (calcium magnesium) of the wastewater in the treatment tank is excessively reduced, for example, below 80mg/L, it is rather difficult to completely remove silicon-based impurities, and at the same time, the effect of removing fluorine is also affected. Therefore, the total hardness of calcium and magnesium in the effluent of the treatment tank is maintained to be higher than 80mg/L, generally 80-500mg/L, preferably 90-450mg/L, preferably 100-400mg/L, such as 110, 150, 200, 250, 300 or 350mg/L, and the pH of the wastewater (W3) is adjusted to be in the above range, so that silicon impurities (SiO 3) in the wastewater in the electrochemical treatment tank can be removed ideally3 2-) And fluorine-based impurities (F)-)。
Further, the inventors have found that, in the case where the pH of the wastewater in the electrochemical treatment tank is adjusted to the above range, and in the case where a water-soluble magnesium salt (for example, magnesium chloride, magnesium sulfate and/or magnesium nitrate, preferably magnesium chloride) is added to the wastewater (W3) to be electrochemically treated (for example, wastewater at the front end or the water inlet end of the electrochemical treatment tank), the treatment tank is maintainedThe calcium-magnesium total hardness of the effluent (W4) is higher than 80mg/L, thereby being capable of leading SiO in the wastewater3 2-The removal rate of (a) is higher than 98%, even higher than 99.5% or higher than 99.9%. The reason for this effect may be the magnesium ion Mg2+With SiO3 2-And optionally other ions (e.g. PO)4 3-Or OH-) A double salt precipitate formed.
Generally, the above-mentioned wastewater (W3) in the electrochemical treatment cell contains a sufficient amount of Ca2+And Mg2+Ions such that F-And SiO3 2-Precipitates were formed separately. In general, in the wastewater (W3) to be treated (e.g., wastewater at the front end or the water inlet end of an electrochemical treatment cell), Ca in the wastewater (W3) should be ensured2+And F-Is 2-400:1, preferably 3-390:1, preferably 4-380:1, preferably 5-370:1, preferably 7-360:1, preferably 8-350:1, preferably 10-340:1, preferably 12-330:1, preferably 15-320:1, preferably 18-310:1, preferably 20-300:1, preferably 22-290:1, preferably 25-280:1, preferably 30-270:1, preferably 35-260:1, preferably 40-250:1, preferably 45-230:1, preferably 50-220:1, preferably 60-210: 1. When Ca is contained in the waste water (W3)2+At lower ion concentrations, a water soluble calcium salt (e.g., calcium chloride) may be added to the wastewater (W3) (e.g., wastewater at the front or inlet end of the electrochemical treatment cell).
In addition, in the wastewater (W3) to be treated (e.g., wastewater at the front end or the water inlet end of the electrochemical treatment cell), Mg (as Mg) in the wastewater (W3) should be ensured2+Calculation): si (in SiO)3 2-In terms of) is 3 to 500:1, preferably 5 to 490:1, preferably 7 to 480:1, preferably 10 to 470:1, preferably 12 to 460:1, preferably 15 to 450:1, preferably 18 to 440:1, preferably 20 to 430:1, preferably 22 to 420:1, preferably 25 to 410:1, preferably 28 to 400:1, preferably 30 to 390:1, preferably 32 to 380:1, preferably 35 to 370:1, preferably 37 to 360:1, preferably 40 to 350:1, preferably 45 to 330:1, preferably 50 to 320:1, preferably 60 to 310: 1. When Mg is contained in the waste water (W3)2+When the concentration of the ions is low, a water-soluble magnesium salt (e.g., magnesium chloride) may be added to the wastewater (W3) (e.g., wastewater at the front end or the water inlet end of the electrochemical treatment cell).
Due to various impurities in the electrochemical treatment cellThe substances interfere with each other, resulting in incomplete removal of all impurities. The inventors have found through experiments that traces of SiO can be thoroughly removed from wastewater by maintaining a higher hardness in the effluent of an electrochemical treatment cell3 2-And F-(it is extremely difficult to remove them in the prior art).
Preferably, the purified wastewater (W4) is obtained by adding sodium carbonate to the effluent (W4) of the electrochemical treatment cell, i.e. to the chemical softening cell (7a), to further soften the wastewater (i.e. reduce the hardness of the wastewater, allowing the calcium and magnesium ions to form a precipitate)4) The hardness is generally in the range of, for example, 2 to 5 mg/L. The formed precipitate is collected in a sludge collection tank for additional solid waste treatment.
Subsequently, the effluent from the electrochemical treatment cell (wastewater W4) is filtered through a multimedia filter (8) to separate and remove suspended substances or particulate matter (of micron size) in the wastewater, obtaining purified wastewater (W5). The wastewater (W6) is then ultrafiltered by an ultrafiltration system (9) to further remove micron-sized suspended matter (i.e., fine particulate matter) in the wastewater to obtain further purified wastewater (W6).
Preferably, the multimedia filter (8) is a multimedia filter comprising a quartz sand filter layer.
Preferably, the ultrafiltration system (9) is a ceramic flat membrane ultrafiltration device. The raw material (or material) of the ceramic ultrafiltration membrane is generally alumina ceramic, silicon carbide or silicon nitride ceramic.
There is no particular limitation on the multimedia filter used in the present application, and multimedia filters commonly used in the art may be used. The present invention preferably uses a multimedia filter including a quartz sand filter layer, for example, a multimedia filter including an activated carbon filter layer, a quartz sand filter layer, and a porous ceramic particle filter layer. Alternatively, for example, the invention may employ the multimedia filter disclosed in CN103239909A, wherein a filter plate is provided at a lower portion of a housing of the filter, a filter layer is provided at an upper side of the filter plate, the filter layer includes, from top to bottom, a coal bed without smoke, a quartz sand layer and a pebble layer, particles in the coal bed without smoke and the pebble layer have a larger particle size than particles in the quartz sand layer, and a water outlet is provided at a bottom of the housing.
Multimedia filtration may also be referred to as sand filtration. By using a multimedia filter, it is possible to remove fine or macroscopic particles, including suspended matter, calcium carbonate particles or colloidal substances, from the wastewater. The multimedia filter may be regenerated by flushing with water, the flushed waste water being returned upstream, or the flushed waste water being collected and pressure filtered.
The ultrafiltration step may further filter out fine suspended matter or particulate matter in the wastewater.
The above method according to the present invention further comprises reverse osmosis concentration. The purified waste water (W6) (hardness about <0.1mg/L) from the previous ultrafiltration step is subjected to one or more stages of reverse osmosis treatment, obtaining fresh water (with COD value between 5 and 15mg/L, TDS value <500mg/L or <200mg/L) as reuse water, together with concentrated water containing sodium chloride (TDS >140000 mg/L).
More preferably, the reverse osmosis concentration step comprises: primary reverse osmosis and secondary reverse osmosis. Further preferably, the first-stage reverse osmosis adopts a first-stage two-stage process; for example, the water inlet pressure is less than or equal to 1.4MPa, a booster pump is arranged between the two sections, and the water yield is controlled to be about 75 percent. The second-stage reverse osmosis adopts a first-stage two-stage process; for example, the water inlet pressure is less than or equal to 3.0MPa, a booster pump is arranged between the two sections, the water yield is controlled to be about 50%, the produced concentrated water is conveyed to an evaporation desalting system (11) for evaporation and crystallization, evaporation condensed water is obtained, and meanwhile, a high-quality industrial salt product with the NaCl purity of more than 99% is obtained. The evaporated condensed water is stored in a water producing tank (12) as reuse water. The reuse water in the water production tank is recycled to the regulating distribution tank (1) for diluting the raw wastewater.
THE ADVANTAGES OF THE PRESENT INVENTION
1. The invention combines deep biochemical treatment and chemical deep treatment, obviously improves the purification effect of the waste water, has ideal removal effect of COD and TDS and has outstanding cost benefit. In addition, the reuse water is recycled for diluting the wastewater in the conditioning cut water tank, reducing water discharge.
2. The original wastewater is subjected to biochemical treatment and electrochemical treatment in turn,wherein the biochemical treatment removes most COD in a low-cost and high-efficiency manner, and avoids the organic matter from carrying out F treatment-、SiO3 2-Encapsulation and complexation of ions and heavy metal ions, and electrochemical treatment of (HF) n and (H)2SiO3) n, etc. are dissociated (dissociates), respectively, from Ca present in the wastewater2+And Mg2+The precipitate is formed, so that most of fluorine and silicon impurities are removed, and the phenomenon that the micropores of various filtering membranes (such as an ultrafiltration membrane) are frequently blocked due to the formation of hard scale in the subsequent process is avoided, so that the service life of the filtering equipment is shortened. The electrochemical treatment can further degrade organic matters which are difficult to degrade in the biochemical treatment by generating active chlorine, thereby further reducing the COD of the wastewater after the biochemical treatment to about 20, such as in the range of 12-30 or 15-25. In addition, if a chemical softening pool (adding sodium carbonate) is further arranged after the electrochemical treatment pool, the effluent of the chemical softening pool can reach the total hardness of 1-10 ppm.
3. When the pH of the wastewater in the electrochemical treatment cell is adjusted to 7.2-13.5, preferably 9-13.2, more preferably 10-13, more preferably 10.5-12.5, more preferably 11-12 during the electrochemical treatment, and the total hardness of calcium and magnesium in the effluent of the cell is maintained above 80mg/L, preferably 80-300mg/L, such as 90, 100, 120, 150, 180 or 200mg/L, silicon and fluorine impurities can be desirably removed. In particular, high Ca levels are maintained during electrochemical treatment by adding water soluble calcium and magnesium salts (e.g., calcium and magnesium chloride) to the wastewater in the treatment tank2+Or Mg2+With SiO3 2-In a molar ratio of (a). The inventors have found through experiments that the addition of magnesium chloride to the wastewater gives a much better effect of removing fluorine, silicon-based impurities than the addition of calcium chloride to the wastewater, that is, silicate and fluoride ions are more thoroughly removed despite the addition of a smaller amount of magnesium chloride.
4. Removing most of calcium and magnesium ions by electrochemical method to make the effluent of electrochemical treatment pool reach total hardness of 20-78ppm, reducing hardness by more than 99% and completely removing heavy metal ionsEffect, however, there are still traces of SiO in the effluent3 2-And F-(although their content is almost negligible). Therefore, it is preferable to maintain the total hardness of calcium and magnesium in the effluent of the electrochemical treatment cell to be higher than 80mg/L, thereby completely removing silicon, fluorine-based impurities, and heavy metal ions in the electrochemical treatment cell.
5. By adding inorganic alkali (e.g. Na) to the waste water in a chemical softening reaction tank2CO3And K2CO3) Further removing the remaining trace Ca2+And Mg2+Ions. That is, calcium and magnesium ions are completely removed through two steps, i.e., electrochemical treatment and chemical softening.
6. The obtained sodium chloride salt reaches or is superior to the national standard of industrial salt, the obtained fresh water reaches or is superior to the standard of surface three types of water, one part of the fresh water is recycled to the wastewater adjusting tank in the step (A), and the rest part of the fresh water can be used as industrial water for enterprises or civil water. Thus, the purpose of recycling the waste water in the industry is achieved.
Drawings
FIG. 1 is a schematic diagram of the operating principle of the electrochemical processing system of the present invention.
701: an electrochemical impurity removal reaction tank; 701 a: an anode plate (sacrificial anode and inert anode; or composite anode); 701 b: a negative plate or bipolar plate; 701 c: a three-dimensional filler; 701 d: a water inlet; 701 e: an air inlet; 701 f: a porous intake pipe (or aeration pipe); 701 g: a water outlet; 701 h: a sewage draining outlet; 701 i: a reaction tank cover plate; 702: a sedimentation and clarification tank; 703: a power supply (pulse adaptive power supply); 704: a water inlet pump; 705: an air pump.
FIG. 2 is a front (longitudinal) cross-sectional view of an electrochemical decontamination system of the invention.
701 j: sediment discharge port equipped with solenoid valve (automatic sediment discharge).
FIG. 3 is a top view of the anode and cathode arrangement in the electrochemical treatment cell of the electrochemical decontamination system of the present invention.
Fig. 4 is a transverse perspective view of the anode and cathode arrangement.
Fig. 5 is a schematic flow diagram of a conventional cellulose ether production facility.
FIG. 6 is a flow chart of wastewater treatment used in example 1 of the present invention.
FIG. 7 is a flow chart of wastewater treatment used in example 4 of the present invention.
1: adjusting the distribution pool; 2: a hydrolysis acidification pool; 3: a primary anaerobic tank; 4: a second-stage anaerobic tank; 5: a primary aerobic tank; 6: a secondary aerobic tank; 7: a chemical deep treatment tank (system); 7 a: a chemical softening tank; 8: a multi-media filter; 9: an ultrafiltration system; 10: RO membrane salt concentration equipment; 11: an evaporative desalination system; 12: a water producing pool; 13: a sludge concentration tank; 14: filter pressing dehydration equipment; 15: a methane collecting device.
Fig. 8 is a partial top view showing the arrangement of the fluidic plates, anode and cathode in an electrochemical processing cell.
701 k: a deflector (or water barrier).
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.
The apparatuses used in the examples are those generally used in the art and commercially available on the market unless otherwise specified.
For the commercially available processing apparatus used in each step, when the processing capacity of a single processing apparatus is low, the parallel use of two or more apparatuses may be considered.
1. Test method
The measurement of the content of other impurities can adopt Chinese national standard GB 8538-.
2. Waste water to be treated
The type and content of ionic impurities in wastewater from cellulose ether production enterprises are related to the water source (e.g. river water or groundwater) of the enterprises. If underground water is used as a water source for enterprise production, the content of fluorine and silicon in the wastewater is high.
The conditions of the wastewater of a certain cellulose ether production enterprise in Hebei province in China are as follows:
waste water (700 m) of cellulose ether production enterprise in Shandong province, China3Day) as follows:
the impurity contents of the waste water of the two enterprises are different in different months.
A schematic flow diagram of a cellulose ether production plant is shown in fig. 5.
Wastewater of cellulose ether production enterprises in Hebei province is taken as an experimental object.
In the 9 th month and 15 th to 20 th day of 2020, the contents of various impurities in the waste water (W1) in the regulating distribution tank (1) are as follows:
chemical Oxygen Demand (COD): 25000 mg/L; TDS (mainly sodium chloride) 24300 mg/L; ammonia Nitrogen (NH)3-N): 3 mg/L; total Phosphorus (TP): 3.5 mg/L; ca2+：140.6mg/L；Mg2+：35.2mg/L；SO4 2-: 40.6 ppm. The contents of other impurities were: fe3++Fe2+: 12.7ppm (i.e., mg/L); cu2+：2.4ppm；Ni2+：1.2ppm；Cd2+：0.7ppm；Zn2+：2.7ppm；Hg++Hg2+：0.3ppm；Cr3+：1.1ppm；Mn2+：0.6ppm；F-：4.3ppm；SiO3 2-：5.7ppm；S2-：0.2ppm；AsO4 3-+AsO3 3-：0.5ppm；PO4 3-：1.2ppm。Mg2+With SiO3 2-Is about 20:1, Ca2+And F-Is about 16: 1.
For very low levels of (non-volatile) impurity ions, this can be measured after vacuum concentration (e.g., 10-fold or 100-fold increase in concentration) of the wastewater sample.
3. Electrochemical treatment cell
In an example, the anode-to-cathode spacing in the electrochemical treatment cell (sacrificial and inert) was 18 cm; 8 iron metal plate anodes, 8 titanium metal plate anodes and 15 graphite cathode plates are arranged in total. The dc voltage typically varies in the range of 10-30V. The current density is generally 10mA/cm3To 60mA/cm3In the meantime. If necessary, a flow guide plate (or water blocking plate) 701k is provided in the electrochemical treatment cell, as shown in fig. 8.
4. Brief description of the Process
4.1 Art Water (catchment)
The process section collects various process wastewater generated in the process of enterprises and carries out chemical analysis of pollutant indexes.
4.2 adjusting the Water distribution
The industrial wastewater which is about to enter the treatment process in the process section is subjected to pH adjustment, then dilution and allocation are carried out, the dilution water is taken from a water supply pipeline for normal operation of enterprises at the beginning, and the later dilution water is taken from condensed water of salt concentration and evaporation desalting in the subsequent process section. Diluting the industrial wastewater to 1.5-3.0% of salt content according to the salt content of the industrial wastewater, and simultaneously adding a proper amount of salt-tolerant strains into the wastewater.
4.3 anaerobic section
According to the characteristics of the enterprise wastewater, through experiments and Chinese style, three process sections of hydrolytic acidification (hydrolytic acidification tank), primary anaerobic treatment and secondary anaerobic treatment are adopted, the COD content of inlet water can be removed by 60-80%, a certain amount of methane can be generated, the methane can be recycled, and certain economic benefit can be generated. The biological strains required by the process section are salt-tolerant high-activity strains, and the carbon source is supplemented to effectively improve the B: the value of C (biochemical oxygen demand BOD/chemical oxygen demand COD) can reach the target of removing the expected pollutant indexes through the adaptive training of the high-activity halotolerant bacteria.
4.4 aerobic section
After the anaerobic process section, the removal rate of COD content of the inlet water can reach 50-60% through two-stage aerobic series connection, and the process section adopts continuous acclimation of aerobic halotolerant bacteria to achieve the aim of removing pollutant indexes such as COD and the like.
4.5 chemical advanced treatment
The process section is arranged behind the secondary aerobic precipitation effluent, and further carries out chemical advanced treatment on pollutants which cannot be biochemically treated by chemical advanced treatment, the adopted processes comprise ozone oxidation process, electrochemical process, chemical catalytic oxidation process, Fenton process, chemical specific reagent treatment process and the like, and the COD removal rate of the process section is 30-40% of the COD of the inlet water, for example.
4.6 Multi-Medium filtration and Ultrafiltration
Through the process section, the indexes of pollutants such as COD (chemical oxygen demand), SS (suspended solid) and the like of the reclaimed water after chemical advanced treatment can be further removed, so that the reclaimed water is ensured to reduce the pollution of the membrane through subsequent processes, and the service life of the membrane is prolonged.
4.7 salt concentration Process
The process section can improve the salt content in the reclaimed water from 1.5-3.0% to about 15% of concentrated water through an electrodialysis process (or a two-stage RO reverse osmosis process), the produced water can be used for water distribution of a 4.2 process section (or used as process water or directly discharged), and the concentrated water enters subsequent evaporation concentration.
4.8 evaporative desalination
4.9 evaporating the condensed Water
Advanced treatment, recycling or discharging.
Example 1
The process flow is shown in figure 6. The electrochemical processing apparatus shown in fig. 1 to 4 and fig. 8 is used.
Raw (raw) waste water (W)0) Is about 28m3H, and the flow rate of the wastewater W1 to be treated is about 155m after dilution with water in the adjustment distribution reservoir 13Therefore, the throughput of the equipment at each step should meet this throughput requirement. In addition, since the average residence time of wastewater in each biochemical treatment tank is about 5 to 7 hours (generally about 6 hours), the capacity of each biochemical treatment tank should be set toIs the above average flow rate 155m3More than 7 times of the volume per hour, and the volume is 1200m3。
The contents of various impurities in the wastewater to be treated (W1) are as follows:
chemical Oxygen Demand (COD): about 25000 mg/L; TDS (mainly sodium chloride) of about 2450 mg/L; ammonia Nitrogen (NH)3-N): 3 mg/L; total Phosphorus (TP): 3.5 mg/L; ca2+：140.6mg/L；Mg2+：35.2mg/L；SO4 2-: 40.6 ppm. The contents of other impurities were: fe3++Fe2+: 12.7ppm (i.e., mg/L); cu2+：2.4ppm；Ni2+：1.2ppm；Cd2+：0.7ppm；Zn2+：2.7ppm；Hg++Hg2+：0.3ppm；Cr3+：1.1ppm；Mn2+：0.6ppm；F-：4.3ppm；SiO3 2-：5.7ppm；S2-：0.2ppm；AsO4 3-+AsO3 3-：0.5ppm；PO4 3-：1.2ppm。Mg2+With SiO3 2-Is about 20:1, Ca2+And F-Is about 16: 1.
The wastewater W1 to be treated has a flow rate of 155m3The anaerobic bacteria are bifidobacteria and clostridium butyricum, the number is about 1:1, and the anaerobic bacteria are sent to a hydrolysis acidification tank 3 for primary biochemical treatment. The effluent of the hydrolysis acidification tank 3 is conveyed to 2 anaerobic sections (3 and 4) and 2 aerobic sections (5 and 6) of the biochemical treatment stage for biochemical treatment. Wherein, the primary aerobic tank and the secondary aerobic tank are continuously aerated for aerobic treatment. The average residence time of wastewater in each biochemical treatment tank was about 6 hours. The anaerobic bacteria are Bifidobacterium and Clostridium butyricum (about 1:1 in number), while the aerobic bacteria include Escherichia coli, Bacillus subtilis and Pichia pastoris (about 1:1:1 in number). A part (20-30 wt%) of the sludge in each biochemical treatment tank is recycled, and the remaining part is collected in a sludge concentration tank 13.
The wastewater W3(COD is about 250-500mg/L, TDS is 24000-25000mg/L) after biochemical treatment is delivered to an electrochemical treatment pool 7 as chemical advanced treatment equipment for electrochemical treatment.
By adding NaOH and Na into the waste water at the front end or the water inlet end of the electrochemical treatment tank 72CO3(weight ratio 2:1) and adjusting the pH value of the inlet water of the electrochemical treatment tank 7 to about 11.5. The direct current power supply is a pulse self-adaptive power supply. And gradually increasing the voltage between the iron metal anode plate and the titanium metal anode plate and the cathode until the generation of active chlorine in the wastewater is detected (according to GB/T5750.11-2006), and then maintaining the voltage to carry out electrochemical treatment on the wastewater. During the electrochemical treatment, the air pump is started to ventilate the wastewater through the air inlet pipe (701f), and a large amount of bubbles are formed. The floating materials on the surface of the wastewater are fished, the electromagnetic valve at the bottom of the electrochemical treatment tank is periodically opened to drain the sediment, and the sediment is conveyed to the sludge concentration tank 13.
The effluent W4 of the electrochemical treatment tank 7 is detected, and the contents of various impurities are as follows:
F-the content is as follows: 0.13 ppm. SiO 23 2-The content is as follows: 0.35 ppm.
Chemical Oxygen Demand (COD): 129 mg/L; TDS (mainly sodium chloride) of about 24600 mg/L; ammonia Nitrogen (NH)3-N): 0.15 mg/L; total Phosphorus (TP): 0.11 mg/L. The total hardness of calcium and magnesium is 72 mg/L. The contents of other metal impurities are: fe3++Fe2+: 0.1ppm (i.e., mg/L); heavy metal ion Cu2+、Ni2+、Cd2+、Zn2+、Hg++Hg2+、Cr3+And Mn2+All contents of (a) are below the detection limit. S2-、PO4 3-And AsO4 3-+AsO3 3-All contents of (a) are below the detection limit.
The effluent W4 of the electrochemical treatment cell 7 is sent to a multi-media filter 8 for filtration to obtain purified wastewater W5.
The waste water W5 is then fed to an ultrafiltration apparatus 9 for ultrafiltration to obtain further purified waste water W6.
The secondary purified wastewater W6 was concentrated by reverse osmosis membrane 10 to yield fresh water (COD <50, TDS <300) and concentrated water (TDS >140000 mg/L).
The obtained concentrated water is evaporated by an evaporation desalting device (11) to respectively obtain salt mud and evaporation condensed water.
Fresh water and evaporated condensate are stored in the product water basin 12.
The reuse water in the production water tank 12 is recycled to the conditioning cut water tank 1 as dilution water.
Example 2
Example 1 was repeated except that MgCl was added at a concentration of 3M to the wastewater (i.e., influent) at the front end of the electrochemical treatment cell 72The solution was added in an amount of 0.3L per 100L of wastewater.
The effluent of the electrochemical treatment tank 7 is detected, and the content of various impurities is as follows:
F-the content is as follows:<0.1ppm。SiO3 2-the content is as follows: 0.1 ppm.
Chemical Oxygen Demand (COD): 135 mg/L; TDS (mainly sodium chloride) about 24400 mg/L; ammonia Nitrogen (NH)3-N): 0.17 mg/L; total Phosphorus (TP):<0.1 mg/L. The total hardness of calcium and magnesium is 83 mg/L. The contents of other metal impurities are: fe3++Fe2+: 0.07ppm (i.e., mg/L); heavy metal ion Cu2+、Ni2+、Cd2+、Zn2+、Hg++Hg2+、Cr3+And Mn2+All contents of (a) are below the detection limit. S2-、PO4 3-And AsO4 3-+AsO3 3-All contents of (a) are below the detection limit.
The above results show that fluorine (F) can be removed ideally by adding magnesium chloride to the influent water of the electrochemical treatment cell 7 to maintain the total hardness of the effluent water of the electrochemical treatment cell to be higher than 80mg/L-) And Silicon (SiO)3 2-)。
Example 3
Example 1 was repeated except that MgCl was added at a concentration of 3M to the wastewater (i.e., influent) at the front end of the electrochemical treatment cell 72The solution was added in an amount of 1.2L per 100L of wastewater.
The effluent of the electrochemical treatment tank 7 is detected, and the content of various impurities is as follows:
F-the content is as follows: below the detection limit. SiO 23 2-The content is as follows: below the detection limit.
Chemical Oxygen Demand (COD): 132.8 mg/L; TDS (mainly sodium chloride) of about 2450 mg/L; ammonia Nitrogen (NH)3-N): 0.15 mg/L; total Phosphorus (TP): below the detection limit. The total hardness of calcium and magnesium is 183 mg/L. The contents of other metal impurities are: fe3++Fe2+: 0.04ppm (i.e., mg/L); heavy metal ion Cu2+、Ni2+、Cd2+、Zn2+、Hg++Hg2+、Cr3+And Mn2+All contents of (a) are below the detection limit. S2-、PO4 3-And AsO4 3-+AsO3 3-All contents of (a) are below the detection limit.
The above results show that the addition of magnesium chloride to the feed water of the electrochemical treatment cell 7 greatly increases Mg content2+With SiO3 2-And maintaining the total hardness of the effluent of the electrochemical treatment cell higher than 180mg/L, enabling the complete removal of fluorine (F)-) And Silicon (SiO)3 2-)。
Example 4
Example 3 was repeated except that the flow was as shown in FIG. 7, and a chemical softening tank 7a was provided after the electrochemical treatment tank 7. The pH of the wastewater in the chemical softening tank 7a was raised slightly to 12.5 by adding sodium carbonate powder in the chemical softening tank 7 a. The total hardness of calcium and magnesium in the effluent of the chemical softening tank 7a is 25 mg/L. The reduction in hardness relieves the subsequent ultrafiltration unit 9 of its burden and extends its life.
Claims (16)
1. A method for treating cellulose ether industrial wastewater with high salt content and high COD value comprises the following steps:
(A) process waste water (W) from cellulose ether production enterprises0) Is conveyed into a regulating distribution pool (1) and diluted by regulating the pH value and adding water to obtain wastewater to be treated (W1) with the total dissolved solids content (TDS) lower than 30000 mg/L;
(B) conveying the wastewater (W1) to be treated in the adjusting distribution tank (1) to a hydrolysis acidification tank (2) for preliminary anaerobic fermentation;
(C) the wastewater flowing out of the hydrolytic acidification tank (2) is conveyed into a primary anaerobic fermentation tank (3) for primary anaerobic fermentation;
(D) the wastewater flowing out of the primary anaerobic fermentation tank (3) is conveyed into a secondary anaerobic fermentation tank (4) for secondary anaerobic fermentation;
(E) the wastewater (W2) flowing out of the secondary anaerobic fermentation tank (4) is conveyed into a primary aerobic aeration tank (5) for primary aerobic biochemical treatment;
(F) the wastewater flowing out of the primary aerobic aeration tank (5) is conveyed into a secondary aerobic aeration tank (6) for secondary aerobic biochemical treatment;
(G) the wastewater (W3) flowing out of the secondary aerobic aeration tank (6) is conveyed to a chemical advanced treatment system (7) for chemical advanced treatment;
(H) filtering the wastewater (W4) flowing out of the chemical advanced treatment system (7) through a multi-media filter (8) to obtain primary purified wastewater (W5);
(I) carrying out ultrafiltration on the primary purified wastewater (W5) by an ultrafiltration system (9) to obtain secondary purified wastewater (W6);
(J) concentrating the secondary purified wastewater (W6) by a reverse osmosis membrane or electrodialysis device (10) to obtain fresh water and concentrated water; and
(K) and (D) evaporating and crystallizing the concentrated water obtained in the step (J) by using an evaporation desalting device (11) to respectively obtain industrial salt sodium chloride and evaporation condensed water.
2. The processing method according to claim 1, wherein: the fresh water of step (J) and, optionally, the evaporated condensate of step (K), are recycled to the conditioning cut-off tank for use as dilution water; and/or
A major portion (e.g., more than 50 wt%, such as 55 to 95 wt%, preferably 60 to 90 wt%, more preferably 65 to 85 wt%) of the sludge collected from the primary anaerobic fermentation tank (3) and the secondary anaerobic fermentation tank (4), and a major portion (e.g., more than 50 wt%, such as 55 to 95 wt%, preferably 60 to 90 wt%, more preferably 65 to 85 wt%) of the sludge collected from the primary aerobic aeration tank (5) and the secondary aerobic aeration tank (6) are sent to the sludge concentration tank (13).
3. The processing method according to claim 1 or 2, wherein: a part of the sludge (for example, 5 to 45 wt% or 10 to 40 wt% or 15 to 35 wt% of the sludge) collected from the primary anaerobic fermentation tank (3) and the secondary anaerobic fermentation tank (4) is returned to the hydrolysis acidification tank (2), the primary anaerobic fermentation tank (3) and/or the secondary anaerobic fermentation tank (4).
4. The processing method according to claim 1 or 2, wherein: a part of the sludge (for example, 5 to 45 wt% or 10 to 40 wt% or 15 to 35 wt% of the sludge) collected from the primary aerobic fermentation tank (5) and the secondary aerobic fermentation tank (6) is returned to the primary aerobic fermentation tank (5) and/or the secondary aerobic fermentation tank (6).
5. The processing method according to claim 1 or 2, wherein: (A) process waste water (W) from cellulose ether production enterprises0) Is transported to a regulating distribution reservoir (1) and diluted by adjusting the pH and adding water to obtain a waste water (W1) having a Total Dissolved Solids (TDS) content of less than 30000mg/L and a COD value of less than 30000mg/L, preferably a TDS value and a COD value of 8-30g/L each, such as 10, 12, 15, 18, 20, 23, 24, 25, 26 or 27 g/L; and/or
The aerobic bacteria used in the aerobic zone comprise one or more of escherichia coli, bacillus subtilis, pichia pastoris, aspergillus niger and penicillium chrysogenum, and/or the anaerobic bacteria used in the anaerobic zone are bifidobacteria and/or clostridium butyricum;
preferably, heterotrophic bacteria are also used in both the anaerobic and aerobic sections, the heterotrophic bacteria including rhizopus and/or penicillium, and/or, autotrophic bacteria are also used in the anaerobic section, the autotrophic bacteria including facultative autotrophic rhizobia, thiobacillus ferrooxidans, thiobacillus thiooxidans or alcaligenes eutrophus.
6. The processing method according to claim 1 or 2, wherein: the chemical deep treatment in the chemical deep treatment system (7) is one or more of the following processes: ozone oxidation process, electrochemical process, chemical catalytic oxidation process, Fenton process or chemical specific medicament treatment process; preferably, the COD removal rate of the influent water of the chemical advanced treatment process section is 30-40% of the COD of the influent water after the influent water is treated by the chemical advanced treatment process section.
7. The treatment method according to claim 1 or 2 or 6, characterized in that the chemical depth treatment in the chemical depth treatment system (7) is an electrochemical process comprising subjecting the effluent (W3) from the secondary aerobic aeration tank (6) to an electrochemical treatment in the chemical depth treatment system (7) comprising an electrochemical treatment tank by applying a direct current voltage between a combined anode or composite anode and cathode to remove ammoniacal impurities, inorganic salts and COD, thereby obtaining a primary purified effluent (W4);
wherein a sacrificial anode and an inert anode are used as a combined anode or an alloy material containing a sacrificial metal and an inert metal is used as a composite anode in an electrochemical treatment cell, and wastewater (W) in the electrochemical treatment cell3) The content of alkali chloride is sufficient to allow the application of a direct voltage between the anode and the cathode in the wastewater (W)3) Can generate chlorine-containing oxidant on site; and
wherein a voltage (V) applied between an inert anode or a composite anode and a cathode as an electrode pair by a DC power supply is used1) Enough to cause the generation of water in the waste water (W)3) In which a chlorine-containing oxidizing agent and optionally an oxygen-containing oxidizing agent can be generated in situ, while a voltage (V) applied between a sacrificial anode or composite anode and a cathode as an electrode pair by a DC power supply is used2) Enough to make the elemental metal of the sacrificial anode or composite anode lose electrons and enter the wastewater (W) in the form of metal cations3) Wherein the voltage (V) exerts a flocculating effect in the wastewater1) And voltage (V)2) The same or different.
8. The method according to claim 7, wherein the wastewater (W) in the electrochemical treatment cell3) The content of NaCl + KCl is between 8g/L and 30g/L, preferably between 10g/L and 29g/L, preferably between 12g/L and 28g/L, more preferably between 15g/LTo 25g/L, more preferably from 18g/L to 23 g/L;
and/or
In the step (G), an inorganic base (for example, Na) is added to the waste water (W3)2CO3And/or NaOH) for conditioning waste water (W)3) To a pH of 7.2 to 13.5, preferably in the range of 9 to 13.2, more preferably in the range of 10 to 13, more preferably 10.5 to 12.5, more preferably 11 to 12, to wastewater (W)3) And carrying out electrochemical treatment.
9. The method of claim 7, wherein the direct voltage (V)1) Or (V)2) Is between 5 and 100V, preferably between 7 and 70V, more preferably between 10 and 36V; and/or
The current density between the anode and the cathode was 10mA/cm2To 60mA/cm2Preferably between 12mA/cm2To 55mA/cm2More preferably between 14mA/cm2To 50mA/cm2To (c) to (d); preferably, plate-like anodes and plate-like cathodes are used in the electrochemical treatment cell.
10. The method of claim 8, wherein in step (G), wastewater (W) within the electrochemical treatment cell is conditioned3) At the pH of (A) and in the wastewater (W)3) With or without the addition of additionally water-soluble calcium salts and/or water-soluble magnesium salts (preferably magnesium chloride):
maintaining the total hardness of the effluent of the electrochemical treatment tank to be higher than 80 mg/L; and/or
Waste water (W)3) Middle Ca2+And F-Is equal to or greater than 1, preferably equal to or greater than 1.5, preferably equal to or greater than 2, preferably equal to or greater than 2.5; and/or
Waste water (W)3) Medium Mg2+With SiO3 2-Is 1.5 or more, preferably 2 or more, preferably 2.5 or more, preferably 3 or more, preferably 3.5 or more.
11. A method according to any one of claims 7-10, wherein in the electrochemical treatment cell, the waste water (W) is treated3) The medium electrolyte concentration is between 0.02mol/L and 0.6mol/L, preferably between 0.035mol/L and 0.5mol/Lmol/L, preferably 0.05mol/L to 0.4mol/L, more preferably 0.06mol/L to 0.3mol/L, more preferably 0.08mol/L to 0.2 mol/L.
12. The method according to any one of claims 7-11, wherein iron or aluminum or an iron-aluminum alloy is used as sacrificial anode when sacrificial anode and inert anode are used as combined anode, or iron-titanium alloy, aluminum-titanium alloy or iron-aluminum-titanium alloy is used as composite anode when alloy material comprising sacrificial metal and inert metal is used as composite anode; and/or
Wherein a plurality of anodes and a plurality of cathodes are alternately arranged or arranged in pairs in the electrochemical treatment cell, or the electrodes are arranged in the electrochemical treatment cell in groups of 2 anodes and 1 cathode.
13. The method of claim 12, wherein a filler or three-dimensional filler is placed between the anode and the cathode in the electrochemical treatment cell; and/or
To the waste water (W) in the electrochemical treatment cell3) In which a coagulant aid or flocculant, such as polyacrylamide, is added.
14. The processing method according to claim 1 or 2, wherein: the multi-medium filter (8) is a multi-medium filter comprising a quartz sand filter layer; and/or
The ultrafiltration system (9) is a ceramic membrane ultrafiltration device, and is more preferably a ceramic flat membrane ultrafiltration device.
15. Method according to claim 1, wherein the waste water (W) to be treated1) The Chemical Oxygen Demand (COD) and TDS of (a) are each independently 8000mg/L to 30000mg/L, preferably 10g/L to 29g/L, such as 12, 15, 20, 22, 25 or 28 g/L; and, waste water (W) to be treated1) Total hardness of medium calcium and magnesium (Ca)2++Mg2+) From 50 to 1500ppm, preferably from 80ppm to 1300ppm, such as 100, 300, 500, 700, 900, 1000 or 1200 ppm.
16. The method of claim 15, whereinIn the waste water (W) to be treated1) In (F)-In an amount of 1ppm to 70ppm, such as 4, 6, 12, 20, 30, 35, 40 or 50 ppm; SiO 23 2-+SiO4 4-Is in an amount of 3ppm to 200ppm, such as 5, 10, 15, 20, 30, 40, 50, 60, 70, 90, 100, 120, 150 or 180 ppm; and, a Total Phosphorus (TP) content of 0ppm or 0.1-100 ppm, such as 1, 4, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80, or 90 ppm; and/or
In the waste water (W) to be treated1) Medium ammonia Nitrogen (NH)3-N) in an amount of 0.2 to 100ppm, such as 1, 5, 20, 30, 40, 50, 60 or 70 or 80 ppm; and, SO4 2-In an amount of 40 to 500ppm, preferably 50 to 470ppm, such as 70, 90, 120, 150, 180, 200, 250, 300, 350, 400 or 450 ppm;
optionally or further or preferably, Fe3+，Fe2+，Cu2+，Ni2+,Cd2+,Zn2+,Hg+,Hg2+，Cr3+,Pb2+Or Mn2+Wherein each heavy metal cation is present in an amount of 0ppm or 1ppm to 20ppm, such as 2, 5, 8, 10, 12 or 15 ppm; and/or, S2-In an amount of 0ppm or 0.2-40ppm, such as 2, 10 or 20 ppm; and/or, AsO4 3-+AsO3 3-The content is 0 or 0.2-30ppm, such as 2, 7, 15, 20 or 25 ppm.
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